# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2004


data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'Yuan-Gen Yao'
_publ_contact_author_address     
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Research on the Structure of Matter,
the Chinese Academy of Sciences,
Fuzhou, Fujian 350002,
P. R. China
;
_publ_contact_author_email       yyg@fjirsm.ac.cn
_publ_contact_author_phone       86-591-3711523
_publ_contact_author_fax         86-591-3714946
_publ_requested_category         EM
_publ_requested_coeditor_name    ?

# 2. TITLE AND AUTHOR LIST

_publ_section_title              
;
A Novel Ligand-unsupported 3D Framework Polymer of Trimeric Copper (I)
and Its NLO Property
;

loop_
_publ_author_name
_publ_author_address

'Yao Kang'
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China

;
'Yuan-Gen Yao'
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China
;
'Ye-Yan Qin'
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China
;
'Jian Zhang'
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China
;
'Yu-Biao Chen'
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China
;
;
Zhao-Ji Li
;
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China
;
'Yi-Hang Wen'
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China
;
'Jian-Kai Cheng'
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China
;
'Rui-Feng Hu'
;
The State Key Laboratory of Structural Chemistry,
Fujian Institute of Reserch on the Structure of Matter,
Chinese Academy of Sciences
Fuzhou, Fujian 350002,
P.R.China
;

data_compound_1
_database_code_depnum_ccdc_archive 'CCDC 230029'
_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C13 H8 Cu3 N3 O4'
_chemical_formula_weight         460.84

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'
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   Pca2(1)

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                   13.7541(4)
_cell_length_b                   7.2352(3)
_cell_length_c                   14.7958(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1472.38(10)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       rectangle
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.16
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.079
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             904
_exptl_absorpt_coefficient_mu    4.315
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      293(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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         none
_diffrn_standards_interval_count none
_diffrn_standards_interval_time  none
_diffrn_standards_decay_%        none
_diffrn_reflns_number            4065
_diffrn_reflns_av_R_equivalents  0.0314
_diffrn_reflns_av_sigmaI/netI    0.0379
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         2.75
_diffrn_reflns_theta_max         25.00
_reflns_number_total             1815
_reflns_number_gt                1590
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Siemens SMART'
_computing_cell_refinement       'Siemens SMART & SAINT'
_computing_data_reduction        'Siemens XPREP'
_computing_structure_solution    'Siemens SHELXTL'
_computing_structure_refinement  'Siemens SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker 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^)+(0.0487P)^2^+2.7063P] 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    mixed
_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   0.21(4)
_refine_ls_number_reflns         1815
_refine_ls_number_parameters     211
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0352
_refine_ls_wR_factor_ref         0.0906
_refine_ls_wR_factor_gt          0.0826
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_restrained_S_all      1.016
_refine_ls_shift/su_max          0.178
_refine_ls_shift/su_mean         0.002

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
Cu2 Cu 0.44733(6) 0.28424(15) 0.46851(7) 0.0383(3) Uani 1 1 d . . .
Cu1 Cu 0.57233(7) 0.46716(14) 0.34958(6) 0.0389(3) Uani 1 1 d . . .
Cu3 Cu 0.39015(9) -0.06430(15) 0.50562(9) 0.0574(4) Uani 1 1 d . . .
N1 N 0.6720(4) 0.4235(9) 0.2545(4) 0.0287(14) Uani 1 1 d . . .
O4 O 0.3561(3) 0.2311(8) 0.3791(4) 0.0402(14) Uani 1 1 d . . .
C4 C 0.8332(5) 0.3390(10) 0.2064(5) 0.0280(16) Uani 1 1 d . . .
H4A H 0.8959 0.3023 0.2214 0.034 Uiso 1 1 calc R . .
C7 C 0.3191(5) 0.1632(12) 0.2271(6) 0.0345(19) Uani 1 1 d . . .
C12 C 0.3896(5) 0.2234(11) 0.2995(6) 0.0321(18) Uani 1 1 d . . .
C1 C 0.6479(5) 0.4493(11) 0.1679(6) 0.0327(18) Uani 1 1 d . . .
H1A H 0.5850 0.4881 0.1546 0.039 Uiso 1 1 calc R . .
C5 C 0.7640(5) 0.3678(11) 0.2732(5) 0.0312(17) Uani 1 1 d . . .
H5A H 0.7814 0.3481 0.3332 0.037 Uiso 1 1 calc R . .
O3 O 0.4750(4) 0.2611(8) 0.2770(4) 0.0447(16) Uani 1 1 d . . .
C3 C 0.8066(5) 0.3664(11) 0.1157(5) 0.0268(16) Uani 1 1 d . . .
C2 C 0.7119(5) 0.4210(11) 0.0972(5) 0.0284(17) Uani 1 1 d . . .
H2A H 0.6916 0.4383 0.0378 0.034 Uiso 1 1 calc R . .
C11 C 0.2249(5) 0.1086(11) 0.2493(6) 0.040(2) Uani 1 1 d . . .
H11A H 0.2034 0.1102 0.3089 0.048 Uiso 1 1 calc R . .
C13 C 0.4643(6) -0.2182(12) 0.4369(5) 0.046(2) Uani 0.494(4) 1 d P . .
N3 N 0.4643(6) -0.2182(12) 0.4369(5) 0.046(2) Uani 0.506(4) 1 d P . .
C14 C 0.5051(6) 0.6657(13) 0.4013(6) 0.053(2) Uani 0.506(4) 1 d P . .
N4 N 0.5051(6) 0.6657(13) 0.4013(6) 0.053(2) Uani 0.494(4) 1 d P . .
C8 C 0.3453(6) 0.1630(11) 0.1372(6) 0.0402(19) Uani 1 1 d . . .
H8A H 0.4068 0.2037 0.1204 0.048 Uiso 1 1 calc R . .
N2 N 0.1907(5) 0.0475(10) 0.0930(6) 0.0456(19) Uani 1 1 d . . .
C9 C 0.2814(7) 0.1032(13) 0.0722(7) 0.050(2) Uani 1 1 d . . .
H9A H 0.3013 0.1011 0.0121 0.060 Uiso 1 1 calc R . .
C10 C 0.1641(6) 0.0518(12) 0.1799(7) 0.044(2) Uani 1 1 d . . .
H10A H 0.1013 0.0146 0.1946 0.053 Uiso 1 1 calc R . .
O1 O 0.8457(4) 0.3279(9) -0.0391(4) 0.0438(15) Uani 1 1 d . . .
O2 O 0.9662(3) 0.3150(8) 0.0636(4) 0.0400(15) Uani 1 1 d . . .
C6 C 0.8769(5) 0.3335(11) 0.0409(5) 0.0334(18) Uani 1 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
Cu2 0.0323(4) 0.0561(6) 0.0266(5) -0.0029(5) -0.0071(4) -0.0064(4)
Cu1 0.0396(5) 0.0460(6) 0.0312(5) -0.0068(5) 0.0081(5) 0.0106(4)
Cu3 0.0647(7) 0.0455(6) 0.0621(8) -0.0168(7) 0.0358(6) 0.0062(5)
N1 0.029(3) 0.028(3) 0.028(3) 0.001(3) 0.003(3) 0.003(3)
O4 0.031(3) 0.063(4) 0.027(3) -0.003(3) -0.007(2) -0.008(3)
C4 0.027(4) 0.030(4) 0.027(4) 0.002(3) 0.002(3) 0.001(3)
C7 0.035(4) 0.030(4) 0.039(5) -0.006(4) -0.010(4) 0.000(3)
C12 0.031(4) 0.030(4) 0.035(5) -0.004(4) -0.010(4) 0.003(3)
C1 0.026(3) 0.041(5) 0.031(4) 0.002(4) -0.005(3) 0.010(3)
C5 0.027(3) 0.044(4) 0.022(4) -0.002(4) -0.002(3) 0.007(4)
O3 0.032(3) 0.060(4) 0.042(3) -0.016(3) -0.004(3) -0.012(3)
C3 0.028(3) 0.026(4) 0.026(4) -0.003(3) 0.002(3) -0.003(3)
C2 0.028(3) 0.038(5) 0.018(4) 0.002(3) -0.008(3) 0.000(3)
C11 0.038(4) 0.038(4) 0.044(5) -0.005(4) -0.007(4) -0.002(4)
C13 0.054(4) 0.038(4) 0.045(5) -0.020(4) 0.027(4) 0.009(4)
N3 0.054(4) 0.038(4) 0.045(5) -0.020(4) 0.027(4) 0.009(4)
C14 0.050(4) 0.067(6) 0.041(5) -0.004(5) 0.009(4) 0.005(5)
N4 0.050(4) 0.067(6) 0.041(5) -0.004(5) 0.009(4) 0.005(5)
C8 0.047(4) 0.041(5) 0.033(5) -0.011(4) -0.008(4) -0.008(4)
N2 0.053(4) 0.036(4) 0.049(5) -0.011(4) -0.023(4) -0.006(3)
C9 0.062(6) 0.049(6) 0.038(5) -0.006(5) -0.006(4) 0.002(5)
C10 0.035(4) 0.044(5) 0.053(6) -0.011(4) -0.013(4) -0.010(4)
O1 0.037(3) 0.071(4) 0.023(3) -0.008(3) 0.005(3) -0.003(3)
O2 0.028(3) 0.066(4) 0.026(3) -0.006(3) 0.004(2) 0.008(3)
C6 0.037(4) 0.033(4) 0.031(4) -0.002(4) -0.001(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
Cu2 O2 1.855(5) 4_655 ?
Cu2 O4 1.863(5) . ?
Cu2 Cu3 2.6980(1) . ?
Cu2 Cu1 2.7935(1) . ?
Cu1 C14 1.872(9) . ?
Cu1 N1 1.989(6) . ?
Cu1 O1 2.236(6) 4_655 ?
Cu1 O3 2.273(5) . ?
Cu3 C13 1.820(7) . ?
Cu3 N2 1.888(7) 4 ?
N1 C1 1.336(1) . ?
N1 C5 1.356(9) . ?
O4 C12 1.266(1) . ?
C4 C5 1.388(1) . ?
C4 C3 1.405(1) . ?
C7 C8 1.378(1) . ?
C7 C11 1.394(1) . ?
C7 C12 1.509(1) . ?
C12 O3 1.251(9) . ?
C1 C2 1.383(1) . ?
C3 C2 1.389(9) . ?
C3 C6 1.488(1) . ?
C11 C10 1.386(1) . ?
C13 N4 1.139(1) 1_545 ?
C13 C14 1.139(1) 1_545 ?
C14 N3 1.139(1) 1_565 ?
C14 C13 1.139(1) 1_565 ?
C8 C9 1.373(1) . ?
N2 C10 1.337(1) . ?
N2 C9 1.347(1) . ?
N2 Cu3 1.888(7) 4_554 ?
O1 C6 1.260(9) . ?
O1 Cu1 2.236(6) 4_654 ?
O2 C6 1.281(8) . ?
O2 Cu2 1.855(5) 4_654 ?

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
O2 Cu2 O4 174.0(3) 4_655 . ?
O2 Cu2 Cu3 98.3(2) 4_655 . ?
O4 Cu2 Cu3 75.85(1) . . ?
O2 Cu2 Cu1 91.52(1) 4_655 . ?
O4 Cu2 Cu1 93.72(1) . . ?
Cu3 Cu2 Cu1 138.62(5) . . ?
C14 Cu1 N1 138.7(3) . . ?
C14 Cu1 O1 107.1(3) . 4_655 ?
N1 Cu1 O1 95.9(2) . 4_655 ?
C14 Cu1 O3 113.9(3) . . ?
N1 Cu1 O3 88.1(2) . . ?
O1 Cu1 O3 110.4(2) 4_655 . ?
C14 Cu1 Cu2 78.6(3) . . ?
N1 Cu1 Cu2 142.59(1) . . ?
O1 Cu1 Cu2 68.47(1) 4_655 . ?
O3 Cu1 Cu2 67.94(1) . . ?
C13 Cu3 N2 167.1(4) . 4 ?
C13 Cu3 Cu2 107.1(3) . . ?
N2 Cu3 Cu2 84.9(2) 4 . ?
C1 N1 C5 117.9(7) . . ?
C1 N1 Cu1 119.0(5) . . ?
C5 N1 Cu1 123.1(5) . . ?
C12 O4 Cu2 115.1(5) . . ?
C5 C4 C3 118.7(7) . . ?
C8 C7 C11 118.0(8) . . ?
C8 C7 C12 121.2(7) . . ?
C11 C7 C12 120.9(8) . . ?
O3 C12 O4 125.4(7) . . ?
O3 C12 C7 118.6(7) . . ?
O4 C12 C7 116.0(7) . . ?
N1 C1 C2 123.2(7) . . ?
N1 C5 C4 122.6(7) . . ?
C12 O3 Cu1 124.8(5) . . ?
C2 C3 C4 118.2(7) . . ?
C2 C3 C6 120.5(7) . . ?
C4 C3 C6 121.2(6) . . ?
C1 C2 C3 119.3(7) . . ?
C10 C11 C7 118.1(9) . . ?
N4 C13 C14 0.0(1) 1_545 1_545 ?
N4 C13 Cu3 170.1(8) 1_545 . ?
C14 C13 Cu3 170.1(8) 1_545 . ?
N3 C14 C13 0.0(9) 1_565 1_565 ?
N3 C14 Cu1 176.5(8) 1_565 . ?
C13 C14 Cu1 176.5(8) 1_565 . ?
C9 C8 C7 120.6(8) . . ?
C10 N2 C9 117.8(8) . . ?
C10 N2 Cu3 120.5(6) . 4_554 ?
C9 N2 Cu3 121.1(7) . 4_554 ?
N2 C9 C8 121.8(9) . . ?
N2 C10 C11 123.6(8) . . ?
C6 O1 Cu1 120.4(5) . 4_654 ?
C6 O2 Cu2 115.4(5) . 4_654 ?
O1 C6 O2 124.7(7) . . ?
O1 C6 C3 118.9(6) . . ?
O2 C6 C3 116.4(7) . . ?

_diffrn_measured_fraction_theta_max 0.990
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.990
_refine_diff_density_max         0.363
_refine_diff_density_min         -0.631
_refine_diff_density_rms         0.090