# Electronic Supplementary Material (ESI) for CrystEngComm # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_IFP-9 _audit_creation_method SHELXL-97 _chemical_name_systematic ; (2-ethoxy-imidazolate-4-amide-5-imidato)-zinc(II) dimethylformamide solvate ; _chemical_formula_moiety 'C7 H8 N4 O3 Zn, 0.5(C3H7O)' _chemical_formula_sum 'C8.5 H11.5 N4.5 O3.5 Zn' _chemical_formula_weight 298.09 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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting trigonal _symmetry_space_group_name_H-M 'R -3' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 18.0166(5) _cell_length_b 18.0166(5) _cell_length_c 18.6077(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 5230.8(2) _cell_formula_units_Z 18 _cell_measurement_temperature 210(2) _cell_measurement_reflns_used 32841 _cell_measurement_theta_min 1.70 _cell_measurement_theta_max 29.69 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.12 _exptl_crystal_density_diffrn 1.703 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2736 _exptl_absorpt_coefficient_mu 2.122 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.6101 _exptl_absorpt_correction_T_max 0.8281 _exptl_absorpt_process_details 'X-Red (Stoe, 2004)' _exptl_special_details ; The crystal was embedded in perfluoropolyalkylether oil. ; _diffrn_ambient_temperature 210(2) _diffrn_measurement_device '2-circle goniometer' _diffrn_measurement_device_type 'STOE IPDS 2' _diffrn_detector 'image plate (34 cm diameter)' _diffrn_detector_type STOE _diffrn_detector_area_resol_mean 6.67 _diffrn_source 'fine-focus sealed tube' _diffrn_source_voltage 50 _diffrn_source_current 40 _diffrn_source_power 2.00 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_monochromator 'plane graphite' _diffrn_measurement_method '\w scan, \d \w = 1.0 deg' _diffrn_measurement_details ; 360 frames, exposure time = 4 min ; _diffrn_reflns_number 29403 _diffrn_reflns_av_R_equivalents 0.0211 _diffrn_reflns_av_sigmaI/netI 0.0079 _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -23 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 1.70 _diffrn_reflns_theta_max 27.49 _reflns_number_total 2681 _reflns_number_gt 2506 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-AREA (Stoe, 2004)' _computing_cell_refinement 'X-AREA (Stoe, 2004)' _computing_data_reduction 'X-RED (Stoe, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0316P)^2^+7.6193P] 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 SHELXL _refine_ls_extinction_coef 0.00011(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2681 _refine_ls_number_parameters 164 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0236 _refine_ls_R_factor_gt 0.0212 _refine_ls_wR_factor_ref 0.0569 _refine_ls_wR_factor_gt 0.0559 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.049 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 _refine_special_details ; The unit cell contains channels filled with disordered solvent molecules. In spite of several attempts, no chemically reasonable solution could be received for the solvent species in the channels of the crystal material. Very high displacement parameters, high esdimates and partial occupany due to the disorder make it impossible to determine accurate atomic positions for that molecules. PLATON/SQUEEZE calculated a solvent-accessible void volume in the unit cell of 1196.2 \%A^3^ (22.9 % of the total cell volume), corresponding to 336 electrons (residual electron density after the last refinement cycle) per cell. This number agrees with about 0.5 molecules of DMF (0.5x40x18=360) per asymmetric unit. The contributions of the disordered solvent species was subtracted from the structure factor calculations, but included in D(calc), F000 & Mol.Wght. The deposited atom data (cif) reflect only known cell content. ; 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 C1 C 0.73565(9) 0.68897(9) 0.21372(8) 0.0230(3) Uani 1 1 d . A . C2 C 0.61742(9) 0.57216(9) 0.23239(7) 0.0206(3) Uani 1 1 d . . . C3 C 0.55293(10) 0.50219(9) 0.27728(8) 0.0238(3) Uani 1 1 d . . . C4 C 0.56903(10) 0.55618(10) 0.09651(8) 0.0256(3) Uani 1 1 d . . . C5 C 0.62273(9) 0.59323(9) 0.16071(7) 0.0211(3) Uani 1 1 d . . . C61 C 0.8716(2) 0.8031(2) 0.18313(19) 0.0337(7) Uani 0.50 1 d P A 1 H61B H 0.8539 0.8345 0.1519 0.040 Uiso 0.50 1 calc PR A 1 H61A H 0.8836 0.7662 0.1532 0.040 Uiso 0.50 1 calc PR A 1 C71 C 0.9519(2) 0.8655(3) 0.2220(3) 0.0461(10) Uani 0.50 1 d P A 1 H71A H 0.9969 0.8966 0.1877 0.069 Uiso 0.50 1 calc PR A 1 H71B H 0.9688 0.8349 0.2542 0.069 Uiso 0.50 1 calc PR A 1 H71C H 0.9415 0.9049 0.2489 0.069 Uiso 0.50 1 calc PR A 1 C62 C 0.8506(2) 0.7933(2) 0.28250(19) 0.0388(8) Uani 0.50 1 d P A 2 H62A H 0.8466 0.7495 0.3152 0.047 Uiso 0.50 1 calc PR A 2 H62B H 0.8219 0.8207 0.3049 0.047 Uiso 0.50 1 calc PR A 2 C72 C 0.9416(3) 0.8577(3) 0.2723(3) 0.0525(11) Uani 0.50 1 d P A 2 H72A H 0.9737 0.8581 0.3137 0.079 Uiso 0.50 1 calc PR A 2 H72B H 0.9474 0.9132 0.2664 0.079 Uiso 0.50 1 calc PR A 2 H72C H 0.9630 0.8436 0.2304 0.079 Uiso 0.50 1 calc PR A 2 N1 N 0.69897(8) 0.66828(8) 0.14924(6) 0.0219(2) Uani 1 1 d . . . N2 N 0.69053(8) 0.63418(8) 0.26624(6) 0.0219(2) Uani 1 1 d . . . N3 N 0.57111(9) 0.50985(9) 0.34538(7) 0.0321(3) Uani 1 1 d . . . H30 H 0.5373(14) 0.4740(14) 0.3685(12) 0.039 Uiso 1 1 d . . . N4 N 0.49648(10) 0.48311(10) 0.10154(8) 0.0379(4) Uani 1 1 d . . . H40 H 0.4677(15) 0.4607(15) 0.0628(13) 0.045 Uiso 1 1 d . . . H41 H 0.4787(14) 0.4569(14) 0.1450(14) 0.045 Uiso 1 1 d . . . O1 O 0.81171(8) 0.75779(9) 0.22504(10) 0.0526(4) Uani 1 1 d . . . O2 O 0.48602(7) 0.44189(7) 0.24700(6) 0.0300(3) Uani 1 1 d . . . O3 O 0.59499(8) 0.59631(7) 0.03834(6) 0.0309(3) Uani 1 1 d . . . Zn1 Zn 0.713574(11) 0.717571(11) 0.046131(8) 0.02051(7) 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 C1 0.0230(7) 0.0211(6) 0.0237(7) -0.0015(5) -0.0014(5) 0.0102(6) C2 0.0241(7) 0.0220(6) 0.0137(6) -0.0023(5) -0.0025(5) 0.0100(6) C3 0.0263(7) 0.0248(7) 0.0145(6) -0.0002(5) -0.0016(5) 0.0083(6) C4 0.0310(8) 0.0252(7) 0.0159(6) 0.0011(5) -0.0015(5) 0.0105(6) C5 0.0247(7) 0.0203(6) 0.0155(6) 0.0007(5) 0.0008(5) 0.0093(5) C61 0.0281(16) 0.0314(16) 0.0337(17) 0.0027(13) 0.0046(13) 0.0089(14) C71 0.0266(18) 0.0331(19) 0.065(3) -0.0093(19) -0.0010(19) 0.0050(15) C62 0.0308(17) 0.0344(17) 0.0296(17) -0.0054(14) -0.0101(14) 0.0000(14) C72 0.032(2) 0.049(2) 0.056(3) -0.013(2) -0.0051(19) 0.0040(17) N1 0.0263(6) 0.0210(6) 0.0174(6) 0.0022(4) 0.0023(5) 0.0111(5) N2 0.0240(6) 0.0247(6) 0.0158(6) -0.0021(4) -0.0025(5) 0.0114(5) N3 0.0319(7) 0.0325(7) 0.0129(6) 0.0019(5) -0.0005(5) 0.0018(6) N4 0.0417(8) 0.0323(7) 0.0148(6) 0.0026(5) -0.0083(6) -0.0002(6) O1 0.0256(6) 0.0284(7) 0.0912(12) -0.0051(7) -0.0114(7) 0.0041(5) O2 0.0300(6) 0.0276(5) 0.0152(5) 0.0021(4) -0.0024(4) 0.0014(5) O3 0.0380(6) 0.0291(6) 0.0142(5) 0.0038(4) -0.0025(4) 0.0084(5) Zn1 0.02712(10) 0.02496(10) 0.01157(10) 0.00083(6) 0.00269(6) 0.01461(7) 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 C1 O1 1.3268(19) . ? C1 N1 1.3300(19) . ? C1 N2 1.3371(19) . ? C2 C5 1.3768(19) . ? C2 N2 1.3815(18) . ? C2 C3 1.474(2) . ? C3 O2 1.2811(18) . ? C3 N3 1.2988(19) . ? C4 O3 1.2550(18) . ? C4 N4 1.315(2) . ? C4 C5 1.4707(19) . ? C5 N1 1.3796(19) . ? C61 O1 1.248(4) . ? C61 C71 1.502(5) . ? C61 H61B 0.9700 . ? C61 H61A 0.9700 . ? C71 H71A 0.9600 . ? C71 H71B 0.9600 . ? C71 H71C 0.9600 . ? C62 O1 1.263(4) . ? C62 C72 1.473(5) . ? C62 H62A 0.9700 . ? C62 H62B 0.9700 . ? C72 H72A 0.9600 . ? C72 H72B 0.9600 . ? C72 H72C 0.9600 . ? N1 Zn1 2.0750(12) . ? N2 Zn1 2.1310(12) 6_565 ? N3 Zn1 1.9972(14) 6_565 ? N3 H30 0.76(2) . ? N4 H40 0.86(2) . ? N4 H41 0.91(2) . ? O2 Zn1 2.0041(11) 14_455 ? O3 Zn1 2.1658(11) . ? Zn1 N3 1.9973(14) 8_654 ? Zn1 O2 2.0042(11) 15 ? Zn1 N2 2.1310(12) 8_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 O1 C1 N1 122.78(15) . . ? O1 C1 N2 122.45(15) . . ? N1 C1 N2 114.77(13) . . ? C5 C2 N2 108.18(12) . . ? C5 C2 C3 134.53(13) . . ? N2 C2 C3 117.28(12) . . ? O2 C3 N3 126.84(14) . . ? O2 C3 C2 118.76(12) . . ? N3 C3 C2 114.40(13) . . ? O3 C4 N4 122.39(14) . . ? O3 C4 C5 117.91(13) . . ? N4 C4 C5 119.70(13) . . ? C2 C5 N1 108.54(12) . . ? C2 C5 C4 136.26(13) . . ? N1 C5 C4 115.20(12) . . ? O1 C61 C71 112.5(3) . . ? O1 C61 H61B 109.1 . . ? C71 C61 H61B 109.1 . . ? O1 C61 H61A 109.1 . . ? C71 C61 H61A 109.1 . . ? H61B C61 H61A 107.8 . . ? C61 C71 H71A 109.5 . . ? C61 C71 H71B 109.5 . . ? H71A C71 H71B 109.5 . . ? C61 C71 H71C 109.5 . . ? H71A C71 H71C 109.5 . . ? H71B C71 H71C 109.5 . . ? O1 C62 C72 114.0(3) . . ? O1 C62 H62A 108.7 . . ? C72 C62 H62A 108.7 . . ? O1 C62 H62B 108.7 . . ? C72 C62 H62B 108.7 . . ? H62A C62 H62B 107.6 . . ? C62 C72 H72A 109.5 . . ? C62 C72 H72B 109.5 . . ? H72A C72 H72B 109.5 . . ? C62 C72 H72C 109.5 . . ? H72A C72 H72C 109.5 . . ? H72B C72 H72C 109.5 . . ? C1 N1 C5 104.29(12) . . ? C1 N1 Zn1 140.83(10) . . ? C5 N1 Zn1 114.43(9) . . ? C1 N2 C2 104.22(12) . . ? C1 N2 Zn1 144.65(10) . 6_565 ? C2 N2 Zn1 108.55(9) . 6_565 ? C3 N3 Zn1 117.96(11) . 6_565 ? C3 N3 H30 114.1(17) . . ? Zn1 N3 H30 127.1(17) 6_565 . ? C4 N4 H40 118.3(15) . . ? C4 N4 H41 119.9(14) . . ? H40 N4 H41 122(2) . . ? C61 O1 C62 96.8(3) . . ? C61 O1 C1 131.5(2) . . ? C62 O1 C1 131.3(2) . . ? C3 O2 Zn1 131.59(10) . 14_455 ? C4 O3 Zn1 114.76(10) . . ? N3 Zn1 O2 120.68(6) 8_654 15 ? N3 Zn1 N1 103.96(5) 8_654 . ? O2 Zn1 N1 89.46(5) 15 . ? N3 Zn1 N2 79.61(5) 8_654 8_654 ? O2 Zn1 N2 105.52(5) 15 8_654 ? N1 Zn1 N2 160.32(5) . 8_654 ? N3 Zn1 O3 120.32(6) 8_654 . ? O2 Zn1 O3 118.99(5) 15 . ? N1 Zn1 O3 77.30(4) . . ? N2 Zn1 O3 84.19(4) 8_654 . ? 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 C5 C2 C3 O2 4.0(3) . . . . ? N2 C2 C3 O2 -177.28(14) . . . . ? C5 C2 C3 N3 -175.29(17) . . . . ? N2 C2 C3 N3 3.4(2) . . . . ? N2 C2 C5 N1 0.06(17) . . . . ? C3 C2 C5 N1 178.82(16) . . . . ? N2 C2 C5 C4 179.76(16) . . . . ? C3 C2 C5 C4 -1.5(3) . . . . ? O3 C4 C5 C2 178.12(17) . . . . ? N4 C4 C5 C2 -2.0(3) . . . . ? O3 C4 C5 N1 -2.2(2) . . . . ? N4 C4 C5 N1 177.69(16) . . . . ? O1 C1 N1 C5 179.16(15) . . . . ? N2 C1 N1 C5 0.22(17) . . . . ? O1 C1 N1 Zn1 -9.6(3) . . . . ? N2 C1 N1 Zn1 171.48(11) . . . . ? C2 C5 N1 C1 -0.16(16) . . . . ? C4 C5 N1 C1 -179.94(13) . . . . ? C2 C5 N1 Zn1 -174.11(10) . . . . ? C4 C5 N1 Zn1 6.12(16) . . . . ? O1 C1 N2 C2 -179.13(14) . . . . ? N1 C1 N2 C2 -0.19(17) . . . . ? O1 C1 N2 Zn1 23.3(3) . . . 6_565 ? N1 C1 N2 Zn1 -157.80(13) . . . 6_565 ? C5 C2 N2 C1 0.07(16) . . . . ? C3 C2 N2 C1 -178.93(13) . . . . ? C5 C2 N2 Zn1 166.63(10) . . . 6_565 ? C3 C2 N2 Zn1 -12.38(15) . . . 6_565 ? O2 C3 N3 Zn1 -170.44(13) . . . 6_565 ? C2 C3 N3 Zn1 8.8(2) . . . 6_565 ? C71 C61 O1 C62 3.7(4) . . . . ? C71 C61 O1 C1 -169.9(2) . . . . ? C72 C62 O1 C61 -6.1(4) . . . . ? C72 C62 O1 C1 167.5(3) . . . . ? N1 C1 O1 C61 -19.5(4) . . . . ? N2 C1 O1 C61 159.4(3) . . . . ? N1 C1 O1 C62 169.1(3) . . . . ? N2 C1 O1 C62 -12.0(4) . . . . ? N3 C3 O2 Zn1 -0.2(3) . . . 14_455 ? C2 C3 O2 Zn1 -179.42(11) . . . 14_455 ? N4 C4 O3 Zn1 177.41(14) . . . . ? C5 C4 O3 Zn1 -2.73(19) . . . . ? C1 N1 Zn1 N3 65.19(17) . . . 8_654 ? C5 N1 Zn1 N3 -124.12(11) . . . 8_654 ? C1 N1 Zn1 O2 -56.37(17) . . . 15 ? C5 N1 Zn1 O2 114.31(10) . . . 15 ? C1 N1 Zn1 N2 163.43(15) . . . 8_654 ? C5 N1 Zn1 N2 -25.9(2) . . . 8_654 ? C1 N1 Zn1 O3 -176.30(17) . . . . ? C5 N1 Zn1 O3 -5.62(10) . . . . ? C4 O3 Zn1 N3 103.48(12) . . . 8_654 ? C4 O3 Zn1 O2 -77.61(12) . . . 15 ? C4 O3 Zn1 N1 4.58(12) . . . . ? C4 O3 Zn1 N2 177.85(12) . . . 8_654 ? 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 N3 H30 N2 0.76(2) 2.50(2) 3.2106(19) 156(2) 18_545 N4 H40 O3 0.86(2) 2.17(2) 3.0299(17) 175(2) 10_665 N4 H41 O2 0.91(2) 1.93(3) 2.7880(18) 156(2) . _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.316 _refine_diff_density_min -0.328 _refine_diff_density_rms 0.050 loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.000 0.000 0.000 106 37 ' ' 2 0.000 0.000 0.500 281 75 ' ' 3 0.333 0.667 0.167 277 75 ' ' 4 0.333 0.667 0.667 107 37 ' ' 5 0.667 0.333 0.833 277 75 ' ' 6 0.667 0.333 0.333 107 37 ' ' _database_code_depnum_ccdc_archive 'CCDC 956082'