# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'G Bowmaker' _publ_contact_author_email G.BOWMAKER@AUCKLAND.AC.NZ _publ_section_title ; Solvent-assisted solid-state synthesis: Separating the chemical from the mechanical in mechanochemical synthesis ; loop_ _publ_author_name 'G Bowmaker' 'John V. Hanna' 'Brian W Skelton' 'Allan H White' # Attachment 'gb0898.cif' data_gb0898 _database_code_depnum_ccdc_archive 'CCDC 712656' _audit_creation_date 2008-11-07T13:23:37-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_sum 'C7 H12 Cu N5 S3' _chemical_formula_moiety 'C7 H12 Cu N5 S3' _chemical_formula_weight 325.94 #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/m 1' _symmetry_space_group_name_Hall -P_2yb loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' '-x, -y, -z' 'x, -y-1/2, z' _cell_length_a 6.0213(2) _cell_length_b 14.5533(4) _cell_length_c 7.1466(2) _cell_angle_alpha 90 _cell_angle_beta 102.484(3) _cell_angle_gamma 90 _cell_volume 611.45(3) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4667 _cell_measurement_theta_min 3.2322 _cell_measurement_theta_max 34.7262 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.37 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.03 _exptl_crystal_density_diffrn 1.77 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 332 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 2.277 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.29 (release 10-06-2008 CrysAlis171 .NET) (compiled Jun 10 2008,16:49:55) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_absorpt_correction_T_min 0.74 _exptl_absorpt_correction_T_max 0.93 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_detector_area_resol_mean 10.4738 _diffrn_orient_matrix_ub_11 0.0012366487 _diffrn_orient_matrix_ub_12 0.0395116911 _diffrn_orient_matrix_ub_13 0.0584325662 _diffrn_orient_matrix_ub_21 0.1204857829 _diffrn_orient_matrix_ub_22 -0.0007102927 _diffrn_orient_matrix_ub_23 0.0222861591 _diffrn_orient_matrix_ub_31 0.0014186896 _diffrn_orient_matrix_ub_32 0.0285756592 _diffrn_orient_matrix_ub_33 -0.0800366948 _diffrn_reflns_av_R_equivalents 0.0465 _diffrn_reflns_av_unetI/netI 0.0512 _diffrn_reflns_number 10048 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.24 _diffrn_reflns_theta_max 34.89 _diffrn_reflns_theta_full 33.5 _diffrn_measured_fraction_theta_full 0.993 _diffrn_measured_fraction_theta_max 0.951 _diffrn_measurement_device_type ; Oxford Diffraction Gemini diffractometer ; _diffrn_measurement_method '\w scans' _reflns_number_total 2625 _reflns_number_gt 2007 _reflns_threshold_expression I>2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.32.29 (release 10-06-2008 CrysAlis171 .NET) (compiled Jun 10 2008,16:49:55) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.29 (release 10-06-2008 CrysAlis171 .NET) (compiled Jun 10 2008,16:49:55) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.29 (release 10-06-2008 CrysAlis171 .NET) (compiled Jun 10 2008,16:49:55) ; _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.0295P)^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_number_reflns 2625 _refine_ls_number_parameters 79 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0598 _refine_ls_R_factor_gt 0.0345 _refine_ls_wR_factor_ref 0.0632 _refine_ls_wR_factor_gt 0.0583 _refine_ls_goodness_of_fit_ref 0.97 _refine_ls_restrained_S_all 0.97 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.563 _refine_diff_density_min -0.596 _refine_diff_density_rms 0.101 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0 '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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 0.66661(5) 0.75 0.76247(4) 0.01281(7) Uani 1 2 d S . . S1 S 0.84886(7) 0.61681(2) 0.82454(5) 0.01354(8) Uani 1 1 d . . . C1 C 0.6445(3) 0.53257(9) 0.78129(19) 0.0115(3) Uani 1 1 d . . . N2 N 0.4241(3) 0.54522(9) 0.7147(2) 0.0196(3) Uani 1 1 d . . . H2 H 0.3623 0.5992 0.6808 0.024 Uiso 1 1 calc R . . C3 C 0.2944(3) 0.45978(10) 0.7038(2) 0.0141(3) Uani 1 1 d . . . H3A H 0.204 0.4491 0.5725 0.017 Uiso 1 1 calc R . . H3B H 0.1914 0.4602 0.7946 0.017 Uiso 1 1 calc R . . C4 C 0.4823(3) 0.38702(10) 0.7601(2) 0.0152(3) Uani 1 1 d . . . H4A H 0.4602 0.3502 0.8711 0.018 Uiso 1 1 calc R . . H4B H 0.4881 0.3454 0.6517 0.018 Uiso 1 1 calc R . . N5 N 0.6870(3) 0.44372(9) 0.8097(2) 0.0199(3) Uani 1 1 d . . . H5 H 0.824 0.4212 0.8537 0.024 Uiso 1 1 calc R . . S11 S 0.00056(11) 0.75 0.30557(9) 0.01948(12) Uani 1 2 d S . . C11 C 0.1945(4) 0.75 0.5028(3) 0.0146(4) Uani 1 2 d S . . N11 N 0.3411(4) 0.75 0.6418(3) 0.0171(4) Uani 1 2 d S . . 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 0.01505(15) 0.00833(12) 0.01420(12) 0 0.00128(10) 0 S1 0.01334(18) 0.00856(15) 0.01762(17) 0.00085(12) 0.00088(14) -0.00052(12) C1 0.0148(7) 0.0093(6) 0.0106(6) 0.0003(5) 0.0035(5) 0.0003(5) N2 0.0138(7) 0.0080(5) 0.0353(7) 0.0024(5) 0.0015(6) 0.0009(5) C3 0.0150(8) 0.0102(6) 0.0168(6) -0.0011(5) 0.0027(6) -0.0019(5) C4 0.0165(8) 0.0091(6) 0.0201(7) -0.0002(5) 0.0044(6) -0.0014(5) N5 0.0138(7) 0.0095(6) 0.0340(7) 0.0028(5) 0.0001(6) -0.0003(5) S11 0.0165(3) 0.0144(2) 0.0243(3) 0 -0.0028(2) 0 C11 0.0129(11) 0.0076(8) 0.0237(10) 0 0.0049(9) 0 N11 0.0157(10) 0.0118(8) 0.0223(9) 0 0.0007(8) 0 #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 N11 1.963(2) . ? Cu1 S1 2.2243(4) 4_575 ? Cu1 S1 2.2243(4) . ? S1 C1 1.7171(16) . ? C1 N2 1.323(2) . ? C1 N5 1.3251(19) . ? N2 C3 1.461(2) . ? N2 H2 0.88 . ? C3 C4 1.538(2) . ? C3 H3A 0.99 . ? C3 H3B 0.99 . ? C4 N5 1.462(2) . ? C4 H4A 0.99 . ? C4 H4B 0.99 . ? N5 H5 0.88 . ? S11 C11 1.625(2) . ? C11 N11 1.178(3) . ? 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 N11 Cu1 S1 119.357(12) . 4_575 ? N11 Cu1 S1 119.357(13) . . ? S1 Cu1 S1 121.25(2) 4_575 . ? C1 S1 Cu1 106.43(5) . . ? N2 C1 N5 109.65(14) . . ? N2 C1 S1 126.14(11) . . ? N5 C1 S1 124.20(13) . . ? C1 N2 C3 112.57(12) . . ? C1 N2 H2 123.7 . . ? C3 N2 H2 123.7 . . ? N2 C3 C4 102.58(13) . . ? N2 C3 H3A 111.3 . . ? C4 C3 H3A 111.3 . . ? N2 C3 H3B 111.3 . . ? C4 C3 H3B 111.3 . . ? H3A C3 H3B 109.2 . . ? N5 C4 C3 102.04(12) . . ? N5 C4 H4A 111.4 . . ? C3 C4 H4A 111.4 . . ? N5 C4 H4B 111.4 . . ? C3 C4 H4B 111.4 . . ? H4A C4 H4B 109.2 . . ? C1 N5 C4 112.90(14) . . ? C1 N5 H5 123.6 . . ? C4 N5 H5 123.6 . . ? N11 C11 S11 177.5(2) . . ? C11 N11 Cu1 149.97(19) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N11 Cu1 S1 C1 -8.76(8) . . . . ? S1 Cu1 S1 C1 173.55(5) 4_575 . . . ? Cu1 S1 C1 N2 3.14(15) . . . . ? Cu1 S1 C1 N5 -177.25(12) . . . . ? N5 C1 N2 C3 3.44(19) . . . . ? S1 C1 N2 C3 -176.91(11) . . . . ? C1 N2 C3 C4 -5.14(17) . . . . ? N2 C3 C4 N5 4.59(15) . . . . ? N2 C1 N5 C4 0.02(19) . . . . ? S1 C1 N5 C4 -179.65(10) . . . . ? C3 C4 N5 C1 -3.11(17) . . . . ? S11 C11 N11 Cu1 0.00(2) . . . . ? S1 Cu1 N11 C11 88.87(3) 4_575 . . . ? S1 Cu1 N11 C11 -88.87(4) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N2 H2 N11 0.88 2.21 3.0479(13) 158.3 . N5 H5 S1 0.88 2.74 3.5019(16) 145.4 3_767 N5 H5 S11 0.88 3.02 3.5829(15) 123.3 3_666 #===END