#------------------------------------------------------------------------------ #$Date: 2008-01-14 00:15:36 +0200 (Mon, 14 Jan 2008) $ #$Revision: 14 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/1100788.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_1100788 _publ_requested_journal 'Organometallics' _publ_section_title ; Cyanamido-Bridged Diiridium Complex: a Reactive Building Block for Polynuclear Cyanamido Complexes ; loop_ _publ_author_name 'Hidenobu Kajitani' 'Yoshiaki Tanabe' 'Shigeki Kuwata' 'Masakazu Iwasaki' _publ_section_synopsis ; [Cp*IrCl2]2 reacts with 2 equiv of Na2NCN to afford the NCN-bridged diiridium complex [Cp*Ir(\m2-NCN-N,N)]2 (5), which undergoes further reactions with donor molecules such as CO and phosphines. Complex 5 works as an excellent building block for the synthesis of the NCN-capped heterotrinuclear complexes [(Cp*Ir)2(ML)(\m3-NCN-N,N,N)2]+ (ML = Rh(cod), CpRu, Pd(\m3-C3H5)) in reactions with cationic group 8-10 metal complexes such as [Rh(cod)(acetone)n]+, [CpRu(MeCN)3]+, and [Pd(\m3-C3H5)(acetone)n]+, while the dimerization of 5 leads to the cubane-type tetrairidium complex [Cp*Ir(\m3-NCN-N,N,N)]4. ; _publ_section_abstract ; [Cp*IrCl2]2 reacts with 2 equiv of Na2NCN to afford the NCN-bridged diiridium complex [Cp*Ir(\m2-NCN-N,N)]2 (5), which undergoes further reactions with donor molecules such as CO and phosphines. Complex 5 works as an excellent building block for the synthesis of the NCN-capped heterotrinuclear complexes [(Cp*Ir)2(ML)(\m3-NCN-N,N,N)2]+ (ML = Rh(cod), CpRu, Pd(\m3-C3H5)) in reactions with cationic group 8-10 metal complexes such as [Rh(cod)(acetone)n]+, [CpRu(MeCN)3]+, and [Pd(\m3-C3H5)(acetone)n]+, while the dimerization of 5 leads to the cubane-type tetrairidium complex [Cp*Ir(\m3-NCN-N,N,N)]4. ; _publ_section_exptl_prep ; Reaction of 1 and 2 equiv Na2NCN at room temperature affords 5. 4 reacts with CO, PMe3, dppm, and [Cp*Rh(acetone)n]+ to afford 6.8d, 9, and 10a, respectively. ; _publ_section_exptl_refinement ; Crystals of 5, 6, 8d, 9, and 10a are obtained by recrystallization from CH2Cl2-ether, toluene-hexane, benzene-hexane, benzene-hexane, and CH2Cl2-methanol, respectively. ; _chemical_formula_sum 'C22 H30 Ir2 N4 ' _chemical_formula_moiety 'C22 H30 Ir2 N4 ' _chemical_formula_weight 734.95 _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P n m a' _symmetry_space_group_name_Hall '-P 2ac 2n' _symmetry_Int_Tables_number 62 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 '+X,+Y,+Z' 2 '1/2-X,1/2+Y,1/2+Z' 3 '+X,1/2-Y,+Z' 4 '1/2-X,-Y,1/2+Z' 5 '-X,-Y,-Z' 6 '1/2+X,1/2-Y,1/2-Z' 7 '-X,1/2+Y,-Z' 8 '1/2+X,+Y,1/2-Z' _cell_length_a 21.365(6) _cell_length_b 15.428(5) _cell_length_c 6.697(5) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 2207(1) _cell_formula_units_Z 4 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 19.8 _cell_measurement_theta_max 20.0 _cell_measurement_temperature 294.1 _exptl_crystal_description 'needle' _exptl_crystal_colour 'dark red' _exptl_crystal_size_max 0.70 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.20 _exptl_crystal_density_diffrn 2.211 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1376.00 _exptl_absorpt_coefficient_mu 12.093 _exptl_absorpt_correction_type psi-scans _exptl_absorpt_process_details '(North, Phillips & Mathews, 1968)' _exptl_absorpt_correction_T_min 0.033 _exptl_absorpt_correction_T_max 0.089 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_measurement_device_type 'Rigaku AFC7R' _diffrn_measurement_method \w _diffrn_reflns_number 2908 _diffrn_reflns_av_R_equivalents ? _diffrn_reflns_theta_max 27.51 _diffrn_measured_fraction_theta_max 0.9898 _diffrn_reflns_theta_full 27.51 _diffrn_measured_fraction_theta_full 0.9898 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 27 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 0 _diffrn_standards_number 3 _diffrn_standards_interval_count 0 _diffrn_standards_decay_% 0.27 _reflns_number_total 2519 _reflns_number_gt 1731 _reflns_threshold_expression F^2^>3.0\s(F^2^) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.0520 _refine_ls_wR_factor_ref 0.0540 _refine_ls_hydrogen_treatment refall _refine_ls_number_reflns 1731 _refine_ls_number_parameters 156 _refine_ls_goodness_of_fit_ref 1.001 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[0.0004Fo^2^ + 4.0000\s(Fo^2^) + 0.5000]' _refine_ls_shift/su_max 0.0000 _refine_diff_density_max 5.93 #(0.459, 0.250, 0.193) _refine_diff_density_min -3.41 _refine_ls_extinction_method none _refine_ls_extinction_coef ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.003 0.002 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; 'H' 'H' 0.000 0.000 ; International Tables for Crystallography (1992, Vol. C, Table 6.1.1.4) ; 'N' 'N' 0.006 0.003 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; 'Ir' 'Ir' -1.444 7.990 ; International Tables for Crystallography (1992, 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 Ir(1) Ir 0.43198(3) 0.2500 0.31218(9) 0.0270(2) Uani 1.00 2 d S . . Ir(2) Ir 0.30015(3) 0.2500 0.3253(1) 0.0288(2) Uani 1.00 2 d S . . N(1) N 0.3668(5) 0.1705(9) 0.429(2) 0.048(4) Uani 1.00 1 d . . . N(2) N 0.3667(7) 0.013(1) 0.365(4) 0.098(6) Uani 1.00 1 d . . . C(1) C 0.3660(7) 0.087(1) 0.391(3) 0.066(5) Uani 1.00 1 d . . . C(2) C 0.4793(7) 0.2032(8) 0.057(2) 0.039(4) Uani 1.00 1 d . . . C(3) C 0.5140(7) 0.1755(9) 0.228(2) 0.042(4) Uani 1.00 1 d . . . C(4) C 0.5311(7) 0.2500 0.335(2) 0.032(5) Uani 1.00 2 d S . . C(5) C 0.4509(9) 0.148(1) -0.104(3) 0.076(6) Uani 1.00 1 d . . . C(6) C 0.524(1) 0.081(1) 0.275(3) 0.087(7) Uani 1.00 1 d . . . C(7) C 0.569(1) 0.25000(1) 0.514(3) 0.079(9) Uani 1.00 2 d S . . C(8) C 0.2485(6) 0.2026(8) 0.070(2) 0.036(4) Uani 1.00 1 d . . . C(9) C 0.2178(6) 0.1756(9) 0.253(2) 0.045(4) Uani 1.00 1 d . . . C(10) C 0.1997(8) 0.2500 0.364(3) 0.036(5) Uani 1.00 2 d S . . C(11) C 0.2749(8) 0.144(1) -0.087(2) 0.055(5) Uani 1.00 1 d . . . C(12) C 0.2074(9) 0.080(1) 0.306(3) 0.076(6) Uani 1.00 1 d . . . C(13) C 0.163(1) 0.25000(1) 0.555(4) 0.077(9) Uani 1.00 2 d S . . H(1) H 0.4218 0.1100 -0.0410 0.091 Uiso 1.00 1 c R . . H(2) H 0.4298 0.1814 -0.2020 0.091 Uiso 1.00 1 c R . . H(3) H 0.4827 0.1142 -0.1668 0.091 Uiso 1.00 1 c R . . H(4) H 0.5041 0.0692 0.3989 0.104 Uiso 1.00 1 c R . . H(5) H 0.5063 0.0455 0.1738 0.104 Uiso 1.00 1 c R . . H(6) H 0.5676 0.0685 0.2864 0.104 Uiso 1.00 1 c R . . H(7) H 0.5475 0.2192 0.6147 0.095 Uiso 0.50 1 c R . . H(8) H 0.6086 0.2227 0.4899 0.095 Uiso 0.50 1 c R . . H(9) H 0.5762 0.3080 0.5561 0.095 Uiso 0.50 1 c R . . H(10) H 0.2423 0.1093 -0.1403 0.066 Uiso 1.00 1 c R . . H(11) H 0.2932 0.1774 -0.1918 0.066 Uiso 1.00 1 c R . . H(12) H 0.3059 0.1082 -0.0288 0.066 Uiso 1.00 1 c R . . H(13) H 0.1639 0.0697 0.3234 0.092 Uiso 1.00 1 c R . . H(14) H 0.2233 0.0430 0.2051 0.092 Uiso 1.00 1 c R . . H(15) H 0.2286 0.0692 0.4282 0.092 Uiso 1.00 1 c R . . H(16) H 0.1571 0.3080 0.5995 0.092 Uiso 0.50 1 c R . . H(17) H 0.1230 0.2236 0.5356 0.092 Uiso 0.50 1 c R . . H(18) H 0.1855 0.2184 0.6527 0.092 Uiso 0.50 1 c R . .