# Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2001
# CCDC Number: 186/2277

data_global
_publ_contact_author_name
;
 S. Midollini
;
_publ_contact_author_address
;
 Istituto per lo Studio della Stereochimica ed Energetica
 dei Composti di Coordinazione, Via Jacopo Nardi, 39
 50132 Firenze (Italy)
;
_publ_requested_journal
;
 'J. Chem. Soc. Dalton Trans.'
;
_publ_section_title
;
'Complexes of the Tripodal Nitrilo-tris(methylenephosphonic) (H6L) and
Nitrilo-tris(methylenephenylphosphinic) (H3Lø) Acids with Divalent Metal
Ions. Synthesis and Characterization of [(H3L)Cu(H2O)](Hpy) and
[(HLø)Cu(py)]2.2acetone'
;
data_Copperdimer

_audit_creation_method            SHELXL
_chemical_name_systematic
;
 bis(nitrilo-tris(methylenephenylphosphinate)copper(II)Pyridine),
 bis-acetone
;
_chemical_name_common             ?
_chemical_formula_moiety          ?
_chemical_formula_structural      ?
_chemical_formula_analytical      ?
_chemical_formula_sum             'C58 H66 Cu2 N4 O14 P6'
_chemical_formula_weight          1356.05
_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'
 'O'  'O'   0.0106   0.0060
 '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'
 'Cu'  'Cu'   0.3201   1.2651
 '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                    11.162(5)
_cell_length_b                    12.414(9)
_cell_length_c                    13.967(6)
_cell_angle_alpha                 63.75(4)
_cell_angle_beta                  85.75(4)
_cell_angle_gamma                 65.04(4)
_cell_volume                      1558.5(15)
_cell_formula_units_Z             1
_cell_measurement_temperature     293(2)
_cell_measurement_reflns_used     ?
_cell_measurement_theta_min       ?
_cell_measurement_theta_max       ?

_exptl_crystal_description        prismatic
_exptl_crystal_colour             pale blue
_exptl_crystal_size_max           0.35
_exptl_crystal_size_mid           ?
_exptl_crystal_size_min           0.20
_exptl_crystal_density_meas       ?
_exptl_crystal_density_diffrn     1.445
_exptl_crystal_density_method     ?
_exptl_crystal_F_000              702
_exptl_absorpt_coefficient_mu     0.902
_exptl_absorpt_correction_type    ?
_exptl_absorpt_correction_T_min   ?
_exptl_absorpt_correction_T_max   ?

_exptl_special_details
;
 ?
;

_diffrn_ambient_temperature       293(2)
_diffrn_radiation_wavelength      0.71070
_diffrn_radiation_type            MoK\a
_diffrn_radiation_source          'fine-focus sealed tube'
_diffrn_radiation_monochromator   graphite
_diffrn_measurement_device        'enraf nonius cad4'
_diffrn_measurement_method        omega-2theta
_diffrn_standards_number          3
_diffrn_standards_interval_count  ?
_diffrn_standards_interval_time   120
_diffrn_standards_decay_%         ?
_diffrn_reflns_number             2905
_diffrn_reflns_av_R_equivalents   0.0000
_diffrn_reflns_av_sigmaI/netI     0.2385
_diffrn_reflns_limit_h_min        -10
_diffrn_reflns_limit_h_max        10
_diffrn_reflns_limit_k_min        -10
_diffrn_reflns_limit_k_max        11
_diffrn_reflns_limit_l_min        0
_diffrn_reflns_limit_l_max        13
_diffrn_reflns_theta_min          2.78
_diffrn_reflns_theta_max          19.98
_reflns_number_total              2905
_reflns_number_observed           1425
_reflns_observed_criterion        >2sigma(I)

_computing_data_collection        ?
_computing_cell_refinement        ?
_computing_data_reduction         ?
_computing_structure_solution     'SIR-92'
_computing_structure_refinement   'SHELXL-93 (Sheldrick, 1993)'
_computing_molecular_graphics     'ORTEP (Johnson, 1976; Zsolnai, 1994)'
_computing_publication_material   ?

_refine_special_details
;
 Refinement on F^2^ for ALL reflections except for 0 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^)+(0.0878P)^2^+0.0000P] 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     ?
_refine_ls_extinction_method      none
_refine_ls_extinction_coef        ?
_refine_ls_number_reflns          2905
_refine_ls_number_parameters      183
_refine_ls_number_restraints      0
_refine_ls_R_factor_all           0.2027
_refine_ls_R_factor_obs           0.0686
_refine_ls_wR_factor_all          0.1899
_refine_ls_wR_factor_obs          0.1435
_refine_ls_goodness_of_fit_all    0.963
_refine_ls_goodness_of_fit_obs    1.068
_refine_ls_restrained_S_all       0.963
_refine_ls_restrained_S_obs       1.068
_refine_ls_shift/esd_max           .634
_refine_ls_shift/esd_mean         0.219

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
Cu1 Cu 0.7090(2) 0.8532(2) 0.92677(14) 0.0374(6) Uani 1 d . .
P1 P 0.6048(4) 1.1000(3) 0.9570(3) 0.0369(10) Uani 1 d . .
P2 P 0.6158(4) 0.8549(4) 0.7292(3) 0.0434(11) Uani 1 d . .
P3 P 0.8735(4) 0.9568(4) 0.7359(4) 0.0533(12) Uani 1 d . .
O1 O 0.7123(8) 0.9586(7) 0.9984(7) 0.044(3) Uani 1 d . .
O2 O 0.5012(8) 1.1302(8) 1.0266(7) 0.048(3) Uani 1 d . .
O3 O 0.6933(8) 0.7664(7) 0.8417(7) 0.043(3) Uani 1 d . .
O4 O 0.6968(10) 0.8566(9) 0.6370(7) 0.060(3) Uani 1 d . .
O5 O 0.9126(8) 0.8536(8) 0.8483(8) 0.055(3) Uani 1 d . .
O6 O 0.8694(9) 0.9176(10) 0.6447(8) 0.070(3) Uani 1 d . .
N1 N 0.6112(10) 1.0353(9) 0.7891(8) 0.032(3) Uiso 1 d . .
C1 C 0.5240(12) 1.1343(12) 0.8286(10) 0.039(4) Uiso 1 d . .
H11 H 0.4391(12) 1.1295(12) 0.8395(10) 0.047 Uiso 1 calc R .
H12 H 0.5066(12) 1.2238(12) 0.7745(10) 0.047 Uiso 1 calc R .
C2 C 0.5339(12) 1.0191(11) 0.7234(10) 0.037(4) Uiso 1 d . .
H21 H 0.5196(12) 1.0863(11) 0.6493(10) 0.045 Uiso 1 calc R .
H22 H 0.4473(12) 1.0325(11) 0.7476(10) 0.045 Uiso 1 calc R .
C3 C 0.7089(12) 1.0888(12) 0.7255(11) 0.048(4) Uiso 1 d . .
H31 H 0.7200(12) 1.1449(12) 0.7519(11) 0.057 Uiso 1 calc R .
H32 H 0.6706(12) 1.1441(12) 0.6502(11) 0.057 Uiso 1 calc R .
N2 N 0.8047(10) 0.6804(10) 1.0561(8) 0.041(3) Uiso 1 d . .
C4 C 0.8312(14) 0.6705(14) 1.1496(12) 0.058(4) Uiso 1 d . .
H4 H 0.8040(14) 0.7483(14) 1.1565(12) 0.070 Uiso 1 calc R .
C5 C 0.8987(14) 0.5483(15) 1.2397(13) 0.073(5) Uiso 1 d . .
H5 H 0.9106(14) 0.5449(15) 1.3063(13) 0.088 Uiso 1 calc R .
C6 C 0.9459(15) 0.4365(16) 1.2295(13) 0.072(5) Uiso 1 d . .
H6 H 0.9938(15) 0.3543(16) 1.2883(13) 0.087 Uiso 1 calc R .
C7 C 0.9245(15) 0.4440(16) 1.1376(13) 0.077(5) Uiso 1 d . .
H7 H 0.9613(15) 0.3660(16) 1.1302(13) 0.093 Uiso 1 calc R .
C8 C 0.8469(15) 0.5661(15) 1.0465(13) 0.074(5) Uiso 1 d . .
H8 H 0.8256(15) 0.5678(15) 0.9825(13) 0.089 Uiso 1 calc R .
C2,1 C 0.8232(8) 1.1545(7) 0.9394(7) 0.054(4) Uiso 1 d G .
H2,1 H 0.8736(8) 1.0654(7) 0.9554(7) 0.065 Uiso 1 calc R .
C3,1 C 0.8863(7) 1.2349(10) 0.9259(8) 0.079(5) Uiso 1 d G .
H3,1 H 0.9789(7) 1.1995(14) 0.9328(12) 0.095 Uiso 1 calc R .
C4,1 C 0.8110(10) 1.3680(10) 0.9020(8) 0.083(5) Uiso 1 d G .
H4,1 H 0.8532(14) 1.4218(13) 0.8929(12) 0.099 Uiso 1 calc R .
C5,1 C 0.6726(10) 1.4209(7) 0.8916(8) 0.097(6) Uiso 1 d G .
H5,1 H 0.6222(14) 1.5100(8) 0.8756(12) 0.117 Uiso 1 calc R .
C6,1 C 0.6095(7) 1.3406(9) 0.9051(8) 0.084(5) Uiso 1 d G .
H6,1 H 0.5169(7) 1.3760(13) 0.8981(12) 0.101 Uiso 1 calc R .
C1,1 C 0.6848(8) 1.2074(8) 0.9290(7) 0.031(3) Uiso 1 d G .
C2,2 C 0.4230(10) 0.7661(10) 0.8045(7) 0.071(5) Uiso 1 d G .
H2,2 H 0.4489(10) 0.7550(10) 0.8713(7) 0.086 Uiso 1 calc R .
C3,2 C 0.3198(10) 0.7368(10) 0.7919(8) 0.084(5) Uiso 1 d G .
H3,2 H 0.2766(14) 0.7060(14) 0.8502(11) 0.101 Uiso 1 calc R .
C4,2 C 0.2811(9) 0.7534(11) 0.6920(11) 0.102(6) Uiso 1 d G .
H4,2 H 0.2120(12) 0.7338(15) 0.6836(15) 0.122 Uiso 1 calc R .
C5,2 C 0.3457(12) 0.7994(12) 0.6048(8) 0.126(7) Uiso 1 d G .
H5,2 H 0.3198(17) 0.8106(17) 0.5380(9) 0.152 Uiso 1 calc R .
C6,2 C 0.4489(11) 0.8288(10) 0.6174(7) 0.099(6) Uiso 1 d G .
H6,2 H 0.4921(15) 0.8595(14) 0.5590(9) 0.119 Uiso 1 calc R .
C1,2 C 0.4876(8) 0.8121(9) 0.7172(9) 0.049(4) Uiso 1 d G .
C2,3 C 1.0485(10) 1.0340(9) 0.7777(6) 0.077(5) Uiso 1 d G .
H2,3 H 1.0369(10) 0.9905(9) 0.8491(6) 0.092 Uiso 1 calc R .
C3,3 C 1.1339(9) 1.0950(10) 0.7529(8) 0.084(5) Uiso 1 d G .
H3,3 H 1.1794(13) 1.0924(15) 0.8076(10) 0.100 Uiso 1 calc R .
C4,3 C 1.1512(9) 1.1601(9) 0.6462(9) 0.082(5) Uiso 1 d G .
H4,3 H 1.2083(12) 1.2009(13) 0.6296(13) 0.098 Uiso 1 calc R .
C5,3 C 1.0831(10) 1.1640(9) 0.5645(6) 0.079(5) Uiso 1 d G .
H5,3 H 1.0946(14) 1.2075(13) 0.4931(7) 0.095 Uiso 1 calc R .
C6,3 C 0.9977(9) 1.1029(10) 0.5894(7) 0.073(5) Uiso 1 d G .
H6,3 H 0.9521(13) 1.1055(14) 0.5347(9) 0.088 Uiso 1 calc R .
C1,3 C 0.9804(8) 1.0379(9) 0.6960(8) 0.052(4) Uiso 1 d G .
O7 O 0.3643(20) 0.3680(20) 0.5535(17) 0.193(8) Uiso 1 d . .
C9 C 0.2876(45) 0.4708(45) 0.4731(37) 0.241(18) Uiso 1 d . .
C10 C 0.2110(35) 0.4469(33) 0.4069(29) 0.238(15) Uiso 1 d . .
C11 C 0.3248(47) 0.5636(50) 0.4104(40) 0.343(26) 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
Cu1 0.0442(12) 0.0259(10) 0.0364(12) -0.0136(9) 0.0014(9) -0.0105(8)
P1 0.037(2) 0.032(2) 0.040(3) -0.016(2) 0.005(2) -0.013(2)
P2 0.052(3) 0.039(2) 0.043(3) -0.022(2) 0.002(2) -0.020(2)
P3 0.044(3) 0.046(3) 0.064(3) -0.028(3) 0.008(2) -0.013(2)
O1 0.049(6) 0.027(5) 0.045(6) -0.011(5) -0.003(5) -0.011(5)
O2 0.053(6) 0.058(6) 0.054(6) -0.035(5) 0.026(5) -0.034(5)
O3 0.050(6) 0.026(5) 0.046(7) -0.017(5) -0.001(5) -0.009(5)
O4 0.089(8) 0.094(8) 0.040(6) -0.051(6) 0.032(6) -0.058(6)
O5 0.048(6) 0.040(6) 0.055(7) -0.011(6) -0.004(5) -0.009(5)
O6 0.070(7) 0.082(8) 0.075(8) -0.054(7) 0.021(6) -0.030(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
Cu1 O3 1.982(8) . ?
Cu1 O1 1.979(8) . ?
Cu1 N2 1.983(10) . ?
Cu1 N1 2.093(10) . ?
Cu1 O2 2.336(9) 2_677 ?
Cu1 O5 2.450(9) . ?
P1 O2 1.487(8) . ?
P1 O1 1.511(8) . ?
P1 C1,1 1.795(7) . ?
P1 C1 1.858(12) . ?
P2 O4 1.516(9) . ?
P2 O3 1.515(9) . ?
P2 C1,2 1.765(8) . ?
P2 C2 1.813(11) . ?
P3 O5 1.466(9) . ?
P3 O6 1.562(10) . ?
P3 C1,3 1.779(8) . ?
P3 C3 1.836(12) . ?
O2 Cu1 2.336(8) 2_677 ?
N1 C2 1.434(14) . ?
N1 C1 1.508(14) . ?
N1 C3 1.538(14) . ?
N2 C4 1.30(2) . ?
N2 C8 1.36(2) . ?
C4 C5 1.39(2) . ?
C5 C6 1.33(2) . ?
C6 C7 1.28(2) . ?
C7 C8 1.42(2) . ?
C2,1 C3,1 1.39 . ?
C2,1 C1,1 1.39 . ?
C3,1 C4,1 1.39 . ?
C4,1 C5,1 1.39 . ?
C5,1 C6,1 1.39 . ?
C6,1 C1,1 1.39 . ?
C2,2 C3,2 1.39 . ?
C2,2 C1,2 1.39 . ?
C3,2 C4,2 1.39 . ?
C4,2 C5,2 1.39 . ?
C5,2 C6,2 1.39 . ?
C6,2 C1,2 1.39 . ?
C2,3 C3,3 1.39 . ?
C2,3 C1,3 1.39 . ?
C3,3 C4,3 1.39 . ?
C4,3 C5,3 1.39 . ?
C5,3 C6,3 1.39 . ?
C6,3 C1,3 1.39 . ?
O7 C9 1.26(4) . ?
C9 C11 1.31(5) . ?
C9 C10 1.50(5) . ?

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
O3 Cu1 O1 173.8(4) . . ?
O3 Cu1 N2 92.9(4) . . ?
O1 Cu1 N2 93.2(4) . . ?
O3 Cu1 N1 87.0(4) . . ?
O1 Cu1 N1 86.9(4) . . ?
N2 Cu1 N1 178.9(4) . . ?
O3 Cu1 O2 87.0(3) . 2_677 ?
O1 Cu1 O2 92.0(3) . 2_677 ?
N2 Cu1 O2 93.4(4) . 2_677 ?
N1 Cu1 O2 87.7(3) . 2_677 ?
O3 Cu1 O5 87.6(3) . . ?
O1 Cu1 O5 92.6(3) . . ?
N2 Cu1 O5 94.2(4) . . ?
N1 Cu1 O5 84.8(3) . . ?
O2 Cu1 O5 170.9(3) 2_677 . ?
O2 P1 O1 118.1(5) . . ?
O2 P1 C1,1 107.8(5) . . ?
O1 P1 C1,1 107.9(5) . . ?
O2 P1 C1 109.4(5) . . ?
O1 P1 C1 104.0(5) . . ?
C1,1 P1 C1 109.4(5) . . ?
O4 P2 O3 116.1(5) . . ?
O4 P2 C1,2 109.2(5) . . ?
O3 P2 C1,2 110.0(5) . . ?
O4 P2 C2 111.1(6) . . ?
O3 P2 C2 103.6(5) . . ?
C1,2 P2 C2 106.3(5) . . ?
O5 P3 O6 119.4(6) . . ?
O5 P3 C1,3 111.8(5) . . ?
O6 P3 C1,3 103.7(5) . . ?
O5 P3 C3 108.0(6) . . ?
O6 P3 C3 108.3(6) . . ?
C1,3 P3 C3 104.6(5) . . ?
P1 O1 Cu1 117.7(5) . . ?
P1 O2 Cu1 147.3(5) . 2_677 ?
P2 O3 Cu1 118.1(4) . . ?
P3 O5 Cu1 108.0(5) . . ?
C2 N1 C1 111.6(9) . . ?
C2 N1 C3 111.4(10) . . ?
C1 N1 C3 106.4(9) . . ?
C2 N1 Cu1 108.9(7) . . ?
C1 N1 Cu1 106.2(7) . . ?
C3 N1 Cu1 112.2(7) . . ?
N1 C1 P1 111.1(8) . . ?
N1 C2 P2 111.7(8) . . ?
N1 C3 P3 113.4(8) . . ?
C4 N2 C8 118.1(12) . . ?
C4 N2 Cu1 123.5(10) . . ?
C8 N2 Cu1 118.4(10) . . ?
N2 C4 C5 122.7(14) . . ?
C6 C5 C4 119.4(16) . . ?
C7 C6 C5 118.9(17) . . ?
C6 C7 C8 122.9(17) . . ?
N2 C8 C7 117.5(15) . . ?
C3,1 C2,1 C1,1 120.0 . . ?
C2,1 C3,1 C4,1 120.0 . . ?
C5,1 C4,1 C3,1 120.0 . . ?
C4,1 C5,1 C6,1 120.0 . . ?
C1,1 C6,1 C5,1 120.0 . . ?
C6,1 C1,1 C2,1 120.0 . . ?
C6,1 C1,1 P1 120.2(5) . . ?
C2,1 C1,1 P1 119.6(5) . . ?
C3,2 C2,2 C1,2 120.0 . . ?
C4,2 C3,2 C2,2 120.0 . . ?
C3,2 C4,2 C5,2 120.0 . . ?
C4,2 C5,2 C6,2 120.0 . . ?
C1,2 C6,2 C5,2 120.0 . . ?
C6,2 C1,2 C2,2 120.0 . . ?
C6,2 C1,2 P2 118.7(7) . . ?
C2,2 C1,2 P2 121.2(7) . . ?
C3,3 C2,3 C1,3 120.0 . . ?
C4,3 C3,3 C2,3 120.0 . . ?
C3,3 C4,3 C5,3 120.0 . . ?
C4,3 C5,3 C6,3 120.0 . . ?
C1,3 C6,3 C5,3 120.0 . . ?
C6,3 C1,3 C2,3 120.0 . . ?
C6,3 C1,3 P3 123.4(6) . . ?
C2,3 C1,3 P3 116.7(7) . . ?
O7 C9 C11 121.4(50) . . ?
O7 C9 C10 115.0(41) . . ?
C11 C9 C10 110.3(45) . . ?

_refine_diff_density_max    0.516
_refine_diff_density_min   -0.385
_refine_diff_density_rms    0.094

data_coppermonomer

_audit_creation_method            SHELXL
_chemical_name_systematic
;
 (Nitrilo-tris(methylenephosphonate)copper(II)(water),Pyridonium
;
_chemical_name_common             ?
_chemical_formula_moiety          ?
_chemical_formula_structural      ?
_chemical_formula_analytical      ?
_chemical_formula_sum             'C8 H17 Cu N2 O10 P3'
_chemical_formula_weight          457.69
_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'
 'O'  'O'   0.0106   0.0060
 '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'
 'Cu'  'Cu'   0.3201   1.2651
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting            orthorhombic
_symmetry_space_group_name_H-M    Pcab

loop_
 _symmetry_equiv_pos_as_xyz
 'x, y, z'
 '-x, -y+1/2, z+1/2'
 'x+1/2, -y, -z+1/2'
 '-x+1/2, y+1/2, -z'
 '-x, -y, -z'
 'x, y-1/2, -z-1/2'
 '-x-1/2, y, z-1/2'
 'x-1/2, -y-1/2, z'

_cell_length_a                    10.982(5)
_cell_length_b                    15.846(9)
_cell_length_c                    18.236(6)
_cell_angle_alpha                 90.00(4)
_cell_angle_beta                  90.00(4)
_cell_angle_gamma                 90.00(4)
_cell_volume                      3173.4(25)
_cell_formula_units_Z             8
_cell_measurement_temperature     293(2)
_cell_measurement_reflns_used     ?
_cell_measurement_theta_min       ?
_cell_measurement_theta_max       ?

_exptl_crystal_description        parallelepiped
_exptl_crystal_colour             'pale blue'
_exptl_crystal_size_max           0.275
_exptl_crystal_size_mid           ?
_exptl_crystal_size_min           0.10
_exptl_crystal_density_meas       ?
_exptl_crystal_density_diffrn     1.916
_exptl_crystal_density_method     ?
_exptl_crystal_F_000              1864
_exptl_absorpt_coefficient_mu     1.734
_exptl_absorpt_correction_type    ?
_exptl_absorpt_correction_T_min   ?
_exptl_absorpt_correction_T_max   ?

_exptl_special_details
;
 ?
;

_diffrn_ambient_temperature       293(2)
_diffrn_radiation_wavelength      0.71070
_diffrn_radiation_type            MoK\a
_diffrn_radiation_source          'fine-focus sealed tube'
_diffrn_radiation_monochromator   graphite
_diffrn_measurement_device        'enraf nonius cad4'
_diffrn_measurement_method        omega-2theta
_diffrn_standards_number          3
_diffrn_standards_interval_count  ?
_diffrn_standards_interval_time   120
_diffrn_standards_decay_%         ?
_diffrn_reflns_number             1941
_diffrn_reflns_av_R_equivalents   0.0000
_diffrn_reflns_av_sigmaI/netI     0.0922
_diffrn_reflns_limit_h_min        0
_diffrn_reflns_limit_h_max        11
_diffrn_reflns_limit_k_min        0
_diffrn_reflns_limit_k_max        16
_diffrn_reflns_limit_l_min        0
_diffrn_reflns_limit_l_max        18
_diffrn_reflns_theta_min          2.52
_diffrn_reflns_theta_max          21.97
_reflns_number_total              1941
_reflns_number_observed           1275
_reflns_observed_criterion        >2sigma(I)

_computing_data_collection        ?
_computing_cell_refinement        ?
_computing_data_reduction         ?
_computing_structure_solution     'SIR-92'
_computing_structure_refinement   'SHELXL-93 (Sheldrick, 1993)'
_computing_molecular_graphics     'ORTEP (Johnson,1976; Zsolnai, 1994)'
_computing_publication_material   ?

_refine_special_details
;
 Refinement on F^2^ for ALL reflections except for 0 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^)+(0.0540P)^2^+12.7661P] 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     ?
_refine_ls_extinction_method      none
_refine_ls_extinction_coef        ?
_refine_ls_number_reflns          1941
_refine_ls_number_parameters      160
_refine_ls_number_restraints      0
_refine_ls_R_factor_all           0.1159
_refine_ls_R_factor_obs           0.0509
_refine_ls_wR_factor_all          0.1313
_refine_ls_wR_factor_obs          0.1097
_refine_ls_goodness_of_fit_all    1.026
_refine_ls_goodness_of_fit_obs    1.082
_refine_ls_restrained_S_all       1.026
_refine_ls_restrained_S_obs       1.082
_refine_ls_shift/esd_max          -.805
_refine_ls_shift/esd_mean         0.244

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 0.14854(9) 0.10023(6) 0.11839(6) 0.0208(3) Uani 1 d . .
P1 P 0.2980(2) 0.04118(14) -0.01236(12) 0.0211(6) Uani 1 d . .
P2 P 0.2886(2) 0.02251(14) 0.23715(12) 0.0228(6) Uani 1 d . .
P3 P 0.2329(2) 0.27772(13) 0.10875(13) 0.0204(6) Uani 1 d . .
N N 0.3350(6) 0.1211(4) 0.1195(3) 0.018(2) Uani 1 d . .
O1 O 0.1651(5) 0.0546(4) 0.0074(3) 0.0257(15) Uani 1 d . .
O2 O 0.3382(5) -0.0488(3) 0.0143(3) 0.029(2) Uani 1 d . .
O3 O 0.3308(6) 0.0560(4) -0.0901(3) 0.038(2) Uani 1 d . .
O4 O 0.1683(5) 0.0197(4) 0.1968(3) 0.034(2) Uani 1 d . .
O5 O 0.2884(6) 0.0909(4) 0.2979(3) 0.036(2) Uani 1 d . .
O6 O 0.3284(5) -0.0611(4) 0.2668(3) 0.031(2) Uani 1 d . .
O7 O 0.1305(5) 0.2196(3) 0.0856(3) 0.0259(15) Uani 1 d . .
O8 O 0.1842(5) 0.3326(4) 0.1735(3) 0.029(2) Uani 1 d . .
O9 O 0.2871(5) 0.3306(4) 0.0494(3) 0.028(2) Uani 1 d . .
OW O -0.0256(5) 0.0786(4) 0.1185(3) 0.034(2) Uani 1 d . .
C1 C 0.3836(8) 0.1144(5) 0.0429(4) 0.019(2) Uiso 1 d . .
H11 H 0.4679(8) 0.0962(5) 0.0448(4) 0.023 Uiso 1 calc R .
H22 H 0.3815(8) 0.1696(5) 0.0200(4) 0.023 Uiso 1 calc R .
C2 C 0.3936(8) 0.0586(5) 0.1693(5) 0.022(2) Uiso 1 d . .
H21 H 0.4633(8) 0.0843(5) 0.1931(5) 0.026 Uiso 1 calc R .
H22 H 0.4226(8) 0.0109(5) 0.1408(5) 0.026 Uiso 1 calc R .
C3 C 0.3484(8) 0.2082(5) 0.1487(4) 0.019(2) Uiso 1 d . .
H31 H 0.4289(8) 0.2295(5) 0.1371(4) 0.023 Uiso 1 calc R .
H32 H 0.3398(8) 0.2075(5) 0.2016(4) 0.023 Uiso 1 calc R .
C4 C -0.0535(6) 0.6347(3) 0.6070(4) 0.047(3) Uiso 1 d G .
H4 H -0.0828(6) 0.5809(3) 0.5967(4) 0.056 Uiso 1 calc R .
C5 C -0.1115(5) 0.6845(4) 0.6591(4) 0.066(4) Uiso 1 d G .
H5 H -0.1797(7) 0.6641(6) 0.6836(5) 0.079 Uiso 1 calc R .
C6 C -0.0676(6) 0.7648(4) 0.6746(4) 0.059(3) Uiso 1 d G .
H6 H -0.1064(9) 0.7982(6) 0.7095(5) 0.071 Uiso 1 calc R .
C7 C 0.0343(7) 0.7953(3) 0.6380(4) 0.062(4) Uiso 1 d G .
H7 H 0.0637(9) 0.8491(4) 0.6483(6) 0.074 Uiso 1 calc R .
C8 C 0.0924(5) 0.7455(4) 0.5859(3) 0.051(3) Uiso 1 d G .
H8 H 0.1605(7) 0.7659(6) 0.5614(5) 0.062 Uiso 1 calc R .
N1 N 0.0485(6) 0.6652(4) 0.5704(3) 0.041(2) Uiso 1 d G .

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 0.0186(6) 0.0221(6) 0.0218(6) 0.0028(5) -0.0014(5) -0.0005(5)
P1 0.0245(14) 0.0227(13) 0.0163(12) -0.0037(11) -0.0022(11) 0.0017(11)
P2 0.0232(14) 0.0250(14) 0.0201(14) 0.0073(11) -0.0023(11) -0.0017(12)
P3 0.0227(13) 0.0147(12) 0.0238(13) -0.0014(10) -0.0019(12) -0.0006(11)
N 0.022(4) 0.018(4) 0.012(4) 0.001(3) 0.002(3) 0.004(3)
O1 0.025(4) 0.027(3) 0.025(3) -0.006(3) -0.006(3) 0.005(3)
O2 0.035(4) 0.021(3) 0.032(4) -0.003(3) -0.006(3) 0.009(3)
O3 0.044(4) 0.052(4) 0.017(3) 0.000(3) 0.002(3) -0.006(4)
O4 0.023(4) 0.037(4) 0.041(4) 0.020(3) -0.007(3) -0.008(3)
O5 0.053(5) 0.025(4) 0.030(4) -0.005(3) 0.004(3) -0.008(3)
O6 0.036(4) 0.026(3) 0.031(4) 0.014(3) -0.001(3) 0.001(3)
O7 0.024(3) 0.014(3) 0.039(4) -0.002(3) -0.009(3) 0.003(3)
O8 0.028(4) 0.029(4) 0.031(4) -0.011(3) 0.010(3) 0.003(3)
O9 0.033(4) 0.020(3) 0.031(4) 0.008(3) 0.002(3) -0.001(3)
OW 0.020(3) 0.044(4) 0.037(4) 0.013(4) 0.002(3) -0.004(3)

_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 O4 1.928(6) . ?
Cu OW 1.943(6) . ?
Cu O7 1.994(6) . ?
Cu N 2.074(7) . ?
Cu O1 2.156(6) . ?
P1 O3 1.481(6) . ?
P1 O1 1.519(6) . ?
P1 O2 1.570(6) . ?
P1 C1 1.802(8) . ?
P2 O6 1.497(6) . ?
P2 O4 1.513(6) . ?
P2 O5 1.551(6) . ?
P2 C2 1.786(8) . ?
P3 O9 1.493(6) . ?
P3 O7 1.515(6) . ?
P3 O8 1.560(6) . ?
P3 C3 1.831(8) . ?
N C3 1.487(10) . ?
N C2 1.490(10) . ?
N C1 1.500(10) . ?
C4 C5 1.39 . ?
C4 N1 1.39 . ?
C5 C6 1.39 . ?
C6 C7 1.39 . ?
C7 C8 1.39 . ?
C8 N1 1.39 . ?

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
O4 Cu OW 89.6(3) . . ?
O4 Cu O7 149.5(3) . . ?
OW Cu O7 94.0(3) . . ?
O4 Cu N 89.3(2) . . ?
OW Cu N 178.9(3) . . ?
O7 Cu N 87.1(2) . . ?
O4 Cu O1 117.7(3) . . ?
OW Cu O1 91.4(2) . . ?
O7 Cu O1 92.5(2) . . ?
N Cu O1 88.8(2) . . ?
O3 P1 O1 116.0(4) . . ?
O3 P1 O2 111.9(4) . . ?
O1 P1 O2 108.9(3) . . ?
O3 P1 C1 107.8(4) . . ?
O1 P1 C1 106.2(4) . . ?
O2 P1 C1 105.3(4) . . ?
O6 P2 O4 113.9(4) . . ?
O6 P2 O5 111.2(4) . . ?
O4 P2 O5 111.6(4) . . ?
O6 P2 C2 110.2(4) . . ?
O4 P2 C2 103.7(4) . . ?
O5 P2 C2 105.8(4) . . ?
O9 P3 O7 115.8(3) . . ?
O9 P3 O8 111.9(3) . . ?
O7 P3 O8 107.2(3) . . ?
O9 P3 C3 110.5(4) . . ?
O7 P3 C3 105.1(3) . . ?
O8 P3 C3 105.8(4) . . ?
C3 N C2 110.9(6) . . ?
C3 N C1 111.3(6) . . ?
C2 N C1 111.4(6) . . ?
C3 N Cu 104.5(5) . . ?
C2 N Cu 109.1(5) . . ?
C1 N Cu 109.3(5) . . ?
P1 O1 Cu 110.6(3) . . ?
P2 O4 Cu 116.1(3) . . ?
P3 O7 Cu 114.8(3) . . ?
N C1 P1 112.4(5) . . ?
N C2 P2 110.8(6) . . ?
N C3 P3 110.3(5) . . ?
C5 C4 N1 120.0 . . ?
C6 C5 C4 120.0 . . ?
C5 C6 C7 120.0 . . ?
C8 C7 C6 120.0 . . ?
C7 C8 N1 120.0 . . ?
C8 N1 C4 120.0 . . ?

_refine_diff_density_max    0.671
_refine_diff_density_min   -0.588
_refine_diff_density_rms    0.116