Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_coden_Cambridge 222 _publ_requested_journal 'Dalton Transactions' loop_ _publ_author_name 'Neil Robertson' 'Stewart J Clark' P.Deplano 'Elaine A. M. Geary' 'Maria Laura Mercuri' S.Parsons 'Luca Pilia' 'Angela Serpe' 'Lesley Yellowlees' _publ_contact_author_name 'Neil Robertson' _publ_contact_author_address ; Department of Chemistry Edinburgh University Joseph Black Building West Mains Road Edinburgh EH9 3JJ UNITED KINGDOM ; _publ_contact_author_email NEIL.ROBERTSON@ED.AC.UK _publ_section_title ; Influence of the R-substituents on the Properties of [Ni(R2pipdt)(dmit)] Complexes and Crystal Structure where R = CH2C6H5 ; data_nr0505 _database_code_depnum_ccdc_archive 'CCDC 656892' #Notes to referee: #Compound 1b in m/s #Checkcif output is given under refine_special_details. _audit_creation_method SHELXL-97 _chemical_compound_source 'Elaine Geary, Reaction EG25F' _exptl_crystal_recrystallization_method 'From saturated DMF solution layered with MeCN and Et2O' _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C21 H18 N2 Ni S7' _chemical_formula_sum 'C21 H18 N2 Ni S7' _chemical_formula_weight 581.50 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P n m a' _symmetry_int_tables_number 62 _symmetry_space_group_name_Hall '-P 2ac 2n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, z+1/2' 'x, -y+1/2, z' '-x+1/2, -y, z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, -z-1/2' '-x, y-1/2, -z' 'x-1/2, y, -z-1/2' _cell_length_a 19.1586(6) _cell_length_b 19.5819(5) _cell_length_c 6.1048(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2290.29(12) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 7912 _cell_measurement_theta_min 2 _cell_measurement_theta_max 27.5 _exptl_crystal_description lath _exptl_crystal_colour green _exptl_crystal_size_max 0.58 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.686 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1192 _exptl_absorpt_coefficient_mu 1.500 _exptl_absorpt_correction_type Multiscan _exptl_absorpt_correction_T_min 0.684 _exptl_absorpt_correction_T_max 0.900 _exptl_absorpt_process_details 'Sadabs v2004/1' _exptl_special_details ; Oxford Cryosystems lt device. ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_probe ? _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Smart APEX CCD' _diffrn_measurement_method Omega _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 25384 _diffrn_reflns_av_R_equivalents 0.0376 _diffrn_reflns_av_sigmaI/netI 0.0271 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 28.75 _reflns_number_total 2941 _reflns_number_gt 2487 _reflns_threshold_expression >2sigma(I) _computing_data_collection Smart _computing_cell_refinement Saint _computing_data_reduction Saint _computing_structure_solution Dirdif _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics XP _computing_publication_material 'Platon, Xcif, Encifer' _refine_special_details ; The molecule lies with its long axis in a crystallographic mirror plane. C42/C52 are disordered about the mirror (occupancies both 0.5). N-C and C-C were lightly restrained to 1.45 and 1.52 Ang. The part weight atoms wre refined with isotropic displacement parameters: refinement of adps for these atoms reduced R1 by only 0.02. Checkcif alerts: 761_ALERT_1_A CIF Contains no X-H Bonds ...................... ? 762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles .......... ? The H-atoms were all placed in calculated positions and treated with a riding model. 912_ALERT_3_B # Missing FCF Reflections Above STH/L=0.6 ...... 116 911_ALERT_3_C # Missing FCF Refl. Between TH(Min) & STH/L=0.6 1 All data to the edge of the detector were included, though this means that the highest resolution shell is incomplete. Stats: #=============================================================================== Resolution & Completeness Statistics (Cumulative) #=============================================================================== Theta sin(th)/Lambda Complete Expected Measured Missing #------------------------------------------------------------------------------- 20.82 0.500 1.000 1236 1236 0 23.01 0.550 1.000 1652 1652 0 25.24 0.600 1.000 2145 2144 1 #----------------------------------------------------------- ACTA Min. Res. ---- 27.51 0.650 0.999 2710 2707 3 28.75 0.677 0.962 3058 2941 117 241_ALERT_2_C Check High Ueq as Compared to Neighbors for S12 The Uij's of Ni1 are expected to be somewhat lower than those of the ligands. The values for S12 are not unreasonably high, though it is possible that some slight positional disorder arises in this site as a result of the disorder of the ligand about the mirror plane (see above): Principal mean square atomic displacements U 0.0216 0.0209 0.0164 Ni1 0.0680 0.0206 0.0178 S12 0.0224 0.0217 0.0165 C22 301_ALERT_3_C Main Residue Disorder ......................... 6.00 Perc. 779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 23.14 Deg. C42 -N32 -C52 1.555 1.555 3.555 795_ALERT_4_C C-Atom in CIF Coordinate List out of Sequence .. C22 No action taken. ; _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^)+(0.0433P)^2^+0.7538P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary Patterson _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment riding _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2941 _refine_ls_number_parameters 144 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0372 _refine_ls_R_factor_gt 0.0298 _refine_ls_wR_factor_ref 0.0758 _refine_ls_wR_factor_gt 0.0738 _refine_ls_goodness_of_fit_ref 1.046 _refine_ls_restrained_S_all 1.046 _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 Ni1 Ni 0.647081(14) 0.2500 0.13242(5) 0.01963(9) Uani 1 2 d S . . S11 S 0.69260(2) 0.33081(2) -0.06226(7) 0.02516(11) Uani 1 1 d . . . C21 C 0.73781(8) 0.28445(8) -0.2575(3) 0.0214(3) Uani 1 1 d . . . S31 S 0.78670(2) 0.32348(2) -0.46334(7) 0.02655(11) Uani 1 1 d . . . C41 C 0.81680(11) 0.2500 -0.5882(4) 0.0226(5) Uani 1 2 d S . . S51 S 0.87032(3) 0.2500 -0.80073(11) 0.03205(16) Uani 1 2 d S . . S12 S 0.59938(3) 0.32812(2) 0.32880(8) 0.03544(14) Uani 1 1 d . . . C22 C 0.55208(8) 0.28771(8) 0.5234(3) 0.0202(3) Uani 1 1 d . . . N32 N 0.51728(7) 0.32092(7) 0.6774(2) 0.0216(3) Uani 1 1 d D . . C42 C 0.4861(2) 0.28722(17) 0.8627(6) 0.0231(7) Uiso 0.50 1 d PD . -1 H42A H 0.4456 0.3141 0.9148 0.028 Uiso 0.50 1 calc PR . -1 H42B H 0.5205 0.2845 0.9835 0.028 Uiso 0.50 1 calc PR . -1 C52 C 0.4625(2) 0.21637(17) 0.8020(6) 0.0227(7) Uiso 0.50 1 d PD . -1 H52A H 0.4511 0.1906 0.9369 0.027 Uiso 0.50 1 calc PR . -1 H52B H 0.4196 0.2194 0.7121 0.027 Uiso 0.50 1 calc PR . -1 C62 C 0.52155(9) 0.39565(8) 0.7071(3) 0.0264(4) Uani 1 1 d . . . H62A H 0.5561 0.4146 0.6031 0.032 Uiso 1 1 calc R . . H62B H 0.5379 0.4058 0.8575 0.032 Uiso 1 1 calc R . . C72 C 0.45191(9) 0.42973(8) 0.6702(3) 0.0246(4) Uani 1 1 d . . . C82 C 0.41821(10) 0.42409(10) 0.4704(3) 0.0358(4) Uani 1 1 d . . . H82 H 0.4390 0.3983 0.3559 0.043 Uiso 1 1 calc R . . C92 C 0.35456(11) 0.45563(12) 0.4357(4) 0.0474(5) Uani 1 1 d . . . H92 H 0.3313 0.4507 0.2992 0.057 Uiso 1 1 calc R . . C102 C 0.32488(11) 0.49437(10) 0.6002(4) 0.0455(5) Uani 1 1 d . . . H102 H 0.2817 0.5170 0.5752 0.055 Uiso 1 1 calc R . . C112 C 0.35749(10) 0.50033(10) 0.7998(4) 0.0393(5) Uani 1 1 d . . . H112 H 0.3368 0.5268 0.9128 0.047 Uiso 1 1 calc R . . C122 C 0.42076(10) 0.46753(9) 0.8359(3) 0.0309(4) Uani 1 1 d . . . H122 H 0.4428 0.4710 0.9748 0.037 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 Ni1 0.01763(16) 0.02087(16) 0.02038(16) 0.000 0.00222(11) 0.000 S11 0.0269(2) 0.0208(2) 0.0278(2) -0.00034(15) 0.00780(17) 0.00014(15) C21 0.0181(8) 0.0269(8) 0.0192(8) 0.0007(6) 0.0017(6) 0.0005(6) S31 0.0264(2) 0.0261(2) 0.0271(2) 0.00293(16) 0.00685(17) -0.00071(16) C41 0.0151(11) 0.0308(12) 0.0221(11) 0.000 -0.0017(9) 0.000 S51 0.0275(3) 0.0462(4) 0.0224(3) 0.000 0.0059(2) 0.000 S12 0.0469(3) 0.0195(2) 0.0399(3) -0.00137(17) 0.0240(2) -0.00373(18) C22 0.0174(7) 0.0210(8) 0.0223(8) -0.0004(6) -0.0004(6) -0.0019(6) N32 0.0196(7) 0.0210(6) 0.0242(7) -0.0026(5) 0.0020(5) -0.0002(5) C62 0.0227(8) 0.0208(7) 0.0358(10) -0.0082(7) 0.0032(7) -0.0015(7) C72 0.0220(8) 0.0185(7) 0.0333(9) -0.0031(7) 0.0043(7) -0.0024(6) C82 0.0373(10) 0.0350(10) 0.0351(11) -0.0042(8) -0.0014(8) 0.0048(8) C92 0.0420(12) 0.0448(12) 0.0555(14) 0.0007(11) -0.0180(10) 0.0025(9) C102 0.0268(10) 0.0302(10) 0.0796(17) 0.0027(10) -0.0015(10) 0.0050(8) C112 0.0306(10) 0.0229(9) 0.0645(14) -0.0077(9) 0.0147(10) 0.0001(7) C122 0.0297(9) 0.0232(8) 0.0397(11) -0.0080(7) 0.0077(8) -0.0036(7) _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 Ni1 S12 2.1477(5) . ? Ni1 S12 2.1477(5) 3 ? Ni1 S11 2.1627(4) . ? Ni1 S11 2.1628(4) 3 ? S11 C21 1.7306(16) . ? C21 C21 1.349(3) 3 ? C21 S31 1.7440(16) . ? S31 C41 1.7274(14) . ? C41 S51 1.654(2) . ? C41 S31 1.7275(13) 3 ? S12 C22 1.6908(16) . ? C22 N32 1.323(2) . ? C22 C22 1.477(3) 3 ? N32 C42 1.440(3) . ? N32 C62 1.477(2) . ? N32 C52 1.488(4) 3 ? C42 C52 1.506(4) . ? C52 N32 1.488(4) 3 ? C62 C72 1.509(2) . ? C72 C82 1.385(3) . ? C72 C122 1.388(2) . ? C82 C92 1.383(3) . ? C92 C102 1.381(3) . ? C102 C112 1.374(3) . ? C112 C122 1.389(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 S12 Ni1 S12 90.84(3) . 3 ? S12 Ni1 S11 87.544(16) . . ? S12 Ni1 S11 178.23(2) 3 . ? S12 Ni1 S11 178.23(2) . 3 ? S12 Ni1 S11 87.541(16) 3 3 ? S11 Ni1 S11 94.07(2) . 3 ? C21 S11 Ni1 101.32(6) . . ? C21 C21 S11 121.65(5) 3 . ? C21 C21 S31 116.00(5) 3 . ? S11 C21 S31 122.35(9) . . ? C41 S31 C21 97.60(9) . . ? S51 C41 S31 123.59(7) . . ? S51 C41 S31 123.59(7) . 3 ? S31 C41 S31 112.81(13) . 3 ? C22 S12 Ni1 106.68(5) . . ? N32 C22 C22 119.43(9) . 3 ? N32 C22 S12 122.64(12) . . ? C22 C22 S12 117.90(5) 3 . ? C22 N32 C42 122.83(18) . . ? C22 N32 C62 123.11(14) . . ? C42 N32 C62 112.38(18) . . ? C22 N32 C52 118.52(17) . 3 ? C42 N32 C52 23.14(16) . 3 ? C62 N32 C52 117.56(17) . 3 ? N32 C42 C52 110.7(3) . . ? N32 C52 C42 111.5(3) 3 . ? N32 C62 C72 111.77(13) . . ? C82 C72 C122 118.94(17) . . ? C82 C72 C62 120.57(15) . . ? C122 C72 C62 120.50(16) . . ? C92 C82 C72 120.67(19) . . ? C102 C92 C82 119.8(2) . . ? C112 C102 C92 120.27(19) . . ? C102 C112 C122 119.86(19) . . ? C72 C122 C112 120.41(19) . . ? _diffrn_measured_fraction_theta_max 0.962 _diffrn_reflns_theta_full 27.51 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.499 _refine_diff_density_min -0.545 _refine_diff_density_rms 0.077