# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2010


data_global

_journal_coden_Cambridge         222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

loop_
_publ_author_name
'Zheng, Li-Min'

_publ_contact_author_name        'Zheng, Li-Min'
_publ_contact_author_email       lmzheng@netra.nju.edu.cn

_publ_section_title              
;
Zn3(4-OOCC6H4PO3)2\"i A polar metal
phosphonate with pillared layered structure showing
SHG-activity and large dielectric anisotropy
;

# Attachment '- Zn.cif'

data_1
_database_code_depnum_ccdc_archive 'CCDC 781095'
#TrackingRef '- Zn.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H8 O10 P2 Zn3 '
_chemical_formula_sum            'C14 H8 O10 P2 Zn3'
_chemical_formula_weight         594.25

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'
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'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pca21
_symmetry_space_group_name_Hall  P2c-2ac

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

_cell_length_a                   10.2807(12)
_cell_length_b                   8.6012(10)
_cell_length_c                   18.634(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1647.7(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    2283
_cell_measurement_theta_min      3.09
_cell_measurement_theta_max      26.81

_exptl_crystal_description       cubic
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.395
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1168
_exptl_absorpt_coefficient_mu    4.586
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.261
_exptl_absorpt_correction_T_max  0.405
_exptl_absorpt_process_details   '(SADABS, Bruker, 2000)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      273(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_type  'Bruker Smart Apex CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8311
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_av_sigmaI/netI    0.0687
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.19
_diffrn_reflns_theta_max         25.99
_reflns_number_total             3062
_reflns_number_gt                2771
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SMART (Bruker, 2000)'
_computing_cell_refinement       SMART
_computing_data_reduction        'SAINT (Bruker, 2000)'
_computing_structure_solution    'SHELXTL (Bruker, 2000)'
_computing_structure_refinement  SHELXTL
_computing_molecular_graphics    SHELXTL
_computing_publication_material  SHELXTL

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness 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 threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) 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
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0100P)^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    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.058(14)
_refine_ls_number_reflns         3062
_refine_ls_number_parameters     262
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0338
_refine_ls_wR_factor_ref         0.0576
_refine_ls_wR_factor_gt          0.0570
_refine_ls_goodness_of_fit_ref   0.971
_refine_ls_restrained_S_all      0.971
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_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_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
Zn1 Zn 0.87769(7) 1.32017(8) 0.60037(3) 0.01846(18) Uani 1 1 d . . .
Zn2 Zn 0.63833(6) 0.85888(7) 0.57733(3) 0.01676(16) Uani 1 1 d . . .
Zn3 Zn 1.03307(7) 0.69438(7) 0.56020(3) 0.01659(16) Uani 1 1 d . . .
P1 P 0.87853(16) 1.01318(18) 0.50623(8) 0.0149(3) Uani 1 1 d . . .
P2 P 0.73965(16) 0.53790(17) 1.01096(8) 0.0147(3) Uani 1 1 d . . .
O1 O 0.6495(5) 0.8190(5) 0.6797(2) 0.0291(12) Uani 1 1 d . . .
O2 O 0.5103(4) 0.6229(5) 0.6741(2) 0.0285(11) Uani 1 1 d . . .
O3 O 0.6094(4) 0.5325(4) 1.05302(18) 0.0164(9) Uani 1 1 d . . .
O4 O 0.7964(4) 0.3742(4) 1.02220(19) 0.0171(10) Uani 1 1 d . . .
O5 O 0.8316(4) 0.6598(4) 1.0343(2) 0.0239(11) Uani 1 1 d . . .
O6 O 0.9501(4) 1.2193(5) 0.1571(2) 0.0310(12) Uani 1 1 d . . .
O7 O 0.7440(5) 1.2716(6) 0.1757(2) 0.0491(15) Uani 1 1 d . . .
O8 O 0.7405(4) 1.0135(4) 0.53439(19) 0.0204(10) Uani 1 1 d . . .
O9 O 0.9532(4) 1.1402(4) 0.54940(18) 0.0150(9) Uani 1 1 d . . .
O10 O 0.9508(4) 0.8621(4) 0.5083(2) 0.0198(10) Uani 1 1 d . . .
C1 C 0.5941(6) 0.7018(7) 0.7046(3) 0.0219(15) Uani 1 1 d . . .
C2 C 0.6324(6) 0.6534(7) 0.7797(3) 0.0188(14) Uani 1 1 d . . .
C3 C 0.5571(7) 0.5497(7) 0.8171(3) 0.0239(16) Uani 1 1 d . . .
H3 H 0.4840 0.5056 0.7959 0.029 Uiso 1 1 calc R . .
C4 C 0.5912(6) 0.5113(7) 0.8871(3) 0.0234(16) Uani 1 1 d . . .
H4 H 0.5405 0.4410 0.9126 0.028 Uiso 1 1 calc R . .
C5 C 0.6991(6) 0.5760(6) 0.9190(3) 0.0141(13) Uani 1 1 d . . .
C6 C 0.7732(7) 0.6801(7) 0.8805(3) 0.0261(17) Uani 1 1 d . . .
H6 H 0.8465 0.7242 0.9015 0.031 Uiso 1 1 calc R . .
C7 C 0.7397(8) 0.7196(8) 0.8109(3) 0.0299(17) Uani 1 1 d . . .
H7 H 0.7897 0.7908 0.7855 0.036 Uiso 1 1 calc R . .
C8 C 0.8501(7) 1.2219(7) 0.1945(3) 0.0229(15) Uani 1 1 d . . .
C9 C 0.8595(7) 1.1640(7) 0.2705(3) 0.0184(14) Uani 1 1 d . . .
C10 C 0.7606(7) 1.2019(6) 0.3176(3) 0.0199(14) Uani 1 1 d . . .
H10 H 0.6886 1.2566 0.3010 0.024 Uiso 1 1 calc R . .
C11 C 0.7674(6) 1.1593(6) 0.3894(3) 0.0185(14) Uani 1 1 d . . .
H11 H 0.7019 1.1891 0.4209 0.022 Uiso 1 1 calc R . .
C12 C 0.8713(6) 1.0728(6) 0.4139(3) 0.0154(13) Uani 1 1 d . . .
C13 C 0.9673(6) 1.0326(8) 0.3660(3) 0.0229(15) Uani 1 1 d . . .
H13 H 1.0375 0.9737 0.3818 0.027 Uiso 1 1 calc R . .
C14 C 0.9617(7) 1.0779(7) 0.2942(3) 0.0237(16) Uani 1 1 d . . .
H14 H 1.0277 1.0494 0.2627 0.028 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
Zn1 0.0197(4) 0.0200(4) 0.0156(4) 0.0025(3) 0.0008(3) 0.0035(3)
Zn2 0.0160(3) 0.0186(3) 0.0157(4) 0.0027(3) -0.0001(3) -0.0021(3)
Zn3 0.0158(4) 0.0187(4) 0.0153(4) -0.0018(3) -0.0019(3) 0.0018(3)
P1 0.0150(8) 0.0156(9) 0.0142(8) 0.0015(7) -0.0018(7) -0.0034(7)
P2 0.0148(9) 0.0153(8) 0.0140(8) 0.0012(7) -0.0014(7) -0.0004(7)
O1 0.046(3) 0.032(3) 0.009(2) 0.0066(19) -0.003(2) -0.011(3)
O2 0.033(3) 0.033(3) 0.020(2) 0.006(2) -0.013(2) -0.004(2)
O3 0.019(2) 0.014(2) 0.016(2) 0.0041(16) 0.0030(19) 0.0055(18)
O4 0.016(2) 0.016(2) 0.019(2) 0.0019(17) -0.0067(18) 0.0009(19)
O5 0.024(3) 0.014(2) 0.033(3) 0.0001(18) -0.006(2) -0.002(2)
O6 0.028(3) 0.047(3) 0.018(2) 0.015(2) 0.006(2) 0.001(2)
O7 0.031(3) 0.100(5) 0.017(2) 0.014(3) -0.008(2) 0.019(3)
O8 0.014(2) 0.017(2) 0.030(2) 0.0093(17) 0.0011(19) -0.005(2)
O9 0.010(2) 0.015(2) 0.019(2) -0.0031(18) -0.0041(18) 0.0007(17)
O10 0.023(3) 0.013(2) 0.023(2) 0.0024(18) -0.003(2) 0.004(2)
C1 0.024(4) 0.026(4) 0.016(3) 0.000(3) 0.002(3) 0.008(3)
C2 0.019(4) 0.025(4) 0.012(3) 0.004(3) 0.001(3) 0.000(3)
C3 0.025(4) 0.025(4) 0.022(4) 0.000(3) -0.008(3) -0.002(3)
C4 0.021(4) 0.021(4) 0.028(4) 0.005(3) 0.002(3) -0.010(3)
C5 0.017(3) 0.014(3) 0.012(3) 0.002(2) 0.002(3) 0.003(3)
C6 0.020(4) 0.035(4) 0.024(4) 0.007(3) -0.012(3) -0.007(3)
C7 0.029(4) 0.037(4) 0.024(4) 0.014(3) 0.007(3) -0.006(4)
C8 0.030(4) 0.024(4) 0.015(3) 0.000(3) -0.005(3) -0.001(3)
C9 0.021(4) 0.024(4) 0.010(3) 0.002(3) -0.001(3) 0.001(3)
C10 0.015(3) 0.026(3) 0.019(3) 0.000(3) -0.010(3) 0.003(4)
C11 0.018(4) 0.022(4) 0.015(3) 0.001(3) 0.001(3) 0.002(3)
C12 0.019(3) 0.015(3) 0.012(3) 0.000(2) -0.004(3) -0.002(3)
C13 0.013(3) 0.031(4) 0.025(4) 0.003(3) -0.001(3) 0.005(3)
C14 0.024(4) 0.029(4) 0.018(4) -0.003(3) 0.009(3) -0.001(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
Zn1 O7 1.927(5) 4_655 ?
Zn1 O9 1.975(4) . ?
Zn1 O2 1.998(4) 3_575 ?
Zn1 O3 2.033(3) 4_664 ?
Zn1 O4 2.354(4) 4_664 ?
Zn1 P2 2.7817(17) 4_664 ?
Zn1 Zn2 3.1202(10) 3_575 ?
Zn2 O8 1.874(4) . ?
Zn2 O5 1.916(4) 4_654 ?
Zn2 O1 1.942(4) . ?
Zn2 O9 1.973(4) 3_475 ?
Zn2 Zn1 3.1202(10) 3_475 ?
Zn3 O10 1.932(4) . ?
Zn3 O6 1.959(4) 2_775 ?
Zn3 O4 1.980(4) 2_764 ?
Zn3 O3 2.026(4) 4_654 ?
P1 O10 1.498(4) . ?
P1 O8 1.513(4) . ?
P1 O9 1.559(4) . ?
P1 C12 1.796(6) . ?
P2 O5 1.477(4) . ?
P2 O4 1.538(4) . ?
P2 O3 1.552(4) . ?
P2 C5 1.793(6) . ?
P2 Zn1 2.7817(17) 4_645 ?
O1 C1 1.246(7) . ?
O2 C1 1.234(7) . ?
O2 Zn1 1.998(4) 3_475 ?
O3 Zn3 2.026(4) 4_655 ?
O3 Zn1 2.033(3) 4_645 ?
O4 Zn3 1.980(4) 2_765 ?
O4 Zn1 2.354(4) 4_645 ?
O5 Zn2 1.916(4) 4_655 ?
O6 C8 1.243(7) . ?
O6 Zn3 1.959(4) 2_774 ?
O7 C8 1.223(8) . ?
O7 Zn1 1.927(5) 4_654 ?
O9 Zn2 1.973(4) 3_575 ?
C1 C2 1.514(8) . ?
C2 C3 1.371(8) . ?
C2 C7 1.371(9) . ?
C3 C4 1.389(8) . ?
C3 H3 0.9300 . ?
C4 C5 1.376(8) . ?
C4 H4 0.9300 . ?
C5 C6 1.377(8) . ?
C6 C7 1.384(8) . ?
C6 H6 0.9300 . ?
C7 H7 0.9300 . ?
C8 C9 1.504(8) . ?
C9 C14 1.359(9) . ?
C9 C10 1.382(9) . ?
C10 C11 1.389(7) . ?
C10 H10 0.9300 . ?
C11 C12 1.380(8) . ?
C11 H11 0.9300 . ?
C12 C13 1.375(8) . ?
C13 C14 1.393(8) . ?
C13 H13 0.9300 . ?
C14 H14 0.9300 . ?

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
O7 Zn1 O9 115.84(19) 4_655 . ?
O7 Zn1 O2 89.69(19) 4_655 3_575 ?
O9 Zn1 O2 104.76(17) . 3_575 ?
O7 Zn1 O3 123.6(2) 4_655 4_664 ?
O9 Zn1 O3 118.02(15) . 4_664 ?
O2 Zn1 O3 91.94(16) 3_575 4_664 ?
O7 Zn1 O4 90.03(18) 4_655 4_664 ?
O9 Zn1 O4 98.99(14) . 4_664 ?
O2 Zn1 O4 153.71(15) 3_575 4_664 ?
O3 Zn1 O4 66.64(13) 4_664 4_664 ?
O7 Zn1 P2 107.53(17) 4_655 4_664 ?
O9 Zn1 P2 114.21(11) . 4_664 ?
O2 Zn1 P2 122.90(13) 3_575 4_664 ?
O3 Zn1 P2 33.21(11) 4_664 4_664 ?
O4 Zn1 P2 33.57(10) 4_664 4_664 ?
O7 Zn1 Zn2 123.41(17) 4_655 3_575 ?
O9 Zn1 Zn2 37.76(11) . 3_575 ?
O2 Zn1 Zn2 68.25(13) 3_575 3_575 ?
O3 Zn1 Zn2 109.14(11) 4_664 3_575 ?
O4 Zn1 Zn2 131.71(9) 4_664 3_575 ?
P2 Zn1 Zn2 128.48(4) 4_664 3_575 ?
O8 Zn2 O5 111.42(18) . 4_654 ?
O8 Zn2 O1 120.79(17) . . ?
O5 Zn2 O1 104.13(18) 4_654 . ?
O8 Zn2 O9 115.16(16) . 3_475 ?
O5 Zn2 O9 92.77(17) 4_654 3_475 ?
O1 Zn2 O9 108.46(17) . 3_475 ?
O8 Zn2 Zn1 152.90(12) . 3_475 ?
O5 Zn2 Zn1 75.81(13) 4_654 3_475 ?
O1 Zn2 Zn1 80.11(14) . 3_475 ?
O9 Zn2 Zn1 37.80(10) 3_475 3_475 ?
O10 Zn3 O6 102.53(18) . 2_775 ?
O10 Zn3 O4 115.51(17) . 2_764 ?
O6 Zn3 O4 111.36(18) 2_775 2_764 ?
O10 Zn3 O3 99.42(16) . 4_654 ?
O6 Zn3 O3 112.64(16) 2_775 4_654 ?
O4 Zn3 O3 114.32(16) 2_764 4_654 ?
O10 P1 O8 117.3(2) . . ?
O10 P1 O9 110.5(2) . . ?
O8 P1 O9 106.4(2) . . ?
O10 P1 C12 107.0(3) . . ?
O8 P1 C12 107.0(3) . . ?
O9 P1 C12 108.3(2) . . ?
O5 P2 O4 111.5(2) . . ?
O5 P2 O3 115.2(2) . . ?
O4 P2 O3 103.4(2) . . ?
O5 P2 C5 107.5(3) . . ?
O4 P2 C5 112.7(2) . . ?
O3 P2 C5 106.7(3) . . ?
O5 P2 Zn1 125.42(17) . 4_645 ?
O4 P2 Zn1 57.78(16) . 4_645 ?
O3 P2 Zn1 45.84(13) . 4_645 ?
C5 P2 Zn1 126.5(2) . 4_645 ?
C1 O1 Zn2 118.7(4) . . ?
C1 O2 Zn1 131.1(4) . 3_475 ?
P2 O3 Zn3 129.5(2) . 4_655 ?
P2 O3 Zn1 100.94(19) . 4_645 ?
Zn3 O3 Zn1 129.50(18) 4_655 4_645 ?
P2 O4 Zn3 131.1(2) . 2_765 ?
P2 O4 Zn1 88.65(19) . 4_645 ?
Zn3 O4 Zn1 113.14(16) 2_765 4_645 ?
P2 O5 Zn2 149.4(3) . 4_655 ?
C8 O6 Zn3 125.7(4) . 2_774 ?
C8 O7 Zn1 149.7(5) . 4_654 ?
P1 O8 Zn2 132.2(2) . . ?
P1 O9 Zn2 127.9(2) . 3_575 ?
P1 O9 Zn1 127.1(2) . . ?
Zn2 O9 Zn1 104.44(16) 3_575 . ?
P1 O10 Zn3 151.4(3) . . ?
O2 C1 O1 126.4(6) . . ?
O2 C1 C2 117.1(6) . . ?
O1 C1 C2 116.6(6) . . ?
C3 C2 C7 120.6(5) . . ?
C3 C2 C1 120.2(6) . . ?
C7 C2 C1 119.2(6) . . ?
C2 C3 C4 119.2(6) . . ?
C2 C3 H3 120.4 . . ?
C4 C3 H3 120.4 . . ?
C5 C4 C3 120.9(6) . . ?
C5 C4 H4 119.5 . . ?
C3 C4 H4 119.5 . . ?
C4 C5 C6 118.9(6) . . ?
C4 C5 P2 121.8(4) . . ?
C6 C5 P2 119.2(5) . . ?
C5 C6 C7 120.6(6) . . ?
C5 C6 H6 119.7 . . ?
C7 C6 H6 119.7 . . ?
C2 C7 C6 119.7(6) . . ?
C2 C7 H7 120.1 . . ?
C6 C7 H7 120.1 . . ?
O7 C8 O6 125.7(6) . . ?
O7 C8 C9 116.2(6) . . ?
O6 C8 C9 118.0(6) . . ?
C14 C9 C10 119.4(5) . . ?
C14 C9 C8 122.4(6) . . ?
C10 C9 C8 118.1(6) . . ?
C9 C10 C11 120.8(6) . . ?
C9 C10 H10 119.6 . . ?
C11 C10 H10 119.6 . . ?
C12 C11 C10 120.1(6) . . ?
C12 C11 H11 120.0 . . ?
C10 C11 H11 120.0 . . ?
C11 C12 C13 118.4(6) . . ?
C11 C12 P1 120.2(5) . . ?
C13 C12 P1 121.4(5) . . ?
C12 C13 C14 121.6(6) . . ?
C12 C13 H13 119.2 . . ?
C14 C13 H13 119.2 . . ?
C9 C14 C13 119.7(6) . . ?
C9 C14 H14 120.1 . . ?
C13 C14 H14 120.1 . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        25.99
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.473
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.131