Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2005 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name A.Downs 'Andrew R.Cowley' 'Hans-Jorg Himmel' 'Sarah Marchant' 'S. Parsons' 'Justin A. Yeoman' _publ_contact_author_name 'Prof A Downs' _publ_contact_author_address ; Inorganic Chemistry Laboratory University of Oxford South Parks Road OXFORD OX1 3QR ; _publ_contact_author_email TONY.DOWNS@CHEM.OX.AC.UK _publ_requested_journal 'Dalton Transactions' _publ_section_title ; 1,1,3,3-Tetramethylguanidine-gallane,(Me2N)2CN(H).GaH3: an unusually strongly bound gallane adduct ; data_COMPOUND3 _database_code_depnum_ccdc_archive 'CCDC 262696' #============================================================= # Diffractometer details #============================================================= _diffrn_measurement_device_type ; Nonius KappaCCD ; _diffrn_radiation_monochromator graphite _computing_data_collection ; KappaCCD software 'Collect' (Nonius, 2000) ; _computing_data_reduction ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; _computing_cell_refinement ; KappaCCD software 'DENZO' (Otwinowski & Minor, 1996) ; #============================================================= # General computing #============================================================= _computing_structure_refinement ; CRYSTALS (Watkin et al, 2001) ; _computing_publication_material ; CRYSTALS (Watkin et al, 2001) ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' _chemical_name_systematic # IUPAC name, in full ; ? ; _chemical_melting_point 'not measured' _refine_ls_matrix_type full _atom_sites_solution_primary direct _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall #============================================================= _cell_length_a 8.4051(3) _cell_angle_alpha 90 _cell_length_b 9.8322(4) _cell_angle_beta 103.2623(18) _cell_length_c 11.6927(5) _cell_angle_gamma 90 _cell_volume 940.5 _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,-y,-z -x+1/2,y+1/2,-z+1/2 x+1/2,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source 'C ' 0.0020 0.0020 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 International_Tables_Vol_IV_Table_2.2B 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 International_Tables_Vol_IV_Table_2.2B 'Ga ' 0.1630 1.6090 15.2354 3.0669 6.7006 0.2412 4.3591 10.7805 2.9623 61.4135 1.7189 International_Tables_Vol_IV_Table_2.2B 'N ' 0.0040 0.0030 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 International_Tables_Vol_IV_Table_2.2B _chemical_formula_sum ' C5 H16 Ga1 N3 ' _chemical_formula_moiety ' C5 H16 Ga1 N3 ' _chemical_compound_source ; synthesis as described ; _chemical_formula_weight 187.92 _cell_measurement_reflns_used 7663 _cell_measurement_theta_min 5 _cell_measurement_theta_max 28 _cell_measurement_temperature 150 _cell_formula_units_Z 4 _exptl_crystal_description ' fragment ' _exptl_crystal_colour ' colourless ' _exptl_crystal_size_min 0.24 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_max 0.26 _exptl_crystal_density_diffrn 1.327 _exptl_crystal_density_meas 'not measured' _exptl_crystal_F_000 392.615 _exptl_absorpt_coefficient_mu 2.861 _diffrn_measurement_method \w _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; Denzo/Scalepack (Otwinowski & Minor, 1996) ; _exptl_absorpt_correction_T_min 0.48 _exptl_absorpt_correction_T_max 0.50 _diffrn_standards_interval_time 0 _diffrn_standards_interval_count 0 _diffrn_standards_number 0 _diffrn_standards_decay_% 0.00 _diffrn_ambient_temperature 150 _diffrn_reflns_number 7663 _reflns_number_total 2135 #2256 unique reflections including absences _diffrn_reflns_av_R_equivalents 0.036 _diffrn_measured_fraction_theta_max 0.996 _reflns_number_gt 1641 _diffrn_reflns_theta_min 5.24 _diffrn_reflns_theta_max 27.48 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _reflns_limit_h_min -10 _reflns_limit_h_max 10 _reflns_limit_k_min 0 _reflns_limit_k_max 12 _reflns_limit_l_min 0 _reflns_limit_l_max 15 _refine_diff_density_min -0.62 _refine_diff_density_max 0.28 _reflns_threshold_expression >3.00\s(I) _refine_ls_number_reflns 1641 _refine_ls_number_parameters 146 _refine_ls_R_factor_gt 0.0281 _refine_ls_wR_factor_ref 0.0341 _refine_ls_goodness_of_fit_ref 0.9080 _refine_ls_shift/su_max 0.035232 _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Chebychev polynomial with 3 parameters (Carruthers & Watkin , 1979) 0.962 0.292 0.595 ; _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 # Uequiv = arithmetic mean of Ui # i.e. Ueqiv = (U1+U2+U3)/3 loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type Ga1 0.31077(3) 0.15871(3) 0.55590(3) 0.0387 1.0000 Uani N1 0.5493(2) 0.1970(2) 0.59832(17) 0.0312 1.0000 Uani C1 0.6290(2) 0.3120(2) 0.62653(17) 0.0259 1.0000 Uani N2 0.5709(2) 0.40660(19) 0.68970(16) 0.0317 1.0000 Uani C2 0.5850(4) 0.5518(3) 0.6699(3) 0.0452 1.0000 Uani C3 0.4656(3) 0.3683(3) 0.7676(2) 0.0422 1.0000 Uani N3 0.7708(2) 0.3400(2) 0.59407(17) 0.0336 1.0000 Uani C4 0.9031(3) 0.4159(3) 0.6699(3) 0.0462 1.0000 Uani C5 0.8174(3) 0.2643(3) 0.5007(3) 0.0447 1.0000 Uani H1 0.308(5) 0.051(4) 0.451(3) 0.07(1) 1.0000 Uiso H2 0.268(5) 0.095(5) 0.660(3) 0.083(12) 1.0000 Uiso H3 0.219(4) 0.295(4) 0.516(3) 0.07(1) 1.0000 Uiso H4 0.602(4) 0.142(3) 0.577(3) 0.039(8) 1.0000 Uiso H21 0.637(4) 0.570(3) 0.605(3) 0.043(8) 1.0000 Uiso H22 0.644(5) 0.598(4) 0.742(3) 0.06(1) 1.0000 Uiso H23 0.480(4) 0.588(3) 0.655(3) 0.048(8) 1.0000 Uiso H31 0.485(4) 0.271(4) 0.788(3) 0.057(9) 1.0000 Uiso H32 0.501(4) 0.417(3) 0.838(3) 0.050(8) 1.0000 Uiso H33 0.358(4) 0.386(3) 0.732(3) 0.051(8) 1.0000 Uiso H41 0.875(4) 0.440(3) 0.743(3) 0.051(8) 1.0000 Uiso H42 0.998(4) 0.363(3) 0.685(3) 0.051(9) 1.0000 Uiso H43 0.924(5) 0.500(4) 0.630(4) 0.077(12) 1.0000 Uiso H51 0.726(4) 0.237(4) 0.445(3) 0.054(9) 1.0000 Uiso H52 0.893(4) 0.186(4) 0.530(3) 0.055(9) 1.0000 Uiso H53 0.875(5) 0.323(4) 0.458(3) 0.06(1) 1.0000 Uiso 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 Ga1 0.02604(15) 0.03350(15) 0.05558(18) 0.00128(12) 0.0074(1) -0.0053(1) N1 0.0269(8) 0.0285(9) 0.039(1) -0.0020(7) 0.0103(7) 0.0014(7) C1 0.0222(9) 0.029(1) 0.0272(9) 0.0020(7) 0.0063(7) 0.0010(7) N2 0.0319(9) 0.0310(9) 0.034(1) -0.0025(7) 0.0123(7) 0.0008(7) C2 0.0469(14) 0.0304(12) 0.0550(16) -0.0036(11) 0.0052(12) 0.004(1) C3 0.0345(12) 0.0592(17) 0.0364(12) -0.0049(11) 0.015(1) 0.0043(11) N3 0.0273(8) 0.039(1) 0.0374(9) -0.0040(8) 0.0131(7) -0.0051(8) C4 0.0287(12) 0.0505(16) 0.0589(16) -0.0086(13) 0.0092(11) -0.0101(11) C5 0.0360(12) 0.0598(17) 0.0443(14) -0.0068(12) 0.0215(11) -0.0009(12) _refine_ls_extinction_method None loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ga1 . N1 . 1.9881(19) yes Ga1 . H1 . 1.61(4) no Ga1 . H2 . 1.49(4) no Ga1 . H3 . 1.57(4) no N1 . C1 . 1.316(3) yes N1 . H4 . 0.78(3) no C1 . N2 . 1.347(3) yes C1 . N3 . 1.360(3) yes N2 . C2 . 1.455(3) yes N2 . C3 . 1.457(3) yes C2 . H21 . 0.97(3) no C2 . H22 . 0.99(4) no C2 . H23 . 0.93(3) no C3 . H31 . 0.99(4) no C3 . H32 . 0.94(3) no C3 . H33 . 0.92(4) no N3 . C4 . 1.458(3) yes N3 . C5 . 1.448(3) yes C4 . H41 . 0.97(3) no C4 . H42 . 0.94(4) no C4 . H43 . 0.98(4) no C5 . H51 . 0.93(3) no C5 . H52 . 1.01(4) no C5 . H53 . 0.96(4) no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 . Ga1 . H1 . 98.8(13) no N1 . Ga1 . H2 . 107.0(16) no H1 . Ga1 . H2 . 112.6(22) no N1 . Ga1 . H3 . 108.0(14) no H1 . Ga1 . H3 . 114.3(18) no H2 . Ga1 . H3 . 114.5(21) no Ga1 . N1 . C1 . 130.60(16) yes Ga1 . N1 . H4 . 113.9(23) no C1 . N1 . H4 . 112.6(23) no N1 . C1 . N2 . 120.21(19) yes N1 . C1 . N3 . 122.15(19) yes N2 . C1 . N3 . 117.64(19) yes C1 . N2 . C2 . 122.5(2) yes C1 . N2 . C3 . 120.8(2) yes C2 . N2 . C3 . 115.9(2) yes N2 . C2 . H21 . 111.9(18) no N2 . C2 . H22 . 111.0(21) no H21 . C2 . H22 . 110.7(27) no N2 . C2 . H23 . 107.5(20) no H21 . C2 . H23 . 110.8(25) no H22 . C2 . H23 . 104.6(28) no N2 . C3 . H31 . 108.1(19) no N2 . C3 . H32 . 107.6(20) no H31 . C3 . H32 . 106.0(28) no N2 . C3 . H33 . 110.0(20) no H31 . C3 . H33 . 112.4(29) no H32 . C3 . H33 . 112.5(28) no C1 . N3 . C4 . 121.9(2) yes C1 . N3 . C5 . 120.8(2) yes C4 . N3 . C5 . 114.9(2) yes N3 . C4 . H41 . 110.9(19) no N3 . C4 . H42 . 109.4(20) no H41 . C4 . H42 . 109.6(27) no N3 . C4 . H43 . 109.7(24) no H41 . C4 . H43 . 108.7(31) no H42 . C4 . H43 . 108.6(30) no N3 . C5 . H51 . 111.0(20) no N3 . C5 . H52 . 113.2(19) no H51 . C5 . H52 . 112.1(29) no N3 . C5 . H53 . 109.6(21) no H51 . C5 . H53 . 104.0(29) no H52 . C5 . H53 . 106.4(28) no data_COMPOUND6 _database_code_depnum_ccdc_archive 'CCDC 262697' _exptl_crystal_recrystallization_method 'decomposition product' _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C18 H56 Ga7 N13' _chemical_formula_sum 'C18 H56 Ga7 N13' _chemical_formula_weight 942.80 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' Ga Ga 0.2307 1.6083 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting rhombohedral _symmetry_space_group_name_H-M 'P 3' _symmetry_int_tables_number 143 _symmetry_space_group_name_Hall 'P 3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' _cell_length_a 19.7013(2) _cell_length_b 19.7013(2) _cell_length_c 8.8318(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 2968.72(8) _cell_formula_units_Z 3 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 6963 _cell_measurement_theta_min 2 _cell_measurement_theta_max 28.5 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.09 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.582 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1416 _exptl_absorpt_coefficient_mu 4.719 _exptl_absorpt_correction_type Multiscan _exptl_absorpt_correction_T_min 0.424 _exptl_absorpt_correction_T_max 0.650 _exptl_absorpt_process_details 'Sadabs v 2004/1' _exptl_special_details ; Oxford Cryosystems LT device. Bruker capillary optic used. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_probe ? _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_source 'fine-focus sealed tube' _diffrn_source_type 'sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart Apex CCD' _diffrn_measurement_method omega _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 28333 _diffrn_reflns_av_R_equivalents 0.0676 _diffrn_reflns_av_sigmaI/netI 0.0613 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -23 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 1.19 _diffrn_reflns_theta_max 24.99 _reflns_number_total 6995 _reflns_number_gt 6766 _reflns_threshold_expression >2sigma(I) _computing_data_collection SMART _computing_cell_refinement SAINT _computing_data_reduction SAINT _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics XP _computing_publication_material 'XCIF, ENCIFER, PLATON' _refine_special_details ; There are three molecules in the asymmetric unit all disposed about 3-fold axes. Molecule 1 contains Ga1-3, molecule 2 Ga4-6 and molecule 3 Ga7-9. Since the data were rather weak, especially at high angle, all three fragments were restrained to be geometrically similar. Similarity restarints were also applied to light-atom adps. H-atoms were attached to Ga in calculated positions, and a common Ga-H distance refined subject to the restraint that they are all of similar length. The distances all refined to 1.25(5), which may be rather on the short side. Methyl groups were treated with the Sheldrick rotating rigid group procedure. **Twinning** The structure is merohedrally twinned via a two fold axis about [110]; the matrix is (0 1 0 / 1 0 0 / 0 0 -1). In addition it is twinned by inversion. The twin scale factors are: 0.20263 0.03215 BASF 1 ...merohedral twinning 0.27218 0.04042 BASF 2 ...inversion domain 1 0.15861 0.03216 BASF 3 ...inversion domain 2 Use sum of basf2 and 3 as Flack parameter. Twinning by a two fold about [-1 1 0] and [0 0 1] were also tried but the scale factors refined to zero. There are two difference map peaks near NMe2 groups in molecule 3. These do not seem to form meaningful fragments with other difference map peaks, and they might be an artefact of the twinning. Checkcif output: ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0853P)^2^+11.8493P] 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 'riding or variable metric rigid group' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _chemical_absolute_configuration ad _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.43(5) _refine_ls_number_reflns 6995 _refine_ls_number_parameters 370 _refine_ls_number_restraints 409 _refine_ls_R_factor_all 0.0661 _refine_ls_R_factor_gt 0.0638 _refine_ls_wR_factor_ref 0.1643 _refine_ls_wR_factor_gt 0.1623 _refine_ls_goodness_of_fit_ref 1.165 _refine_ls_restrained_S_all 1.145 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_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_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ga1 Ga 0.59323(11) 0.22778(10) 0.00640(19) 0.0273(4) Uani 1 1 d DU . . H1 H 0.535(2) 0.1930(13) 0.091(3) 0.041 Uiso 1 1 calc RD . . Ga2 Ga 0.48284(12) 0.27051(14) -0.1855(2) 0.0379(5) Uani 1 1 d DU . . H21 H 0.419(2) 0.211(2) -0.1507(13) 0.057 Uiso 1 1 calc RD . . H22 H 0.4747(3) 0.2984(10) -0.307(4) 0.057 Uiso 1 1 calc RD . . Ga3 Ga 0.6667 0.3333 -0.2861(3) 0.0308(7) Uani 1 3 d SDU . . H3 H 0.6667 0.3333 -0.428(5) 0.046 Uiso 1 3 calc SRD . . N11 N 0.6510(8) 0.1732(7) -0.0215(12) 0.041(3) Uani 1 1 d DU . . C21 C 0.6431(10) 0.1183(7) 0.0655(13) 0.035(3) Uani 1 1 d DU . . N31 N 0.6434(11) 0.0531(8) 0.0217(16) 0.050(3) Uani 1 1 d DU . . N41 N 0.6311(9) 0.1186(7) 0.2220(12) 0.042(3) Uani 1 1 d DU . . C51 C 0.6828(12) 0.0180(10) 0.102(2) 0.056(5) Uani 1 1 d DU . . H51A H 0.7396 0.0512 0.0908 0.085 Uiso 1 1 calc R . . H51B H 0.6660 -0.0342 0.0608 0.085 Uiso 1 1 calc R . . H51C H 0.6691 0.0133 0.2102 0.085 Uiso 1 1 calc R . . C61 C 0.6230(12) 0.0259(11) -0.1306(18) 0.051(5) Uani 1 1 d DU . . H61A H 0.6079 0.0597 -0.1851 0.076 Uiso 1 1 calc R . . H61B H 0.5790 -0.0280 -0.1302 0.076 Uiso 1 1 calc R . . H61C H 0.6681 0.0276 -0.1809 0.076 Uiso 1 1 calc R . . C71 C 0.5798(12) 0.0483(9) 0.307(2) 0.047(4) Uani 1 1 d DU . . H71A H 0.5435 0.0074 0.2378 0.070 Uiso 1 1 calc R . . H71B H 0.5500 0.0601 0.3812 0.070 Uiso 1 1 calc R . . H71C H 0.6114 0.0300 0.3603 0.070 Uiso 1 1 calc R . . C81 C 0.6619(13) 0.1929(9) 0.3048(18) 0.053(6) Uani 1 1 d DU . . H81A H 0.7193 0.2207 0.3026 0.079 Uiso 1 1 calc R . . H81B H 0.6437 0.1822 0.4100 0.079 Uiso 1 1 calc R . . H81C H 0.6431 0.2254 0.2569 0.079 Uiso 1 1 calc R . . N91 N 0.6667 0.3333 0.0691(15) 0.020(3) Uani 1 3 d SDU . . H91 H 0.6667 0.3333 0.1744 0.023 Uiso 1 3 calc SR . . N101 N 0.5687(4) 0.2475(5) -0.1974(9) 0.030(2) Uani 1 1 d DU . . C111 C 0.5388(9) 0.1774(7) -0.2968(16) 0.047(3) Uani 1 1 d DU . . H11A H 0.5820 0.1683 -0.3231 0.070 Uiso 1 1 calc R . . H11B H 0.5169 0.1862 -0.3895 0.070 Uiso 1 1 calc R . . H11C H 0.4979 0.1315 -0.2434 0.070 Uiso 1 1 calc R . . Ga4 Ga 0.40824(9) 0.77271(9) -0.11226(17) 0.0174(3) Uani 1 1 d DU . . H4 H 0.467(2) 0.8068(12) -0.197(3) 0.026 Uiso 1 1 calc RD . . Ga5 Ga 0.51590(10) 0.72602(12) 0.07938(19) 0.0283(4) Uani 1 1 d DU . . H51 H 0.5219(2) 0.6959(11) 0.200(4) 0.042 Uiso 1 1 calc RD . . H52 H 0.580(2) 0.785(2) 0.0484(11) 0.042 Uiso 1 1 calc RD . . Ga6 Ga 0.3333 0.6667 0.1800(3) 0.0206(6) Uani 1 3 d SDU . . H6 H 0.3333 0.6667 0.322(5) 0.031 Uiso 1 3 calc SRD . . N12 N 0.3501(6) 0.8275(6) -0.0881(11) 0.022(2) Uani 1 1 d DU . . C22 C 0.3614(9) 0.8841(7) -0.1742(12) 0.028(2) Uani 1 1 d DU . . N32 N 0.3614(10) 0.9493(8) -0.1292(16) 0.047(3) Uani 1 1 d DU . . N42 N 0.3737(8) 0.8824(6) -0.3301(12) 0.037(3) Uani 1 1 d DU . . C52 C 0.3348(18) 0.9942(15) -0.216(3) 0.086(7) Uani 1 1 d DU . . H52A H 0.3791 1.0468 -0.2353 0.128 Uiso 1 1 calc R . . H52B H 0.2945 0.9985 -0.1583 0.128 Uiso 1 1 calc R . . H52C H 0.3127 0.9678 -0.3123 0.128 Uiso 1 1 calc R . . C62 C 0.3870(14) 0.9784(12) 0.021(2) 0.064(6) Uani 1 1 d DU . . H62A H 0.3429 0.9518 0.0912 0.096 Uiso 1 1 calc R . . H62B H 0.4063 1.0350 0.0229 0.096 Uiso 1 1 calc R . . H62C H 0.4291 0.9685 0.0505 0.096 Uiso 1 1 calc R . . C72 C 0.4283(14) 0.9503(10) -0.418(2) 0.062(6) Uani 1 1 d DU . . H72A H 0.4062 0.9480 -0.5187 0.093 Uiso 1 1 calc R . . H72B H 0.4780 0.9506 -0.4288 0.093 Uiso 1 1 calc R . . H72C H 0.4377 0.9982 -0.3664 0.093 Uiso 1 1 calc R . . C82 C 0.3421(9) 0.8080(7) -0.4119(14) 0.027(3) Uani 1 1 d DU . . H82A H 0.3834 0.7948 -0.4257 0.041 Uiso 1 1 calc R . . H82B H 0.3226 0.8130 -0.5110 0.041 Uiso 1 1 calc R . . H82C H 0.2989 0.7665 -0.3536 0.041 Uiso 1 1 calc R . . N92 N 0.3333 0.6667 -0.1748(18) 0.026(3) Uani 1 3 d SDU . . H92 H 0.3333 0.6667 -0.2801 0.031 Uiso 1 3 calc SR . . N102 N 0.4320(5) 0.7521(5) 0.0916(9) 0.0239(19) Uani 1 1 d DU . . C112 C 0.4629(8) 0.8226(7) 0.1887(15) 0.042(3) Uani 1 1 d DU . . H11D H 0.5122 0.8642 0.1460 0.064 Uiso 1 1 calc R . . H11E H 0.4724 0.8097 0.2908 0.064 Uiso 1 1 calc R . . H11F H 0.4247 0.8405 0.1935 0.064 Uiso 1 1 calc R . . Ga7 Ga -0.00469(10) 0.09206(9) 0.60650(19) 0.0252(3) Uani 1 1 d DU . . H7 H -0.0447(14) 0.1090(6) 0.521(3) 0.038 Uiso 1 1 calc RD . . Ga8 Ga -0.16152(10) 0.00041(11) 0.7971(2) 0.0313(4) Uani 1 1 d DU . . H81 H -0.1918(11) -0.0360(13) 0.917(4) 0.047 Uiso 1 1 calc RD . . H82 H -0.1895(10) 0.0433(15) 0.7652(12) 0.047 Uiso 1 1 calc RD . . Ga9 Ga 0.0000 0.0000 0.8987(3) 0.0223(6) Uani 1 3 d SDU . . H9 H 0.0000 0.0000 1.040(5) 0.033 Uiso 1 3 calc SRD . . N13 N 0.1038(5) 0.1749(5) 0.6303(10) 0.027(2) Uani 1 1 d DU . . C23 C 0.1351(8) 0.2334(7) 0.5422(12) 0.036(3) Uani 1 1 d DU . . N33 N 0.1859(8) 0.3080(6) 0.5825(14) 0.049(4) Uani 1 1 d DU . . N43 N 0.1219(11) 0.2274(7) 0.3856(11) 0.052(4) Uani 1 1 d DU . . C53 C 0.2541(12) 0.3611(11) 0.494(2) 0.067(6) Uani 1 1 d DU . . H53A H 0.2689 0.3307 0.4275 0.100 Uiso 1 1 calc R . . H53B H 0.2977 0.3937 0.5616 0.100 Uiso 1 1 calc R . . H53C H 0.2416 0.3947 0.4317 0.100 Uiso 1 1 calc R . . C63 C 0.1902(9) 0.3321(9) 0.7354(17) 0.039(4) Uani 1 1 d DU . . H63A H 0.1373 0.3073 0.7786 0.058 Uiso 1 1 calc R . . H63B H 0.2138 0.3892 0.7395 0.058 Uiso 1 1 calc R . . H63C H 0.2224 0.3163 0.7935 0.058 Uiso 1 1 calc R . . C73 C 0.1190(18) 0.2891(12) 0.300(2) 0.084(7) Uani 1 1 d DU . . H73A H 0.1288 0.3322 0.3689 0.126 Uiso 1 1 calc R . . H73B H 0.0671 0.2682 0.2541 0.126 Uiso 1 1 calc R . . H73C H 0.1591 0.3084 0.2211 0.126 Uiso 1 1 calc R . . C83 C 0.0910(8) 0.1536(8) 0.3018(15) 0.035(3) Uani 1 1 d DU . . H83A H 0.1234 0.1299 0.3224 0.053 Uiso 1 1 calc R . . H83B H 0.0918 0.1639 0.1931 0.053 Uiso 1 1 calc R . . H83C H 0.0370 0.1177 0.3339 0.053 Uiso 1 1 calc R . . N93 N 0.0000 0.0000 0.5461(18) 0.027(3) Uani 1 3 d SDU . . H93 H 0.0000 0.0000 0.4408 0.033 Uiso 1 3 calc SR . . N103 N -0.0467(5) 0.0605(5) 0.8105(9) 0.0284(19) Uani 1 1 d DU . . C113 C -0.0317(9) 0.1271(7) 0.9091(15) 0.038(3) Uani 1 1 d DU . . H11G H 0.0205 0.1491 0.9543 0.056 Uiso 1 1 calc R . . H11H H -0.0712 0.1089 0.9895 0.056 Uiso 1 1 calc R . . H11I H -0.0345 0.1675 0.8489 0.056 Uiso 1 1 calc R . . 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 Ga1 0.0273(10) 0.0251(9) 0.0255(8) -0.0018(8) 0.0031(7) 0.0100(7) Ga2 0.0365(11) 0.0577(14) 0.0265(11) -0.0106(9) -0.0089(8) 0.0288(11) Ga3 0.0365(11) 0.0365(11) 0.0195(16) 0.000 0.000 0.0182(6) N11 0.071(10) 0.035(6) 0.026(6) -0.016(5) -0.015(6) 0.034(7) C21 0.035(8) 0.037(7) 0.039(5) -0.008(4) -0.008(6) 0.022(6) N31 0.058(9) 0.029(6) 0.063(8) -0.008(6) -0.009(7) 0.022(6) N41 0.050(9) 0.038(6) 0.042(5) 0.007(4) -0.002(6) 0.026(6) C51 0.056(12) 0.020(9) 0.091(13) 0.016(9) 0.009(10) 0.018(8) C61 0.048(11) 0.040(10) 0.056(8) -0.012(7) 0.019(8) 0.016(9) C71 0.060(12) 0.038(7) 0.054(9) 0.005(7) 0.007(8) 0.032(8) C81 0.057(12) 0.048(7) 0.028(8) -0.004(6) 0.011(9) 0.007(9) N91 0.024(4) 0.024(4) 0.011(8) 0.000 0.000 0.0119(19) N101 0.015(5) 0.044(7) 0.026(5) -0.013(4) -0.005(4) 0.012(4) C111 0.050(10) 0.042(7) 0.042(7) -0.016(7) -0.001(8) 0.019(5) Ga4 0.0140(8) 0.0150(8) 0.0205(8) 0.0000(6) 0.0016(6) 0.0050(6) Ga5 0.0239(9) 0.0428(11) 0.0168(9) -0.0074(8) -0.0073(7) 0.0156(9) Ga6 0.0261(9) 0.0261(9) 0.0096(12) 0.000 0.000 0.0130(4) N12 0.019(6) 0.028(5) 0.020(5) -0.002(4) 0.002(5) 0.014(5) C22 0.021(7) 0.031(6) 0.032(5) 0.005(4) -0.002(6) 0.013(5) N32 0.041(8) 0.043(7) 0.070(8) 0.001(6) 0.003(7) 0.031(7) N42 0.035(7) 0.028(6) 0.040(5) 0.020(4) 0.018(6) 0.010(6) C52 0.094(16) 0.076(14) 0.119(16) 0.038(13) 0.020(14) 0.067(13) C62 0.043(11) 0.045(11) 0.093(11) -0.031(9) -0.010(11) 0.013(9) C72 0.058(13) 0.042(7) 0.049(10) 0.022(8) 0.018(10) -0.002(10) C82 0.029(7) 0.037(5) 0.009(5) 0.016(4) 0.001(5) 0.011(5) N92 0.016(4) 0.016(4) 0.045(10) 0.000 0.000 0.0081(19) N102 0.036(5) 0.013(5) 0.027(5) 0.005(4) 0.004(4) 0.014(4) C112 0.031(8) 0.041(6) 0.047(7) -0.026(7) -0.020(7) 0.012(4) Ga7 0.0294(9) 0.0232(8) 0.0243(8) 0.0010(6) -0.0027(6) 0.0140(7) Ga8 0.0280(9) 0.0402(10) 0.0277(8) -0.0025(7) 0.0004(7) 0.0185(8) Ga9 0.0226(8) 0.0226(8) 0.0217(13) 0.000 0.000 0.0113(4) N13 0.029(5) 0.033(4) 0.009(4) 0.000(4) 0.003(4) 0.008(4) C23 0.032(7) 0.035(5) 0.031(5) 0.009(4) 0.011(6) 0.011(4) N33 0.051(8) 0.030(5) 0.046(6) 0.012(5) 0.022(6) 0.007(5) N43 0.084(10) 0.043(7) 0.027(4) 0.020(4) 0.017(6) 0.030(7) C53 0.057(11) 0.050(10) 0.050(9) 0.020(9) 0.021(9) -0.005(7) C63 0.025(8) 0.036(8) 0.059(7) -0.007(6) 0.017(6) 0.018(7) C73 0.123(19) 0.066(10) 0.066(12) 0.036(10) 0.008(13) 0.050(13) C83 0.016(7) 0.052(7) 0.026(6) 0.008(5) 0.015(6) 0.009(6) N93 0.019(4) 0.019(4) 0.044(9) 0.000 0.000 0.0094(19) N103 0.024(4) 0.031(6) 0.028(5) 0.004(4) 0.000(4) 0.013(4) C113 0.042(7) 0.039(7) 0.037(6) -0.009(6) -0.004(7) 0.024(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 Ga1 N91 1.928(4) . ? Ga1 N11 1.933(8) . ? Ga1 N101 1.953(8) . ? Ga2 N101 1.960(8) . ? Ga2 N11 1.972(12) 3_665 ? Ga3 N101 1.984(8) 2_655 ? Ga3 N101 1.984(8) . ? Ga3 N101 1.984(8) 3_665 ? N11 C21 1.271(12) . ? N11 Ga2 1.972(12) 2_655 ? C21 N31 1.346(12) . ? C21 N41 1.403(12) . ? N31 C61 1.429(15) . ? N31 C51 1.457(14) . ? N41 C71 1.450(13) . ? N41 C81 1.469(13) . ? N91 Ga1 1.928(4) 2_655 ? N91 Ga1 1.928(4) 3_665 ? N101 C111 1.487(11) . ? Ga4 N12 1.938(8) . ? Ga4 N92 1.940(5) . ? Ga4 N102 1.953(8) . ? Ga5 N102 1.964(8) . ? Ga5 N12 1.969(9) 3_565 ? Ga6 N102 1.987(8) 3_565 ? Ga6 N102 1.987(8) . ? Ga6 N102 1.987(8) 2_665 ? N12 C22 1.274(12) . ? N12 Ga5 1.968(9) 2_665 ? C22 N32 1.346(12) . ? C22 N42 1.401(12) . ? N32 C62 1.430(15) . ? N32 C52 1.451(14) . ? N42 C72 1.454(13) . ? N42 C82 1.464(13) . ? N92 Ga4 1.940(5) 3_565 ? N92 Ga4 1.940(5) 2_665 ? N102 C112 1.479(11) . ? Ga7 N93 1.936(5) . ? Ga7 N13 1.946(8) . ? Ga7 N103 1.950(8) . ? Ga8 N13 1.962(10) 2 ? Ga8 N103 1.963(8) . ? Ga9 N103 1.993(8) 3 ? Ga9 N103 1.993(8) . ? Ga9 N103 1.993(8) 2 ? N13 C23 1.267(12) . ? N13 Ga8 1.962(10) 3 ? C23 N33 1.349(13) . ? C23 N43 1.402(12) . ? N33 C63 1.419(15) . ? N33 C53 1.453(14) . ? N43 C73 1.454(13) . ? N43 C83 1.465(13) . ? N93 Ga7 1.936(5) 3 ? N93 Ga7 1.936(5) 2 ? N103 C113 1.477(12) . ? 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 N91 Ga1 N11 107.7(4) . . ? N91 Ga1 N101 100.2(4) . . ? N11 Ga1 N101 105.4(4) . . ? N101 Ga2 N11 100.0(4) . 3_665 ? N101 Ga3 N101 105.4(3) 2_655 . ? N101 Ga3 N101 105.4(3) 2_655 3_665 ? N101 Ga3 N101 105.4(3) . 3_665 ? C21 N11 Ga1 122.7(9) . . ? C21 N11 Ga2 121.0(9) . 2_655 ? Ga1 N11 Ga2 116.2(5) . 2_655 ? N11 C21 N31 125.6(10) . . ? N11 C21 N41 122.8(10) . . ? N31 C21 N41 111.6(10) . . ? C21 N31 C61 119.5(11) . . ? C21 N31 C51 124.8(11) . . ? C61 N31 C51 113.6(11) . . ? C21 N41 C71 123.1(11) . . ? C21 N41 C81 120.5(10) . . ? C71 N41 C81 115.9(10) . . ? Ga1 N91 Ga1 112.1(3) 2_655 3_665 ? Ga1 N91 Ga1 112.1(3) 2_655 . ? Ga1 N91 Ga1 112.1(3) 3_665 . ? C111 N101 Ga1 112.5(8) . . ? C111 N101 Ga2 105.1(7) . . ? Ga1 N101 Ga2 108.9(4) . . ? C111 N101 Ga3 108.8(7) . . ? Ga1 N101 Ga3 107.5(4) . . ? Ga2 N101 Ga3 114.1(4) . . ? N12 Ga4 N92 106.7(3) . . ? N12 Ga4 N102 106.5(4) . . ? N92 Ga4 N102 99.8(5) . . ? N102 Ga5 N12 100.7(4) . 3_565 ? N102 Ga6 N102 105.6(3) 3_565 . ? N102 Ga6 N102 105.6(3) 3_565 2_665 ? N102 Ga6 N102 105.6(3) . 2_665 ? C22 N12 Ga4 121.9(8) . . ? C22 N12 Ga5 123.0(7) . 2_665 ? Ga4 N12 Ga5 115.1(4) . 2_665 ? N12 C22 N32 125.2(10) . . ? N12 C22 N42 121.5(10) . . ? N32 C22 N42 113.3(10) . . ? C22 N32 C62 119.2(11) . . ? C22 N32 C52 126.8(13) . . ? C62 N32 C52 113.9(12) . . ? C22 N42 C72 124.1(11) . . ? C22 N42 C82 121.1(9) . . ? C72 N42 C82 114.0(10) . . ? Ga4 N92 Ga4 112.2(4) . 3_565 ? Ga4 N92 Ga4 112.2(4) . 2_665 ? Ga4 N92 Ga4 112.2(4) 3_565 2_665 ? C112 N102 Ga4 111.6(7) . . ? C112 N102 Ga5 105.7(7) . . ? Ga4 N102 Ga5 108.9(4) . . ? C112 N102 Ga6 109.7(7) . . ? Ga4 N102 Ga6 107.7(4) . . ? Ga5 N102 Ga6 113.3(4) . . ? N93 Ga7 N13 105.5(4) . . ? N93 Ga7 N103 99.6(5) . . ? N13 Ga7 N103 106.3(4) . . ? N13 Ga8 N103 100.3(4) 2 . ? N103 Ga9 N103 105.7(3) 3 . ? N103 Ga9 N103 105.7(3) 3 2 ? N103 Ga9 N103 105.7(3) . 2 ? C23 N13 Ga7 121.8(9) . . ? C23 N13 Ga8 122.2(8) . 3 ? Ga7 N13 Ga8 116.0(4) . 3 ? N13 C23 N33 126.1(10) . . ? N13 C23 N43 123.0(10) . . ? N33 C23 N43 110.9(10) . . ? C23 N33 C63 120.2(10) . . ? C23 N33 C53 123.9(12) . . ? C63 N33 C53 113.2(11) . . ? C23 N43 C73 121.5(12) . . ? C23 N43 C83 123.3(10) . . ? C73 N43 C83 113.5(11) . . ? Ga7 N93 Ga7 112.7(4) 3 . ? Ga7 N93 Ga7 112.7(4) 3 2 ? Ga7 N93 Ga7 112.7(4) . 2 ? C113 N103 Ga7 113.4(8) . . ? C113 N103 Ga8 103.3(7) . . ? Ga7 N103 Ga8 108.3(4) . . ? C113 N103 Ga9 110.7(7) . . ? Ga7 N103 Ga9 107.6(4) . . ? Ga8 N103 Ga9 113.6(4) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 2.198 _refine_diff_density_min -0.736 _refine_diff_density_rms 0.196