# 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        'Prof Maochun Hong'
_publ_contact_author_address     
;
Chinese Academy of Sciences
Fujian Institute of Research on the Structure of Matter
Fuzhou
350002
CHINA
;

_publ_contact_author_email       HMC@MS.FJIRSM.AC.CN

_publ_section_title              
;
Red luminescent polymeric cuprous organosulfide
generated by solvothermal redox reaction
;
loop_
_publ_author_name
'Maochun Hong'
'Lei Han'
'Zhengzhong Lin'
'Benyong Lou'
'Ruihu Wang'
'Benlaid Wu'
'Ying Xu'

data_compound_1
_database_code_depnum_ccdc_archive 'CCDC 241012'

_audit_creation_method           'by CrystalClear v1.3'
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C12 H9 Cu3 N6 S3'
_chemical_formula_weight         524.05

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'
Cu Cu 0.3201 1.2651 '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'
S S 0.1246 0.1234 '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'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   P212121

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

_cell_length_a                   11.84(3)
_cell_length_b                   7.874(7)
_cell_length_c                   17.51(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1632(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       prism
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.132
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1032
_exptl_absorpt_coefficient_mu    4.263
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.8681
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   ?

_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  'Mercury CCD'
_diffrn_measurement_method       '\w scan'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            12794
_diffrn_reflns_av_R_equivalents  0.0862
_diffrn_reflns_av_sigmaI/netI    0.0909
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.33
_diffrn_reflns_theta_max         27.48
_reflns_number_total             3734
_reflns_number_gt                3059
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrystalClear (Rigaku, 2000)'
_computing_cell_refinement       CrystalClear
_computing_data_reduction        CrystalClear
_computing_structure_solution    'SHELXTL (Siemens, 1994)'
_computing_structure_refinement  SHELXTL
_computing_molecular_graphics    'SHELXTL (Bruker, 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_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^)+(0.0370P)^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    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(2)
_refine_ls_number_reflns         3734
_refine_ls_number_parameters     218
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0759
_refine_ls_R_factor_gt           0.0579
_refine_ls_wR_factor_ref         0.1044
_refine_ls_wR_factor_gt          0.0962
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_restrained_S_all      1.061
_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
Cu1 Cu 0.88434(7) 0.05857(12) 0.85503(5) 0.0185(2) Uani 1 1 d . . .
Cu2 Cu 0.94467(7) 0.32940(11) 0.76079(5) 0.0170(2) Uani 1 1 d . . .
Cu3 Cu 0.84086(8) 0.05373(12) 0.66874(5) 0.0201(2) Uani 1 1 d . . .
S1 S 0.73730(15) 0.0782(2) 0.77563(10) 0.0166(4) Uani 1 1 d . . .
S2 S 0.98298(14) -0.1850(2) 0.85796(10) 0.0159(4) Uani 1 1 d . . .
S3 S 1.07535(14) 0.3053(2) 0.85303(10) 0.0157(4) Uani 1 1 d . . .
N1 N 0.7852(5) 0.4117(7) 0.7740(3) 0.0148(12) Uani 1 1 d . . .
N2 N 0.5893(5) 0.3321(7) 0.7786(3) 0.0203(14) Uani 1 1 d . . .
N3 N 1.0852(5) -0.0498(8) 0.9807(3) 0.0204(14) Uani 1 1 d . . .
N4 N 1.1839(5) -0.2678(8) 0.9126(3) 0.0182(14) Uani 1 1 d . . .
N5 N 0.9060(5) 0.2193(7) 0.9441(3) 0.0159(13) Uani 1 1 d . . .
N6 N 1.0510(6) 0.3897(8) 1.0013(3) 0.0223(15) Uani 1 1 d . . .
C1 C 0.7009(6) 0.2940(8) 0.7758(4) 0.0129(15) Uani 1 1 d U . .
C2 C 0.5629(7) 0.4991(9) 0.7801(4) 0.0217(17) Uani 1 1 d . . .
H2A H 0.4855 0.5307 0.7817 0.026 Uiso 1 1 calc R . .
C3 C 0.6434(6) 0.6258(9) 0.7795(4) 0.0180(16) Uani 1 1 d . . .
H3A H 0.6231 0.7424 0.7815 0.022 Uiso 1 1 calc R . .
C4 C 0.7538(6) 0.5755(8) 0.7761(4) 0.0151(15) Uani 1 1 d . . .
H4A H 0.8109 0.6602 0.7751 0.018 Uiso 1 1 calc R . .
C5 C 1.0953(6) -0.1635(9) 0.9237(4) 0.0125(14) Uani 1 1 d U . .
C6 C 1.1747(7) -0.0391(11) 1.0263(4) 0.0276(19) Uani 1 1 d . . .
H6A H 1.1721 0.0405 1.0671 0.033 Uiso 1 1 calc R . .
C7 C 1.2711(7) -0.1357(10) 1.0184(4) 0.0263(19) Uani 1 1 d . . .
H7A H 1.3340 -0.1228 1.0515 0.032 Uiso 1 1 calc R . .
C8 C 1.2709(7) -0.2512(10) 0.9602(4) 0.0244(18) Uani 1 1 d . . .
H8A H 1.3351 -0.3221 0.9534 0.029 Uiso 1 1 calc R . .
C9 C 1.0035(6) 0.3086(9) 0.9415(4) 0.0162(15) Uani 1 1 d . . .
C10 C 0.9950(7) 0.3763(10) 1.0676(4) 0.027(2) Uani 1 1 d . . .
H10A H 1.0266 0.4281 1.1117 0.033 Uiso 1 1 calc R . .
C11 C 0.8930(7) 0.2906(10) 1.0751(4) 0.0286(19) Uani 1 1 d . . .
H11A H 0.8539 0.2858 1.1224 0.034 Uiso 1 1 calc R . .
C12 C 0.8518(6) 0.2136(10) 1.0112(4) 0.0197(17) Uani 1 1 d . . .
H12A H 0.7823 0.1539 1.0143 0.024 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
Cu1 0.0157(4) 0.0181(5) 0.0217(4) 0.0013(4) -0.0023(4) 0.0002(4)
Cu2 0.0137(4) 0.0202(4) 0.0171(4) 0.0002(4) 0.0002(4) 0.0001(4)
Cu3 0.0204(5) 0.0164(5) 0.0234(5) -0.0013(4) 0.0019(4) 0.0008(4)
S1 0.0134(9) 0.0146(9) 0.0217(9) 0.0006(8) -0.0007(8) 0.0012(8)
S2 0.0141(9) 0.0167(9) 0.0170(8) -0.0006(8) 0.0007(7) -0.0014(8)
S3 0.0146(9) 0.0156(9) 0.0169(8) -0.0014(8) -0.0008(7) -0.0013(8)
N1 0.013(3) 0.017(3) 0.014(3) 0.001(3) 0.002(2) -0.003(3)
N2 0.014(3) 0.018(3) 0.028(3) 0.000(3) -0.001(3) 0.000(3)
N3 0.023(4) 0.022(3) 0.016(3) 0.002(3) -0.008(3) 0.006(3)
N4 0.019(3) 0.021(3) 0.014(3) 0.006(3) 0.001(3) 0.002(3)
N5 0.020(3) 0.015(3) 0.012(3) 0.000(2) 0.002(3) 0.006(3)
N6 0.025(4) 0.021(4) 0.021(3) -0.005(3) -0.002(3) -0.001(3)
C1 0.012(2) 0.015(2) 0.012(2) -0.0031(17) -0.0017(17) -0.0019(17)
C2 0.017(4) 0.022(4) 0.027(4) 0.004(3) -0.001(4) 0.008(3)
C3 0.016(4) 0.013(3) 0.024(4) 0.006(3) -0.001(3) 0.003(3)
C4 0.019(4) 0.011(3) 0.015(3) 0.002(3) -0.002(3) -0.004(3)
C5 0.014(2) 0.011(2) 0.013(2) 0.0026(17) 0.0014(17) 0.0004(17)
C6 0.033(5) 0.029(5) 0.021(4) -0.004(4) -0.009(4) -0.003(4)
C7 0.028(5) 0.024(4) 0.026(4) 0.005(4) -0.011(4) 0.001(4)
C8 0.017(4) 0.023(4) 0.033(5) 0.005(4) -0.004(4) 0.009(4)
C9 0.018(4) 0.010(4) 0.021(4) 0.003(3) -0.004(3) -0.001(3)
C10 0.033(5) 0.034(5) 0.015(4) -0.015(3) -0.001(4) 0.006(4)
C11 0.036(5) 0.035(5) 0.015(4) 0.003(3) 0.009(4) -0.001(4)
C12 0.012(4) 0.024(5) 0.023(4) 0.003(3) 0.001(3) -0.006(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
Cu1 N5 2.025(6) . ?
Cu1 S1 2.233(4) . ?
Cu1 S2 2.246(3) . ?
Cu1 Cu2 2.789(3) . ?
Cu2 N1 2.010(7) . ?
Cu2 S3 2.245(4) . ?
Cu2 S2 2.252(5) 4_756 ?
Cu2 Cu3 2.970(3) . ?
Cu3 N4 2.022(7) 4_756 ?
Cu3 S3 2.226(3) 4_746 ?
Cu3 S1 2.246(4) . ?
S1 C1 1.753(7) . ?
S2 C5 1.767(8) . ?
S2 Cu2 2.252(5) 4_746 ?
S3 C9 1.767(8) . ?
S3 Cu3 2.226(3) 4_756 ?
N1 C4 1.342(9) . ?
N1 C1 1.363(9) . ?
N2 C2 1.352(9) . ?
N2 C1 1.356(9) . ?
N3 C6 1.330(9) . ?
N3 C5 1.346(9) . ?
N4 C8 1.331(10) . ?
N4 C5 1.347(9) . ?
N4 Cu3 2.022(7) 4_746 ?
N5 C12 1.339(9) . ?
N5 C9 1.352(9) . ?
N6 C10 1.341(10) . ?
N6 C9 1.350(9) . ?
C2 C3 1.380(10) . ?
C3 C4 1.367(10) . ?
C6 C7 1.378(12) . ?
C7 C8 1.366(11) . ?
C10 C11 1.390(12) . ?
C11 C12 1.363(10) . ?

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
N5 Cu1 S1 122.36(19) . . ?
N5 Cu1 S2 116.75(19) . . ?
S1 Cu1 S2 118.59(10) . . ?
N5 Cu1 Cu2 86.9(2) . . ?
S1 Cu1 Cu2 77.20(12) . . ?
S2 Cu1 Cu2 122.22(11) . . ?
N1 Cu2 S3 126.3(2) . . ?
N1 Cu2 S2 118.68(17) . 4_756 ?
S3 Cu2 S2 113.45(18) . 4_756 ?
N1 Cu2 Cu1 86.44(17) . . ?
S3 Cu2 Cu1 71.71(12) . . ?
S2 Cu2 Cu1 127.24(9) 4_756 . ?
N1 Cu2 Cu3 84.80(19) . . ?
S3 Cu2 Cu3 127.88(9) . . ?
S2 Cu2 Cu3 67.64(12) 4_756 . ?
Cu1 Cu2 Cu3 69.90(13) . . ?
N4 Cu3 S3 123.69(19) 4_756 4_746 ?
N4 Cu3 S1 116.6(2) 4_756 . ?
S3 Cu3 S1 117.47(9) 4_746 . ?
N4 Cu3 Cu2 86.2(2) 4_756 . ?
S3 Cu3 Cu2 123.42(12) 4_746 . ?
S1 Cu3 Cu2 73.20(13) . . ?
C1 S1 Cu1 104.9(2) . . ?
C1 S1 Cu3 102.7(2) . . ?
Cu1 S1 Cu3 95.0(2) . . ?
C5 S2 Cu1 108.9(3) . . ?
C5 S2 Cu2 108.1(3) . 4_746 ?
Cu1 S2 Cu2 97.69(9) . 4_746 ?
C9 S3 Cu3 110.6(2) . 4_756 ?
C9 S3 Cu2 107.3(3) . . ?
Cu3 S3 Cu2 96.30(12) 4_756 . ?
C4 N1 C1 116.8(6) . . ?
C4 N1 Cu2 125.0(5) . . ?
C1 N1 Cu2 118.1(4) . . ?
C2 N2 C1 116.2(6) . . ?
C6 N3 C5 114.6(7) . . ?
C8 N4 C5 116.9(6) . . ?
C8 N4 Cu3 128.4(5) . 4_746 ?
C5 N4 Cu3 114.4(5) . 4_746 ?
C12 N5 C9 117.2(6) . . ?
C12 N5 Cu1 126.4(5) . . ?
C9 N5 Cu1 114.0(5) . . ?
C10 N6 C9 115.3(7) . . ?
N2 C1 N1 124.3(6) . . ?
N2 C1 S1 117.0(5) . . ?
N1 C1 S1 118.6(5) . . ?
N2 C2 C3 122.9(7) . . ?
C4 C3 C2 116.8(7) . . ?
N1 C4 C3 123.0(7) . . ?
N3 C5 N4 125.6(6) . . ?
N3 C5 S2 118.7(5) . . ?
N4 C5 S2 115.7(5) . . ?
N3 C6 C7 124.4(7) . . ?
C8 C7 C6 116.2(7) . . ?
N4 C8 C7 122.3(7) . . ?
N6 C9 N5 125.1(7) . . ?
N6 C9 S3 119.1(6) . . ?
N5 C9 S3 115.7(5) . . ?
N6 C10 C11 123.4(7) . . ?
C12 C11 C10 116.7(7) . . ?
N5 C12 C11 122.3(7) . . ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        27.48
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.650
_refine_diff_density_min         -0.632
_refine_diff_density_rms         0.148