# Copyright The Royal Society of Chemistry, 1999 # CCDC Number: 186/1271 data_global _publ_contact_author 'Andrei S.Batsanov' _publ_contact_author_email a.s.batsanov@durham.ac.uk loop_ _publ_author_name 'Batsanov, Andrei S.' 'Churakov, Andrei V.' 'Easson, Morag A. M.' 'Govenlock, Linda J.' 'Howard, Judith A. K.' 'Moloney, Janet M.' 'Parker, David' loop_ _publ_author_address ; Department of Chemistry South Road Durham DH1 3LE (UK) ; _journal_name_full 'Journal of the Chemical Society, Dalton Transactions' _journal_volume '?' _journal_page_first '?' _journal_page_last '?' _journal_year '1998' _ccdc_journal_depnumber '?' _publ_section_title ; Dimethylthiophosphoryl hydrazide ligands and their copper(I) complexes: X-ray crystal structures and analysis of their solution complexation behaviour by electrospray mass spectroscopy. ; #====================================================================== data_L1 _ccdc_compound_id 'L^2^' _ccdc_biological_activity '?' _ccdc_polymorph '?' _refine_ls_abs_structure_details '?' _ccdc_disorder ; ? ; _ccdc_comments '?' _audit_creation_method SHELXL _chemical_name_systematic ; butane-2,3-bis[(dimethylthiophosphoryl)hydrazide] ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C18 H24 N4 P2 S2' _chemical_formula_weight 422.47 _chemical_melting_point '>523 K' _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.588(1) _cell_length_b 11.402(1) _cell_length_c 11.620(1) _cell_angle_alpha 69.43(1) _cell_angle_beta 87.11(1) _cell_angle_gamma 69.74(1) _cell_volume 1112.1(2) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used all _cell_measurement_theta_min 1.9 _cell_measurement_theta_max 25.5 _exptl_crystal_description fragment _exptl_crystal_colour yellow _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.5 _exptl_crystal_size_min 0.3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.262 _exptl_crystal_density_method ? _exptl_crystal_F_000 444 _exptl_absorpt_coefficient_mu 0.393 _exptl_absorpt_correction_type 'semi-empirical (equivalents)' _exptl_absorpt_correction_T_min 0.828 _exptl_absorpt_correction_T_max 0.906 _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens SMART CCD detector' _diffrn_measurement_method '\w scans' _diffrn_standards_number '50 frames' _diffrn_standards_interval_count ? _diffrn_standards_interval_time '12 hours' _diffrn_standards_decay_% ? _diffrn_reflns_number 4911 _diffrn_reflns_av_R_equivalents 0.0270 _diffrn_reflns_av_sigmaI/netI 0.0213 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.88 _diffrn_reflns_theta_max 25.52 _reflns_number_total 3567 _reflns_number_observed 3319 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Siemens SMART' _computing_data_reduction 'Siemens SAINT' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'SHELXTL-PLUS' _computing_publication_material 'SHELXL-93' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 14 with very negative F^2^ and 8 flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses of fit S are based on F^2^, conventional R- factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.046P)^2^+0.67P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0099(22) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 3545 _refine_ls_number_parameters 332 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0354 _refine_ls_R_factor_obs 0.0324 _refine_ls_wR_factor_all 0.0944 _refine_ls_wR_factor_obs 0.0846 _refine_ls_goodness_of_fit_all 1.054 _refine_ls_goodness_of_fit_obs 1.040 _refine_ls_restrained_S_all 1.116 _refine_ls_restrained_S_obs 1.040 _refine_ls_shift/esd_max -0.006 _refine_ls_shift/esd_mean 0.001 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group P1 P 0.69368(5) 0.70560(5) 0.35561(4) 0.0266(2) Uani 1 d . . P2 P 0.23889(5) 0.84935(5) 0.58372(4) 0.0279(2) Uani 1 d . . S1 S 0.61337(7) 0.89428(5) 0.25709(5) 0.0421(2) Uani 1 d . . S2 S 0.13232(6) 0.76538(5) 0.51888(5) 0.0398(2) Uani 1 d . . N1 N 0.7176(2) 0.5633(2) 0.59346(14) 0.0287(4) Uani 1 d . . N2 N 0.6933(2) 0.6879(2) 0.5054(2) 0.0365(4) Uani 1 d . . H2N H 0.6627(25) 0.7567(25) 0.5242(21) 0.038(6) Uiso 1 d . . N3 N 0.4993(2) 0.7602(2) 0.71320(14) 0.0282(4) Uani 1 d . . N4 N 0.4029(2) 0.7301(2) 0.6535(2) 0.0324(4) Uani 1 d . . H4N H 0.4361(25) 0.6630(24) 0.6323(21) 0.036(6) Uiso 1 d . . C1 C 0.6925(2) 0.5554(2) 0.7057(2) 0.0247(4) Uani 1 d . . C2 C 0.6348(2) 0.6770(2) 0.7423(2) 0.0251(4) Uani 1 d . . C3 C 0.5894(4) 0.6085(3) 0.3401(3) 0.0560(7) Uani 1 d . . H3A H 0.5928(33) 0.6144(30) 0.2601(30) 0.068(9) Uiso 1 d . . H3B H 0.4876(42) 0.6536(36) 0.3596(32) 0.091(11) Uiso 1 d . . H3C H 0.6348(32) 0.5170(32) 0.3920(28) 0.065(8) Uiso 1 d . . C4 C 0.8820(3) 0.6182(3) 0.3352(3) 0.0606(8) Uani 1 d . . H4A H 0.8865(35) 0.6259(32) 0.2517(33) 0.080(10) Uiso 1 d . . H4B H 0.9209(35) 0.5232(35) 0.3883(31) 0.077(9) Uiso 1 d . . H4C H 0.9391(48) 0.6617(42) 0.3517(39) 0.116(16) Uiso 1 d . . C5 C 0.1500(2) 0.9142(2) 0.6980(2) 0.0345(5) Uani 1 d . . H5A H 0.0591(29) 0.9876(26) 0.6646(23) 0.050(7) Uiso 1 d . . H5B H 0.2132(28) 0.9449(24) 0.7294(23) 0.047(7) Uiso 1 d . . H5C H 0.1243(27) 0.8475(27) 0.7615(25) 0.050(7) Uiso 1 d . . C6 C 0.2823(3) 0.9844(2) 0.4719(2) 0.0410(5) Uani 1 d . . H6A H 0.1896(29) 1.0566(26) 0.4407(23) 0.047(7) Uiso 1 d . . H6B H 0.3299(27) 0.9552(24) 0.4111(23) 0.045(7) Uiso 1 d . . H6C H 0.3465(30) 1.0111(26) 0.5146(24) 0.054(7) Uiso 1 d . . C11 C 0.7129(2) 0.4223(2) 0.7996(2) 0.0242(4) Uani 1 d . . C12 C 0.7776(2) 0.3057(2) 0.7727(2) 0.0294(4) Uani 1 d . . H12 H 0.8095(23) 0.3092(20) 0.6981(21) 0.029(5) Uiso 1 d . . C13 C 0.7859(2) 0.1828(2) 0.8584(2) 0.0358(5) Uani 1 d . . H13 H 0.8294(26) 0.1089(25) 0.8393(21) 0.042(6) Uiso 1 d . . C14 C 0.7303(3) 0.1739(2) 0.9725(2) 0.0386(5) Uani 1 d . . H14 H 0.7339(26) 0.0956(26) 1.0266(23) 0.045(6) Uiso 1 d . . C15 C 0.6673(2) 0.2882(2) 1.0007(2) 0.0346(4) Uani 1 d . . H15 H 0.6284(26) 0.2845(23) 1.0799(23) 0.042(6) Uiso 1 d . . C16 C 0.6587(2) 0.4119(2) 0.9153(2) 0.0287(4) Uani 1 d . . H16 H 0.6167(24) 0.4900(23) 0.9345(20) 0.035(6) Uiso 1 d . . C21 C 0.7366(2) 0.7009(2) 0.8163(2) 0.0263(4) Uani 1 d . . C22 C 0.8900(2) 0.6386(2) 0.8197(2) 0.0366(5) Uani 1 d . . H22 H 0.9279(26) 0.5834(24) 0.7719(22) 0.045(6) Uiso 1 d . . C23 C 0.9859(3) 0.6573(2) 0.8916(2) 0.0434(5) Uani 1 d . . H23 H 1.0884(32) 0.6136(26) 0.8904(24) 0.056(7) Uiso 1 d . . C24 C 0.9301(3) 0.7379(2) 0.9601(2) 0.0414(5) Uani 1 d . . H24 H 0.9995(27) 0.7506(23) 1.0087(22) 0.043(6) Uiso 1 d . . C25 C 0.7785(3) 0.8007(2) 0.9568(2) 0.0407(5) Uani 1 d . . H25 H 0.7389(27) 0.8568(24) 1.0035(23) 0.047(7) Uiso 1 d . . C26 C 0.6809(2) 0.7830(2) 0.8854(2) 0.0337(4) Uani 1 d . . H26 H 0.5794(27) 0.8275(23) 0.8824(20) 0.039(6) Uiso 1 d . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 P1 0.0297(3) 0.0260(3) 0.0237(3) -0.0083(2) 0.0020(2) -0.0100(2) P2 0.0296(3) 0.0245(3) 0.0265(3) -0.0087(2) -0.0009(2) -0.0059(2) S1 0.0624(4) 0.0267(3) 0.0306(3) -0.0042(2) 0.0053(2) -0.0142(2) S2 0.0421(3) 0.0348(3) 0.0430(3) -0.0175(2) -0.0096(2) -0.0086(2) N1 0.0346(9) 0.0235(8) 0.0254(8) -0.0053(7) 0.0042(6) -0.0108(7) N2 0.0602(12) 0.0231(9) 0.0250(9) -0.0083(7) 0.0095(8) -0.0144(8) N3 0.0314(9) 0.0267(8) 0.0266(8) -0.0092(7) 0.0011(6) -0.0104(7) N4 0.0323(9) 0.0264(9) 0.0386(10) -0.0167(8) -0.0065(7) -0.0040(7) C1 0.0240(9) 0.0252(9) 0.0245(9) -0.0080(8) 0.0016(7) -0.0089(7) C2 0.0289(10) 0.0237(9) 0.0216(9) -0.0064(7) 0.0045(7) -0.0099(8) C3 0.074(2) 0.0395(14) 0.055(2) -0.0051(13) -0.0259(14) -0.0277(14) C4 0.0438(15) 0.066(2) 0.044(2) -0.0084(14) 0.0151(12) 0.0015(13) C5 0.0354(11) 0.0331(11) 0.0311(11) -0.0127(9) 0.0007(9) -0.0061(9) C6 0.0455(13) 0.0306(11) 0.0371(12) -0.0044(10) 0.0063(10) -0.0098(10) C11 0.0211(9) 0.0256(9) 0.0256(9) -0.0077(8) 0.0000(7) -0.0091(7) C12 0.0322(10) 0.0285(10) 0.0282(10) -0.0109(8) 0.0045(8) -0.0109(8) C13 0.0460(12) 0.0245(10) 0.0368(11) -0.0109(9) 0.0023(9) -0.0123(9) C14 0.0496(13) 0.0295(11) 0.0326(11) -0.0006(9) 0.0007(9) -0.0195(10) C15 0.0379(11) 0.0367(11) 0.0268(10) -0.0070(9) 0.0067(8) -0.0154(9) C16 0.0283(10) 0.0295(10) 0.0276(10) -0.0100(8) 0.0023(7) -0.0094(8) C21 0.0330(10) 0.0235(9) 0.0222(9) -0.0051(7) 0.0032(7) -0.0132(8) C22 0.0324(11) 0.0400(12) 0.0431(12) -0.0205(10) 0.0062(9) -0.0142(9) C23 0.0305(11) 0.0487(13) 0.0556(14) -0.0214(11) 0.0012(10) -0.0162(10) C24 0.0480(13) 0.0458(13) 0.0370(12) -0.0110(10) -0.0032(10) -0.0271(11) C25 0.0514(13) 0.0429(12) 0.0389(12) -0.0218(10) 0.0056(10) -0.0226(11) C26 0.0347(11) 0.0327(11) 0.0362(11) -0.0154(9) 0.0042(8) -0.0119(9) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag P1 N2 1.680(2) . ? P1 C3 1.784(2) . ? P1 C4 1.785(3) . ? P1 S1 1.9346(8) . ? P2 N4 1.689(2) . ? P2 C5 1.782(2) . ? P2 C6 1.794(2) . ? P2 S2 1.9469(7) . ? N1 C1 1.292(2) . ? N1 N2 1.376(2) . ? N3 C2 1.291(2) . ? N3 N4 1.380(2) . ? C1 C11 1.478(3) . ? C1 C2 1.506(2) . ? C2 C21 1.483(3) . ? C11 C16 1.397(3) . ? C11 C12 1.397(3) . ? C12 C13 1.383(3) . ? C13 C14 1.387(3) . ? C14 C15 1.381(3) . ? C15 C16 1.387(3) . ? C21 C22 1.390(3) . ? C21 C26 1.394(3) . ? C22 C23 1.388(3) . ? C23 C24 1.377(3) . ? C24 C25 1.376(3) . ? C25 C26 1.390(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N2 P1 C3 104.85(13) . . ? N2 P1 C4 105.03(12) . . ? C3 P1 C4 105.6(2) . . ? N2 P1 S1 108.72(7) . . ? C3 P1 S1 115.42(9) . . ? C4 P1 S1 116.21(11) . . ? N4 P2 C5 105.77(10) . . ? N4 P2 C6 106.82(10) . . ? C5 P2 C6 104.97(11) . . ? N4 P2 S2 107.18(6) . . ? C5 P2 S2 115.52(8) . . ? C6 P2 S2 115.86(9) . . ? C1 N1 N2 118.1(2) . . ? N1 N2 P1 119.30(13) . . ? C2 N3 N4 117.9(2) . . ? N3 N4 P2 119.89(13) . . ? N1 C1 C11 118.2(2) . . ? N1 C1 C2 122.5(2) . . ? C11 C1 C2 119.17(15) . . ? N3 C2 C21 118.8(2) . . ? N3 C2 C1 122.4(2) . . ? C21 C2 C1 118.8(2) . . ? C16 C11 C12 118.7(2) . . ? C16 C11 C1 120.0(2) . . ? C12 C11 C1 121.2(2) . . ? C13 C12 C11 120.5(2) . . ? C12 C13 C14 120.2(2) . . ? C15 C14 C13 119.8(2) . . ? C14 C15 C16 120.3(2) . . ? C15 C16 C11 120.4(2) . . ? C22 C21 C26 119.0(2) . . ? C22 C21 C2 119.9(2) . . ? C26 C21 C2 121.0(2) . . ? C23 C22 C21 120.3(2) . . ? C24 C23 C22 120.4(2) . . ? C25 C24 C23 119.8(2) . . ? C24 C25 C26 120.6(2) . . ? C25 C26 C21 120.0(2) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag S1 P1 N2 N1 167.36(13) . . . . ? P1 N2 N1 C1 -168.68(14) . . . . ? N2 N1 C1 C2 1.4(3) . . . . ? N1 C1 C2 N3 71.9(2) . . . . ? C1 C2 N3 N4 4.4(3) . . . . ? C2 N3 N4 P2 -165.62(14) . . . . ? N3 N4 P2 S2 -177.05(13) . . . . ? _refine_diff_density_max 0.264 _refine_diff_density_min -0.300 _refine_diff_density_rms 0.042 #====================================================================END data_L2 _ccdc_compound_id 'L^1^' _ccdc_biological_activity '?' _ccdc_polymorph '?' _refine_ls_abs_structure_details '?' _ccdc_disorder ; ? ; _ccdc_comments '?' _audit_creation_method SHELXL _chemical_name_systematic ; diphenyl-1,2-ethane-1,2-bis[(dimethylthiophosphoryl)hydrazide] ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C8 H20 N4 P2 S2' _chemical_formula_weight 298.34 _chemical_melting_point '437-440 K' _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 6.2200(1) _cell_length_b 12.1463(2) _cell_length_c 10.1414(1) _cell_angle_alpha 90.00 _cell_angle_beta 97.937(1) _cell_angle_gamma 90.00 _cell_volume 758.843(15) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.306 _exptl_crystal_density_method ? _exptl_crystal_F_000 316 _exptl_absorpt_coefficient_mu 0.545 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.726 _exptl_absorpt_correction_T_max 0.843 _exptl_special_details ; ? ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens SMART CCD' _diffrn_measurement_method \w _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 5381 _diffrn_reflns_av_R_equivalents 0.0238 _diffrn_reflns_av_sigmaI/netI 0.0201 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.63 _diffrn_reflns_theta_max 27.45 _reflns_number_total 1735 _reflns_number_observed 1595 _reflns_observed_criterion I>2\s(I) _computing_data_collection 'Siemens SMART (1995)' _computing_cell_refinement 'Siemens SAINT (1995)' _computing_data_reduction 'Siemens SAINT (1995)' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement on F^2^ for ALL reflections except for 17 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses of fit S are based on F^2^, conventional R- factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating R(obs) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0339P)^2^+0.3258P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0057(22) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 1718 _refine_ls_number_parameters 114 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0284 _refine_ls_R_factor_obs 0.0253 _refine_ls_wR_factor_all 0.0726 _refine_ls_wR_factor_obs 0.0661 _refine_ls_goodness_of_fit_all 1.056 _refine_ls_goodness_of_fit_obs 1.066 _refine_ls_restrained_S_all 1.121 _refine_ls_restrained_S_obs 1.066 _refine_ls_shift/esd_max 0.001 _refine_ls_shift/esd_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group P P 0.19688(5) 0.17399(3) 0.87116(3) 0.01674(11) Uani 1 d . . S S 0.09806(5) 0.17851(3) 1.04591(3) 0.02527(12) Uani 1 d . . N1 N 0.0508(2) 0.08016(10) 0.77636(10) 0.0242(3) Uani 1 d . . N2 N 0.0957(2) 0.06921(8) 0.64735(10) 0.0187(2) Uani 1 d . . C1 C -0.0291(2) 0.00536(9) 0.56792(11) 0.0161(2) Uani 1 d . . C2 C -0.2217(2) -0.05479(11) 0.60656(13) 0.0217(3) Uani 1 d . . C3 C 0.4789(2) 0.13885(14) 0.8730(2) 0.0299(3) Uani 1 d . . C4 C 0.1602(2) 0.29928(11) 0.77624(13) 0.0217(3) Uani 1 d . . H1 H -0.0339(31) 0.0373(16) 0.8072(18) 0.040(5) Uiso 1 d . . H2A H -0.3258(32) -0.0021(17) 0.6316(18) 0.044(5) Uiso 1 d . . H2B H -0.1817(30) -0.1004(16) 0.6782(19) 0.040(5) Uiso 1 d . . H2C H -0.2903(29) -0.0988(15) 0.5375(18) 0.036(5) Uiso 1 d . . H3A H 0.5033(31) 0.0647(17) 0.9133(19) 0.047(5) Uiso 1 d . . H3B H 0.5653(33) 0.1910(16) 0.9304(20) 0.042(5) Uiso 1 d . . H3C H 0.5133(30) 0.1388(16) 0.7866(19) 0.037(5) Uiso 1 d . . H4A H 0.0037(32) 0.3146(14) 0.7519(18) 0.033(5) Uiso 1 d . . H4B H 0.2251(32) 0.3547(17) 0.8310(20) 0.044(5) Uiso 1 d . . H4C H 0.2245(29) 0.2920(15) 0.6986(18) 0.034(4) Uiso 1 d . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 P 0.0167(2) 0.0222(2) 0.0115(2) -0.00269(10) 0.00234(11) -0.00128(11) S 0.0267(2) 0.0379(2) 0.0119(2) -0.00488(12) 0.00516(12) -0.00475(13) N1 0.0361(6) 0.0259(6) 0.0120(5) -0.0045(4) 0.0087(4) -0.0122(5) N2 0.0275(5) 0.0179(5) 0.0115(5) -0.0013(4) 0.0062(4) -0.0016(4) C1 0.0218(6) 0.0146(5) 0.0122(5) 0.0013(4) 0.0037(4) 0.0016(4) C2 0.0249(6) 0.0259(6) 0.0151(6) -0.0018(5) 0.0051(5) -0.0057(5) C3 0.0215(7) 0.0425(8) 0.0262(7) 0.0057(6) 0.0051(6) 0.0078(6) C4 0.0233(6) 0.0214(6) 0.0208(6) -0.0020(5) 0.0045(5) -0.0021(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag P N1 1.6757(11) . ? P C4 1.7984(14) . ? P C3 1.8026(14) . ? P S 1.9550(4) . ? N1 N2 1.3817(14) . ? N1 H1 0.83(2) . ? N2 C1 1.296(2) . ? C1 C1 1.478(2) 3_556 ? C1 C2 1.500(2) . ? C2 H2A 0.97(2) . ? C2 H2B 0.92(2) . ? C2 H2C 0.94(2) . ? C3 H3A 0.99(2) . ? C3 H3B 0.97(2) . ? C3 H3C 0.93(2) . ? C4 H4A 0.99(2) . ? C4 H4B 0.93(2) . ? C4 H4C 0.94(2) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 P C4 104.47(6) . . ? N1 P C3 107.15(7) . . ? C4 P C3 104.90(7) . . ? N1 P S 109.01(4) . . ? C4 P S 115.40(5) . . ? C3 P S 115.11(5) . . ? N2 N1 P 116.36(9) . . ? N2 N1 H1 121.1(13) . . ? P N1 H1 122.1(13) . . ? C1 N2 N1 117.63(10) . . ? N2 C1 C1 115.41(13) . 3_556 ? N2 C1 C2 124.07(10) . . ? C1 C1 C2 120.52(13) 3_556 . ? C1 C2 H2A 109.5(12) . . ? C1 C2 H2B 111.2(12) . . ? H2A C2 H2B 108.0(15) . . ? C1 C2 H2C 112.4(11) . . ? H2A C2 H2C 108.7(15) . . ? H2B C2 H2C 107.0(16) . . ? P C3 H3A 108.2(11) . . ? P C3 H3B 108.0(12) . . ? H3A C3 H3B 107.8(15) . . ? P C3 H3C 109.9(11) . . ? H3A C3 H3C 110.2(16) . . ? H3B C3 H3C 112.6(16) . . ? P C4 H4A 109.9(10) . . ? P C4 H4B 106.4(12) . . ? H4A C4 H4B 110.1(15) . . ? P C4 H4C 109.5(11) . . ? H4A C4 H4C 109.2(15) . . ? H4B C4 H4C 111.7(16) . . ? _refine_diff_density_max 0.382 _refine_diff_density_min -0.266 _refine_diff_density_rms 0.050 #====================================================================END data_L3 _ccdc_compound_id 'L^3^' _ccdc_biological_activity '?' _ccdc_polymorph '?' _refine_ls_abs_structure_details '?' _ccdc_disorder ; ? ; _ccdc_comments '?' _audit_creation_method SHELXL _chemical_name_systematic ; 2-(dimethylthiophosphorylamino)-6-picoline ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C8 H13 N2 P S' _chemical_formula_weight 200.23 _chemical_melting_point '411-413 K' _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'Monoclinic' _symmetry_space_group_name_H-M 'P 1 21/c 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 11.415(1) _cell_length_b 8.348(1) _cell_length_c 11.983(1) _cell_angle_alpha 90.00 _cell_angle_beta 114.54(1) _cell_angle_gamma 90.00 _cell_volume 1038.7(2) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 447 _cell_measurement_theta_min 12 _cell_measurement_theta_max 20 _exptl_crystal_description 'lump ' _exptl_crystal_colour 'colourless ' _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.280 _exptl_crystal_density_method ? _exptl_crystal_F_000 424 _exptl_absorpt_coefficient_mu 0.416 _exptl_absorpt_correction_type 'semiempirical' _exptl_absorpt_correction_T_min 0.8574 _exptl_absorpt_correction_T_max 0.9518 _exptl_special_details ; Semi-empirical absorption correction based on Laue equivalents and repeatedly measured reflections with different \y; before it R(int)=0.036. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'CCD area detector' _diffrn_measurement_method '\w scan in 0.3\% frames, 15 s/frame' _diffrn_standards_number '178 (50 frames)' _diffrn_standards_interval_count ? _diffrn_standards_interval_time '10 h' _diffrn_standards_decay_% 0.2 _diffrn_reflns_number 8012 _diffrn_reflns_av_R_equivalents 0.0279 _diffrn_reflns_av_sigmaI/netI 0.0266 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.96 _diffrn_reflns_theta_max 30.43 _reflns_number_total 2815 _reflns_number_observed 2425 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Siemens SMART' _computing_data_reduction 'Siemens SAINT' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'SHELXTL Vesion 5/VMS (1995)' _computing_publication_material 'SHELXTL Vesion 5/VMS (1995)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 9 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses of fit S are based on F^2^, conventional R- factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0216P)^2^+0.6285P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2806 _refine_ls_number_parameters 161 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0432 _refine_ls_R_factor_obs 0.0329 _refine_ls_wR_factor_all 0.0824 _refine_ls_wR_factor_obs 0.0727 _refine_ls_goodness_of_fit_all 1.163 _refine_ls_goodness_of_fit_obs 1.151 _refine_ls_restrained_S_all 1.205 _refine_ls_restrained_S_obs 1.151 _refine_ls_shift/esd_max -0.001 _refine_ls_shift/esd_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group S S 0.57931(3) 0.69613(5) 0.14493(4) 0.02691(11) Uani 1 d . . P P 0.39608(3) 0.73756(5) 0.10176(3) 0.01858(10) Uani 1 d . . N1 N 0.10632(11) 0.69690(15) -0.02776(11) 0.0189(2) Uani 1 d . . N2 N 0.30790(12) 0.6056(2) -0.00596(12) 0.0217(3) Uani 1 d . . H2 H 0.3457(20) 0.5423(26) -0.0290(18) 0.033(5) Uiso 1 d . . C2 C 0.17350(13) 0.5985(2) -0.06713(13) 0.0181(3) Uani 1 d . . C3 C 0.11609(15) 0.4909(2) -0.16426(15) 0.0258(3) Uani 1 d . . H3 H 0.1653(18) 0.4242(23) -0.1886(16) 0.026(5) Uiso 1 d . . C4 C -0.0169(2) 0.4867(2) -0.2214(2) 0.0289(4) Uani 1 d . . H4 H -0.0579(19) 0.4140(26) -0.2869(18) 0.036(5) Uiso 1 d . . C5 C -0.08843(14) 0.5879(2) -0.18149(15) 0.0242(3) Uani 1 d . . H5 H -0.1793(18) 0.5846(23) -0.2178(17) 0.029(5) Uiso 1 d . . C6 C -0.02387(13) 0.6910(2) -0.08457(14) 0.0195(3) Uani 1 d . . C7 C -0.0960(2) 0.8052(2) -0.0387(2) 0.0275(3) Uani 1 d . . H71 H -0.0928(20) 0.9117(28) -0.0664(19) 0.039(6) Uiso 1 d . . H72 H -0.0554(21) 0.8133(26) 0.0495(22) 0.043(6) Uiso 1 d . . H73 H -0.1830(23) 0.7704(27) -0.0626(21) 0.044(6) Uiso 1 d . . C8 C 0.3546(2) 0.7175(3) 0.2304(2) 0.0311(4) Uani 1 d . . H81 H 0.2648(21) 0.7392(25) 0.2066(19) 0.037(6) Uiso 1 d . . H82 H 0.4013(21) 0.7899(26) 0.2914(21) 0.039(6) Uiso 1 d . . H83 H 0.3759(22) 0.6068(30) 0.2618(21) 0.049(7) Uiso 1 d . . C9 C 0.3467(2) 0.9355(2) 0.0415(2) 0.0268(3) Uani 1 d . . H91 H 0.2556(20) 0.9422(25) 0.0110(18) 0.035(5) Uiso 1 d . . H92 H 0.3837(21) 1.0047(28) 0.1097(20) 0.044(6) Uiso 1 d . . H93 H 0.3759(22) 0.9559(29) -0.0218(21) 0.051(7) Uiso 1 d . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 S 0.0126(2) 0.0306(2) 0.0332(2) -0.0058(2) 0.00529(14) 0.00160(14) P 0.0130(2) 0.0219(2) 0.0194(2) -0.00281(14) 0.00530(13) 0.00046(14) N1 0.0160(5) 0.0201(6) 0.0199(6) 0.0001(5) 0.0069(5) 0.0000(5) N2 0.0131(5) 0.0236(6) 0.0256(6) -0.0074(5) 0.0052(5) 0.0019(5) C2 0.0146(6) 0.0198(7) 0.0178(6) 0.0012(5) 0.0047(5) 0.0009(5) C3 0.0200(7) 0.0281(8) 0.0266(8) -0.0085(6) 0.0069(6) 0.0025(6) C4 0.0201(7) 0.0295(8) 0.0293(8) -0.0098(7) 0.0026(6) -0.0011(6) C5 0.0144(6) 0.0251(8) 0.0285(8) 0.0000(6) 0.0041(6) -0.0003(6) C6 0.0158(6) 0.0193(7) 0.0233(7) 0.0037(6) 0.0081(5) 0.0013(5) C7 0.0198(7) 0.0284(8) 0.0359(9) -0.0026(7) 0.0131(7) 0.0027(6) C8 0.0251(8) 0.0474(11) 0.0216(8) -0.0042(8) 0.0103(6) -0.0044(8) C9 0.0207(7) 0.0225(8) 0.0352(9) -0.0023(7) 0.0096(7) 0.0009(6) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag S P 1.9655(5) . ? P N2 1.6771(13) . ? P C9 1.797(2) . ? P C8 1.799(2) . ? N1 C2 1.336(2) . ? N1 C6 1.354(2) . ? N2 C2 1.400(2) . ? N2 H2 0.80(2) . ? C2 C3 1.399(2) . ? C3 C4 1.382(2) . ? C3 H3 0.92(2) . ? C4 C5 1.391(2) . ? C4 H4 0.95(2) . ? C5 C6 1.386(2) . ? C5 H5 0.94(2) . ? C6 C7 1.505(2) . ? C7 H71 0.95(2) . ? C7 H72 0.96(2) . ? C7 H73 0.96(2) . ? C8 H81 0.96(2) . ? C8 H82 0.93(2) . ? C8 H83 0.99(2) . ? C9 H91 0.95(2) . ? C9 H92 0.95(2) . ? C9 H93 0.96(2) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N2 P C9 107.84(8) . . ? N2 P C8 108.14(8) . . ? C9 P C8 106.24(9) . . ? N2 P S 108.66(5) . . ? C9 P S 112.91(6) . . ? C8 P S 112.83(6) . . ? C2 N1 C6 118.11(13) . . ? C2 N2 P 127.43(11) . . ? C2 N2 H2 115.0(15) . . ? P N2 H2 117.5(15) . . ? N1 C2 C3 123.30(13) . . ? N1 C2 N2 116.98(13) . . ? C3 C2 N2 119.72(13) . . ? C4 C3 C2 117.84(15) . . ? C4 C3 H3 121.2(11) . . ? C2 C3 H3 121.0(12) . . ? C3 C4 C5 119.70(15) . . ? C3 C4 H4 119.3(12) . . ? C5 C4 H4 121.0(12) . . ? C6 C5 C4 118.77(14) . . ? C6 C5 H5 120.3(12) . . ? C4 C5 H5 120.9(12) . . ? N1 C6 C5 122.28(14) . . ? N1 C6 C7 116.51(13) . . ? C5 C6 C7 121.20(13) . . ? C6 C7 H71 110.8(13) . . ? C6 C7 H72 110.9(13) . . ? H71 C7 H72 104.2(18) . . ? C6 C7 H73 110.8(14) . . ? H71 C7 H73 111.3(18) . . ? H72 C7 H73 108.5(18) . . ? P C8 H81 110.8(13) . . ? P C8 H82 110.2(14) . . ? H81 C8 H82 107.7(18) . . ? P C8 H83 107.6(14) . . ? H81 C8 H83 110.6(18) . . ? H82 C8 H83 109.8(18) . . ? P C9 H91 108.6(13) . . ? P C9 H92 105.2(14) . . ? H91 C9 H92 108.7(18) . . ? P C9 H93 109.1(14) . . ? H91 C9 H93 111.6(18) . . ? H92 C9 H93 113.4(19) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag S P N2 C2 -176.19(12) . . . . ? P N2 C2 N1 -7.2(2) . . . . ? _refine_diff_density_max 0.353 _refine_diff_density_min -0.255 _refine_diff_density_rms 0.053 #===================================================================END data_(5) _ccdc_compound_id '5' _ccdc_biological_activity '?' _ccdc_polymorph '?' _refine_ls_abs_structure_details '?' _ccdc_disorder ; Cl and Br atoms are statistically mixed, occupying the same coordination site at Cu. Refinement of the occupancy factors gave 27% for Br and 73% for Cl. Coordinates and displacement parameters were kept the same for both atoms; attempts to elucidate separate positions for Cl and Br failed. ; _ccdc_comments '?' _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C16 H40 Br0.54 Cl1.46 Cu2 N8 P4 S4' _chemical_formula_weight 818.67 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'P' 'P' 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cl' 'Cl' 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Cu' 'Cu' 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Br' 'Br' -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'Monoclinic' _symmetry_space_group_name_H-M 'P 1 21/c 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 11.649(1) _cell_length_b 15.064(1) _cell_length_c 9.682(1) _cell_angle_alpha 90.00 _cell_angle_beta 94.11(1) _cell_angle_gamma 90.00 _cell_volume 1694.7(2) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 511 _cell_measurement_theta_min 5.41 _cell_measurement_theta_max 28.71 _exptl_crystal_description 'Square plate' _exptl_crystal_colour 'Colorless' _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.35 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.604 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 835 _exptl_absorpt_coefficient_mu 2.465 _exptl_absorpt_correction_type 'Integration' _exptl_absorpt_correction_T_min 0.44221 _exptl_absorpt_correction_T_max 0.78675 _exptl_special_details ; Area detector data were collected at 10 s per frame and 0.3 \w-scan width. Detector swing angle was 58 deg 2\q, the limiting sphere was sampled in batches of 202, 145 and 76 deg with \p settings of 0, 88, and 180 deg. 66 deg of additional data were collected at +29 deg 2\q. Settings angles for cell refinement were obtained from reflections with I/\s(I) > 20 in the resolution range of 0.5 to 4 \%A. Generator settings were 50kV and 45mA. The crystal to detector distance was 4.51 cm and a 0.8 mm collimator was used. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'Siemens SMART-CCD' _diffrn_measurement_method '\w-scans' _diffrn_standards_number 'none measured' _diffrn_standards_interval_count 'not measured' _diffrn_standards_interval_time 'not measured' _diffrn_standards_decay_% 'none' _diffrn_reflns_number 13814 _diffrn_reflns_av_R_equivalents 0.0407 _diffrn_reflns_av_sigmaI/netI 0.0324 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.75 _diffrn_reflns_theta_max 30.18 _reflns_number_total 4600 _reflns_number_observed 4085 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens SMART' _computing_cell_refinement 'Siemens SAINT' _computing_data_reduction 'Siemens SAINT' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 12 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R- factors wR and all goodnesses of fit S are based on F^2^, conventional R- factors R are based on F, with F set to zero for negative F^2^. The observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+3.1714P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment ref _refine_ls_extinction_method none _refine_ls_extinction_coef noref _refine_ls_number_reflns 4588 _refine_ls_number_parameters 241 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0486 _refine_ls_R_factor_obs 0.0390 _refine_ls_wR_factor_all 0.0856 _refine_ls_wR_factor_obs 0.0790 _refine_ls_goodness_of_fit_all 1.308 _refine_ls_goodness_of_fit_obs 1.323 _refine_ls_restrained_S_all 1.346 _refine_ls_restrained_S_obs 1.323 _refine_ls_shift/esd_max 0.211 _refine_ls_shift/esd_mean 0.007 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Cu Cu 0.17262(3) 0.54688(2) 0.29146(4) 0.02307(10) Uani 1 d . . Cl Cl 0.24490(5) 0.60802(3) 0.49645(5) 0.0275(2) Uani 0.728(3) d P . Br Br 0.24490(5) 0.60802(3) 0.49645(5) 0.0275(2) Uani 0.272(3) d P . P1 P 0.21289(6) 0.34999(5) 0.45943(7) 0.01854(14) Uani 1 d . . P2 P 0.81873(6) 0.37975(5) 1.02845(7) 0.01601(14) Uani 1 d . . S1 S 0.18258(7) 0.39714(5) 0.26854(7) 0.0237(2) Uani 1 d . . S2 S 0.92787(6) 0.37675(5) 0.87861(7) 0.02002(14) Uani 1 d . . N2 N 0.3943(2) 0.3512(2) 0.6393(2) 0.0197(5) Uani 1 d . . N1 N 0.3297(2) 0.3983(2) 0.5383(3) 0.0233(5) Uani 1 d . . H1 H 0.3294(30) 0.4514(24) 0.5371(36) 0.025(9) Uiso 1 d . . N3 N 0.6205(2) 0.3808(2) 0.8911(2) 0.0192(5) Uani 1 d . . N4 N 0.6895(2) 0.3325(2) 0.9884(3) 0.0203(5) Uani 1 d . . H4 H 0.6931(29) 0.2818(24) 0.9769(36) 0.024 Uiso 1 d . . C1 C 0.4717(2) 0.3938(2) 0.7163(3) 0.0185(5) Uani 1 d . . C2 C 0.5435(2) 0.3378(2) 0.8147(3) 0.0185(5) Uani 1 d . . C11 C 0.2409(3) 0.2327(2) 0.4585(4) 0.0294(7) Uani 1 d . . H11A H 0.1711(36) 0.2095(27) 0.4341(42) 0.043(11) Uiso 1 d . . H11B H 0.2636(33) 0.2125(26) 0.5445(43) 0.040(11) Uiso 1 d . . H11C H 0.2942(37) 0.2216(28) 0.3926(46) 0.050(12) Uiso 1 d . . C12 C 0.0934(3) 0.3672(3) 0.5642(4) 0.0376(8) Uani 1 d . . H12A H 0.0304(39) 0.3427(30) 0.5228(46) 0.053(13) Uiso 1 d . . H12B H 0.0781(33) 0.4309(28) 0.5692(40) 0.039(11) Uiso 1 d . . H12C H 0.1085(33) 0.3407(26) 0.6533(43) 0.041(11) Uiso 1 d . . C21 C 0.8742(3) 0.3168(2) 1.1748(3) 0.0249(6) Uani 1 d . . H21A H 0.8290(43) 0.3272(33) 1.2480(52) 0.071(16) Uiso 1 d . . H21B H 0.9534(34) 0.3340(26) 1.2005(39) 0.039(10) Uiso 1 d . . H21C H 0.8703(38) 0.2551(32) 1.1529(46) 0.059(14) Uiso 1 d . . C22 C 0.7860(3) 0.4905(2) 1.0819(3) 0.0255(6) Uani 1 d . . H22A H 0.8536(30) 0.5220(22) 1.0961(34) 0.023(8) Uiso 1 d . . H22B H 0.7461(36) 0.4861(27) 1.1588(45) 0.046(12) Uiso 1 d . . H22C H 0.7369(33) 0.5134(26) 1.0080(41) 0.037(10) Uiso 1 d . . C3 C 0.4937(3) 0.4920(2) 0.7131(4) 0.0263(6) Uani 1 d . . H3A H 0.5713(53) 0.5022(38) 0.6905(60) 0.096(12) Uiso 1 d . . H3B H 0.4862(52) 0.5160(39) 0.7913(65) 0.096(12) Uiso 1 d . . H3C H 0.4524(52) 0.5304(38) 0.6473(62) 0.096(12) Uiso 1 d . . C4 C 0.5275(3) 0.2388(2) 0.8180(4) 0.0259(6) Uani 1 d . . H4A H 0.4623(35) 0.2205(26) 0.7635(41) 0.042(11) Uiso 1 d . . H4B H 0.5139(28) 0.2162(23) 0.9174(36) 0.025(9) Uiso 1 d . . H4C H 0.5924(39) 0.2097(29) 0.7840(45) 0.054(13) Uiso 1 d . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu 0.0230(2) 0.0271(2) 0.0189(2) 0.00235(14) -0.00053(13) 0.00118(14) Cl 0.0368(3) 0.0206(3) 0.0232(3) -0.0044(2) -0.0107(2) 0.0049(2) Br 0.0368(3) 0.0206(3) 0.0232(3) -0.0044(2) -0.0107(2) 0.0049(2) P1 0.0156(3) 0.0229(3) 0.0166(3) 0.0030(3) -0.0031(2) -0.0042(3) P2 0.0150(3) 0.0169(3) 0.0155(3) 0.0000(2) -0.0027(2) -0.0018(2) S1 0.0309(4) 0.0229(3) 0.0162(3) 0.0022(3) -0.0053(3) -0.0047(3) S2 0.0178(3) 0.0250(3) 0.0171(3) 0.0002(3) -0.0001(2) 0.0024(3) N2 0.0167(10) 0.0224(12) 0.0193(11) 0.0047(9) -0.0041(9) -0.0002(9) N1 0.0228(12) 0.0181(12) 0.0272(12) 0.0055(10) -0.0113(10) -0.0047(10) N3 0.0157(10) 0.0208(11) 0.0204(11) 0.0048(9) -0.0038(8) 0.0004(9) N4 0.0184(11) 0.0180(11) 0.0234(12) 0.0040(9) -0.0062(9) -0.0022(9) C1 0.0133(11) 0.0219(13) 0.0200(12) 0.0026(10) -0.0004(9) -0.0028(10) C2 0.0141(11) 0.0195(13) 0.0215(13) 0.0017(10) -0.0011(10) -0.0005(10) C11 0.031(2) 0.022(2) 0.033(2) 0.0068(13) -0.0074(14) -0.0083(13) C12 0.026(2) 0.059(3) 0.029(2) 0.002(2) 0.0067(13) -0.006(2) C21 0.0223(14) 0.032(2) 0.0195(13) 0.0068(12) -0.0060(11) -0.0024(12) C22 0.0247(14) 0.0236(15) 0.029(2) -0.0068(12) 0.0051(12) -0.0022(12) C3 0.0217(13) 0.0190(14) 0.037(2) 0.0064(12) -0.0075(12) -0.0021(11) C4 0.0212(13) 0.0194(14) 0.035(2) 0.0044(12) -0.0113(12) -0.0033(11) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu S2 2.2648(7) 3_666 ? Cu S1 2.2702(8) . ? Cu Cl 2.2929(6) . ? Cu Br 2.2929(6) . ? P1 N1 1.678(2) . ? P1 C11 1.797(3) . ? P1 C12 1.799(4) . ? P1 S1 1.9880(10) . ? P2 N4 1.685(2) . ? P2 C21 1.787(3) . ? P2 C22 1.796(3) . ? P2 S2 1.9968(10) . ? S2 Cu 2.2648(7) 3_666 ? N2 C1 1.296(3) . ? N2 N1 1.386(3) . ? N1 H1 0.80(4) . ? N3 C2 1.296(3) . ? N3 N4 1.398(3) . ? N4 H4 0.77(4) . ? C1 C2 1.485(4) . ? C1 C3 1.503(4) . ? C2 C4 1.503(4) . ? C11 H11A 0.90(4) . ? C11 H11B 0.91(4) . ? C11 H11C 0.94(4) . ? C12 H12A 0.89(5) . ? C12 H12B 0.98(4) . ? C12 H12C 0.96(4) . ? C21 H21A 0.93(5) . ? C21 H21B 0.97(4) . ? C21 H21C 0.95(5) . ? C22 H22A 0.92(3) . ? C22 H22B 0.91(4) . ? C22 H22C 0.95(4) . ? C3 H3A 0.96(6) . ? C3 H3B 0.85(6) . ? C3 H3C 0.96(6) . ? C4 H4A 0.93(4) . ? C4 H4B 1.04(3) . ? C4 H4C 0.95(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag S2 Cu S1 117.45(3) 3_666 . ? S2 Cu Cl 124.33(3) 3_666 . ? S1 Cu Cl 117.75(3) . . ? S2 Cu Br 124.33(3) 3_666 . ? S1 Cu Br 117.75(3) . . ? Cl Cu Br 0.00(4) . . ? N1 P1 C11 106.72(14) . . ? N1 P1 C12 108.4(2) . . ? C11 P1 C12 107.0(2) . . ? N1 P1 S1 110.64(10) . . ? C11 P1 S1 111.53(12) . . ? C12 P1 S1 112.31(13) . . ? N4 P2 C21 103.00(13) . . ? N4 P2 C22 104.72(14) . . ? C21 P2 C22 109.7(2) . . ? N4 P2 S2 115.35(10) . . ? C21 P2 S2 110.56(12) . . ? C22 P2 S2 112.93(11) . . ? P1 S1 Cu 105.73(4) . . ? P2 S2 Cu 101.18(3) . 3_666 ? C1 N2 N1 118.2(2) . . ? N2 N1 P1 118.7(2) . . ? N2 N1 H1 121.6(26) . . ? P1 N1 H1 115.1(25) . . ? C2 N3 N4 117.7(2) . . ? N3 N4 P2 113.3(2) . . ? N3 N4 H4 116.8(26) . . ? P2 N4 H4 113.1(26) . . ? N2 C1 C2 115.1(2) . . ? N2 C1 C3 126.0(3) . . ? C2 C1 C3 118.9(2) . . ? N3 C2 C1 114.7(2) . . ? N3 C2 C4 124.5(2) . . ? C1 C2 C4 120.8(2) . . ? P1 C11 H11A 102.8(26) . . ? P1 C11 H11B 111.5(25) . . ? H11A C11 H11B 108.1(35) . . ? P1 C11 H11C 107.9(26) . . ? H11A C11 H11C 112.4(36) . . ? H11B C11 H11C 113.6(35) . . ? P1 C12 H12A 109.4(29) . . ? P1 C12 H12B 108.6(23) . . ? H12A C12 H12B 106.4(36) . . ? P1 C12 H12C 110.4(24) . . ? H12A C12 H12C 109.0(37) . . ? H12B C12 H12C 112.8(33) . . ? P2 C21 H21A 108.9(31) . . ? P2 C21 H21B 110.2(23) . . ? H21A C21 H21B 109.9(37) . . ? P2 C21 H21C 109.4(27) . . ? H21A C21 H21C 108.2(40) . . ? H21B C21 H21C 110.2(34) . . ? P2 C22 H22A 108.9(21) . . ? P2 C22 H22B 107.4(26) . . ? H22A C22 H22B 113.5(33) . . ? P2 C22 H22C 104.4(23) . . ? H22A C22 H22C 112.9(31) . . ? H22B C22 H22C 109.1(34) . . ? C1 C3 H3A 109.1(34) . . ? C1 C3 H3B 111.9(41) . . ? H3A C3 H3B 107.1(50) . . ? C1 C3 H3C 121.8(34) . . ? H3A C3 H3C 100.8(45) . . ? H3B C3 H3C 104.8(49) . . ? C2 C4 H4A 112.1(24) . . ? C2 C4 H4B 111.7(19) . . ? H4A C4 H4B 104.7(30) . . ? C2 C4 H4C 110.3(27) . . ? H4A C4 H4C 107.6(35) . . ? H4B C4 H4C 110.2(32) . . ? _refine_diff_density_max 0.461 _refine_diff_density_min -0.441 _refine_diff_density_rms 0.104 #===================================================================END