#------------------------------------------------------------------------------ #$Date: 2010-01-30 15:59:17 +0200 (Sat, 30 Jan 2010) $ #$Revision: 966 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/1100789.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_1100789 _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 'C24 H30 Ir2 N4 O2' _[local]_cod_chemical_formula_sum_orig 'C24 H30 Ir2 N4 O2 ' _chemical_formula_moiety 'C24 H30 Ir2 N4 O2 ' _chemical_formula_weight 790.97 _chemical_melting_point ? _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 '+X,+Y,+Z' 2 '-X,-Y,-Z' _cell_length_a 8.888(5) _cell_length_b 11.704(4) _cell_length_c 12.696(4) _cell_angle_alpha 88.75(3) _cell_angle_beta 86.05(4) _cell_angle_gamma 76.30(4) _cell_volume 1280.2(9) _cell_formula_units_Z 2 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 19.9 _cell_measurement_theta_max 20.0 _cell_measurement_temperature 294.1 _exptl_crystal_description 'needle' _exptl_crystal_colour 'dark brown' _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.10 _exptl_crystal_density_diffrn 2.052 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 744.00 _exptl_absorpt_coefficient_mu 10.440 _exptl_absorpt_correction_type psi-scans _exptl_absorpt_process_details '(North, Phillips & Mathews, 1968)' _exptl_absorpt_correction_T_min 0.144 _exptl_absorpt_correction_T_max 0.352 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.7107 _diffrn_measurement_device_type 'Rigaku AFC7R' _diffrn_measurement_method \w-2\q _diffrn_reflns_number 6165 _diffrn_reflns_av_R_equivalents 0.021 _diffrn_reflns_theta_max 27.51 _diffrn_measured_fraction_theta_max 0.9959 _diffrn_reflns_theta_full 27.51 _diffrn_measured_fraction_theta_full 0.9959 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_standards_number 3 _diffrn_standards_interval_count 0 _diffrn_standards_decay_% 0.01 _reflns_number_total 5779 _reflns_number_gt 4755 _reflns_threshold_expression F^2^>3.0\s(F^2^) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.0260 _refine_ls_wR_factor_ref 0.0260 _refine_ls_hydrogen_treatment refall _refine_ls_number_reflns 4755 _refine_ls_number_parameters 320 _refine_ls_goodness_of_fit_ref 1.006 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[0.0001Fo^2^ + 1.8000\s(Fo^2^) + 0.5000]' _refine_ls_shift/su_max 0.0000 _refine_diff_density_max 1.21 #(0.690, 0.888, 0.803) _refine_diff_density_min -1.35 _refine_ls_extinction_method 'Larson (1970) Crystallographic Computing eq. 22' _refine_ls_extinction_coef 38(3) 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) ; 'O' 'O' 0.011 0.006 ; 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 0.75251(3) 0.64738(2) 0.76861(2) 0.04492(7) Uani 1.00 1 d . . . Ir(2) Ir 0.66854(2) 0.96071(2) 0.77909(1) 0.03169(6) Uani 1.00 1 d . . . O(1) O 0.4675(5) 0.7028(5) 0.6589(5) 0.090(2) Uani 1.00 1 d . . . O(2) O 0.550(1) 0.5936(7) 0.9517(7) 0.185(4) Uani 1.00 1 d . . . N(1) N 0.5312(5) 0.8681(4) 0.7117(4) 0.045(1) Uani 1.00 1 d . . . N(2) N 0.2909(7) 0.9836(6) 0.6348(5) 0.084(2) Uani 1.00 1 d . . . N(3) N 0.7620(5) 0.8053(4) 0.8366(3) 0.041(1) Uani 1.00 1 d . . . N(4) N 0.9530(7) 0.7755(5) 0.9740(4) 0.064(2) Uani 1.00 1 d . . . C(1) C 0.5558(7) 0.7451(6) 0.7048(5) 0.055(2) Uani 1.00 1 d . . . C(2) C 0.4020(7) 0.9287(6) 0.6686(5) 0.055(2) Uani 1.00 1 d . . . C(3) C 0.8637(7) 0.7898(5) 0.9090(4) 0.044(1) Uani 1.00 1 d . . . C(4) C 0.630(1) 0.6151(7) 0.8821(7) 0.096(3) Uani 1.00 1 d . . . C(5) C 0.8825(7) 0.6176(5) 0.6097(4) 0.053(2) Uani 1.00 1 d . . . C(6) C 0.9921(7) 0.6261(5) 0.6832(5) 0.054(2) Uani 1.00 1 d . . . C(7) C 1.0015(8) 0.5352(6) 0.7591(6) 0.066(2) Uani 1.00 1 d . . . C(8) C 0.896(1) 0.4674(5) 0.7326(6) 0.070(2) Uani 1.00 1 d . . . C(9) C 0.8193(8) 0.5174(6) 0.6400(5) 0.064(2) Uani 1.00 1 d . . . C(10) C 0.845(1) 0.6928(8) 0.5139(6) 0.095(3) Uani 1.00 1 d . . . C(11) C 1.0834(8) 0.7184(7) 0.6812(7) 0.085(3) Uani 1.00 1 d . . . C(12) C 1.114(1) 0.5056(8) 0.8448(7) 0.107(3) Uani 1.00 1 d . . . C(13) C 0.872(2) 0.3563(7) 0.7861(8) 0.129(4) Uani 1.00 1 d . . . C(14) C 0.711(1) 0.4690(8) 0.5789(7) 0.102(3) Uani 1.00 1 d . . . C(15) C 0.7708(6) 1.0918(5) 0.7028(4) 0.040(1) Uani 1.00 1 d . . . C(16) C 0.8218(6) 1.0733(4) 0.8096(4) 0.037(1) Uani 1.00 1 d . . . C(17) C 0.6868(6) 1.1019(4) 0.8792(4) 0.041(1) Uani 1.00 1 d . . . C(18) C 0.5512(6) 1.1408(5) 0.8164(4) 0.046(1) Uani 1.00 1 d . . . C(19) C 0.6068(6) 1.1381(5) 0.7080(4) 0.046(2) Uani 1.00 1 d . . . C(20) C 0.8761(8) 1.0735(6) 0.6044(4) 0.058(2) Uani 1.00 1 d . . . C(21) C 0.9854(6) 1.0350(5) 0.8390(5) 0.048(2) Uani 1.00 1 d . . . C(22) C 0.6838(8) 1.0992(6) 0.9975(4) 0.061(2) Uani 1.00 1 d . . . C(23) C 0.3867(8) 1.1828(7) 0.8595(6) 0.076(2) Uani 1.00 1 d . . . C(24) C 0.5117(8) 1.1785(6) 0.6159(5) 0.071(2) Uani 1.00 1 d . . . H(1) H 0.8071 0.7733 0.5321 0.105 Uiso 1.00 1 c R . . H(2) H 0.9345 0.6844 0.4666 0.105 Uiso 1.00 1 c R . . H(3) H 0.7671 0.6659 0.4809 0.105 Uiso 1.00 1 c R . . H(4) H 1.1474 0.7046 0.7393 0.102 Uiso 1.00 1 c R . . H(5) H 1.1467 0.7123 0.6172 0.102 Uiso 1.00 1 c R . . H(6) H 1.0171 0.7950 0.6865 0.102 Uiso 1.00 1 c R . . H(7) H 1.0630 0.4980 0.9120 0.120 Uiso 1.00 1 c R . . H(8) H 1.1884 0.4345 0.8281 0.120 Uiso 1.00 1 c R . . H(9) H 1.1647 0.5684 0.8465 0.120 Uiso 1.00 1 c R . . H(10) H 0.8265 0.3794 0.8546 0.154 Uiso 1.00 1 c R . . H(11) H 0.8015 0.3259 0.7483 0.154 Uiso 1.00 1 c R . . H(12) H 0.9651 0.2975 0.7920 0.154 Uiso 1.00 1 c R . . H(13) H 0.6194 0.5294 0.5740 0.126 Uiso 1.00 1 c R . . H(14) H 0.7560 0.4471 0.5100 0.126 Uiso 1.00 1 c R . . H(15) H 0.6869 0.4027 0.6142 0.126 Uiso 1.00 1 c R . . H(16) H 0.9811 1.0426 0.6197 0.072 Uiso 1.00 1 c R . . H(17) H 0.8436 1.0198 0.5611 0.072 Uiso 1.00 1 c R . . H(18) H 0.8669 1.1466 0.5684 0.072 Uiso 1.00 1 c R . . H(19) H 0.9987 0.9655 0.8808 0.060 Uiso 1.00 1 c R . . H(20) H 1.0506 1.0198 0.7760 0.060 Uiso 1.00 1 c R . . H(21) H 1.0120 1.0953 0.8776 0.060 Uiso 1.00 1 c R . . H(22) H 0.5799 1.1242 1.0262 0.073 Uiso 1.00 1 c R . . H(23) H 0.7263 1.0209 1.0198 0.073 Uiso 1.00 1 c R . . H(24) H 0.7438 1.1496 1.0213 0.073 Uiso 1.00 1 c R . . H(25) H 0.3478 1.2625 0.8395 0.086 Uiso 1.00 1 c R . . H(26) H 0.3266 1.1353 0.8308 0.086 Uiso 1.00 1 c R . . H(27) H 0.3805 1.1763 0.9343 0.086 Uiso 1.00 1 c R . . H(28) H 0.5468 1.2403 0.5800 0.085 Uiso 1.00 1 c R . . H(29) H 0.5232 1.1141 0.5693 0.085 Uiso 1.00 1 c R . . H(30) H 0.4054 1.2055 0.6390 0.085 Uiso 1.00 1 c R . . _cod_database_code 1100789