Incorporation of Pendant Bases into Rh(diphosphine)2 Complexes: Synthesis, Thermodynamic Studies, And Catalytic CO2 Hydrogenation Activity of [Rh(P2N2)2](+) Complexes.
Lilio, Alyssia M.; Reineke, Mark H.; Moore, Curtis E.; Rheingold, Arnold L.; Takase, Michael K.; Kubiak, Clifford P.; Journal of the American Chemical Society 137 (2015) 8251–8260; doi:10.1021/jacs.5b04291

data_4123899
_publ_section_title
;
 Incorporation of Pendant Bases into Rh(diphosphine)2 Complexes:
 Synthesis, Thermodynamic Studies, And Catalytic CO2 Hydrogenation
 Activity of [Rh(P2N2)2](+) Complexes.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8251
_journal_page_last               8260
_journal_paper_doi               10.1021/jacs.5b04291
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C56 H81 N4 P4 Rh'
_chemical_formula_sum            'C56 H81 N4 P4 Rh'
_chemical_formula_weight         1037.03
_space_group_crystal_system      tetragonal
_space_group_IT_number           82
_space_group_name_Hall           'I -4'
_space_group_name_H-M_alt        'I -4'
_symmetry_space_group_name_Hall  'I -4'
_symmetry_space_group_name_H-M   'I -4'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-11-26
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.11.25 svn.r3098 for OlexSys, GUI svn.r4951)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.7640(7)
_cell_length_b                   22.7640(7)
_cell_length_c                   20.1397(5)
_cell_measurement_reflns_used    9879
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.479
_cell_measurement_theta_min      2.241
_cell_volume                     10436.4(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker Photon-100 area detector'
_diffrn_detector_area_resol_mean 10.5
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'four-circle KAPPA diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0487
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_laue_measured_fraction_full 0.999
_diffrn_reflns_laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            76059
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.491
_diffrn_reflns_theta_min         2.242
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\mus'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.491
_exptl_absorpt_correction_T_max  0.0942
_exptl_absorpt_correction_T_min  0.0691
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/4 (Bruker,2014/4) was used for absorption correction. wR2(int) was 0.0683 before and 0.0611 after correction. The Ratio of minimum to maximum transmission is 0.7335. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       prism
_exptl_crystal_F_000             4400
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.254
_refine_diff_density_min         -0.745
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.45(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     591
_refine_ls_number_reflns         11992
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0573
_refine_ls_R_factor_gt           0.0446
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0424P)^2^+22.5519P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0972
_refine_ls_wR_factor_ref         0.1035
_reflns_Friedel_coverage         0.943
_reflns_friedel_fraction_full    1.000
_reflns_friedel_fraction_max     1.000
_reflns_number_gt                10477
_reflns_number_total             11992
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b04291_si_008.cif
_cod_data_source_block           mo_p14016_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/usr/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 3271 2015-04-21 07:52:19Z andrius 
;
_cod_original_cell_volume        10436.4(7)
_cod_database_code               4123899
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.875
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H1A(0.04) H1B(0.04) H2A(0.05) H2B(0.05) H3A(0.048) H3B(0.048)
 H4A(0.047) H4B(0.047) H5A(0.08) H5B(0.08) H6A(0.059) H6B(0.059) H7A(0.079)
 H7B(0.079) H8A(0.05) H8B(0.05) H9(0.035) H10A(0.044) H10B(0.044) H11A(0.048)
 H11B(0.048) H12A(0.054) H12B(0.054) H13A(0.054) H13B(0.054) H14A(0.042)
 H14B(0.042) H16(0.046) H17(0.056) H18(0.061) H19(0.06) H20(0.05) H22(0.05)
 H23(0.058) H24(0.061) H25(0.059) H26(0.049) H27(0.039) H28A(0.049) H28B(0.049)
 H29A(0.055) H29B(0.055) H30A(0.062) H30B(0.062) H31A(0.067) H31B(0.067)
 H32A(0.053) H32B(0.053) H33(0.042) H34A(0.05) H34B(0.05) H35A(0.061)
 H35B(0.061) H36A(0.063) H36B(0.063) H37A(0.071) H37B(0.071) H38A(0.06)
 H38B(0.06) H40(0.056) H41(0.067) H42(0.065) H43(0.068) H44(0.051) H46(0.055)
 H47(0.07) H48(0.075) H49(0.073) H50(0.059) H51(0.05) H52A(0.065) H52B(0.065)
 H53A(0.068) H53B(0.068) H54A(0.066) H54B(0.066) H55A(0.061) H55B(0.061)
 H56A(0.05) H56B(0.05)
 Fixed X: H1A(0.2135) H1B(0.2408) H2A(0.3344) H2B(0.2709) H3A(0.1108)
 H3B(0.1094) H4A(0.2063) H4B(0.1702) H5A(0.3677) H5B(0.3188) H6A(0.2229)
 H6B(0.2117) H7A(0.3054) H7B(0.2671) H8A(0.1512) H8B(0.1477) H9(0.1397)
 H10A(0.2158) H10B(0.2282) H11A(0.1946) H11B(0.151) H12A(0.0956) H12B(0.1306)
 H13A(0.039) H13B(0.0542) H14A(0.0727) H14B(0.115) H16(0.0835) H17(0.0194)
 H18(0.0088) H19(0.0649) H20(0.1288) H22(0.3125) H23(0.3932) H24(0.4801)
 H25(0.482) H26(0.4001) H27(0.3063) H28A(0.3663) H28B(0.3866) H29A(0.4097)
 H29B(0.444) H30A(0.3986) H30B(0.3765) H31A(0.2954) H31B(0.3135) H32A(0.2368)
 H32B(0.2731) H33(0.3938) H34A(0.3428) H34B(0.3544) H35A(0.4241) H35B(0.4441)
 H36A(0.463) H36B(0.5134) H37A(0.4962) H37B(0.5087) H38A(0.4059) H38B(0.4259)
 H40(0.4037) H41(0.4465) H42(0.3892) H43(0.2877) H44(0.2441) H46(0.2842)
 H47(0.2549) H48(0.1563) H49(0.0875) H50(0.1141) H51(0.1116) H52A(0.1351)
 H52B(0.1499) H53A(0.0488) H53B(0.0649) H54A(0.0298) H54B(-0.022) H55A(-0.0005)
 H55B(-0.0154) H56A(0.0681) H56B(0.0841)
 Fixed Y: H1A(0.2201) H1B(0.1584) H2A(0.3052) H2B(0.3082) H3A(0.266)
 H3B(0.2334) H4A(0.3815) H4B(0.3654) H5A(0.264) H5B(0.2335) H6A(0.2812)
 H6B(0.3409) H7A(0.1333) H7B(0.1115) H8A(0.1658) H8B(0.2038) H9(0.1252)
 H10A(0.0906) H10B(0.0791) H11A(-0.0081) H11B(0.0107) H12A(-0.0147)
 H12B(0.0325) H13A(0.0733) H13B(0.0616) H14A(0.1613) H14B(0.1433) H16(0.2635)
 H17(0.3104) H18(0.4114) H19(0.4666) H20(0.4217) H22(0.1126) H23(0.0624)
 H24(0.1128) H25(0.2147) H26(0.2666) H27(0.4047) H28A(0.3402) H28B(0.3425)
 H29A(0.4432) H29B(0.408) H30A(0.4948) H30B(0.4371) H31A(0.4946) H31B(0.4987)
 H32A(0.43) H32B(0.394) H33(0.156) H34A(0.0903) H34B(0.1329) H35A(0.0564)
 H35B(0.0714) H36A(0.145) H36B(0.1116) H37A(0.1706) H37B(0.2121) H38A(0.2283)
 H38B(0.2481) H40(0.3315) H41(0.4134) H42(0.4923) H43(0.4873) H44(0.4058)
 H46(0.0779) H47(0.0047) H48(-0.0103) H49(0.0519) H50(0.1272) H51(0.3031)
 H52A(0.3522) H52B(0.3829) H53A(0.3962) H53B(0.4256) H54A(0.3395) H54B(0.3657)
 H55A(0.2974) H55B(0.2639) H56A(0.2224) H56B(0.2466)
 Fixed Z: H1A(0.2709) H1B(0.2493) H2A(0.2273) H2B(0.261) H3A(0.1474)
 H3B(0.2176) H4A(0.2089) H4B(0.1433) H5A(-0.0738) H5B(-0.1189) H6A(-0.1291)
 H6B(-0.0897) H7A(-0.0916) H7B(-0.0301) H8A(-0.0388) H8B(-0.1051) H9(0.2073)
 H10A(0.0995) H10B(0.1766) H11A(0.1232) H11B(0.1818) H12A(0.0876) H12B(0.0437)
 H13A(0.0765) H13B(0.153) H14A(0.1286) H14B(0.0686) H16(0.3057) H17(0.3771)
 H18(0.3773) H19(0.3032) H20(0.2293) H22(0.2431) H23(0.2783) H24(0.3092)
 H25(0.3002) H26(0.2663) H27(0.1697) H28A(0.067) H28B(0.1431) H29A(0.1337)
 H29B(0.0767) H30A(0.0354) H30B(-0.0027) H31A(0.021) H31B(0.0977) H32A(0.0868)
 H32B(0.0322) H33(-0.0316) H34A(0.039) H34B(0.1009) H35A(0.1029) H35B(0.0286)
 H36A(0.142) H36B(0.1012) H37A(0.0084) H37B(0.0711) H38A(0.0845) H38B(0.0116)
 H40(-0.1097) H41(-0.1542) H42(-0.1904) H43(-0.1772) H44(-0.1289) H46(-0.1567)
 H47(-0.228) H48(-0.2526) H49(-0.2077) H50(-0.1351) H51(-0.0762) H52A(0.0525)
 H52B(-0.0169) H53A(-0.0386) H53B(0.0315) H54A(0.0888) H54B(0.0436) H55A(-
 0.0402) H55B(0.0276) H56A(-0.0248) H56B(0.0476)
;
_shelx_res_checksum              59035
_shelx_hkl_checksum              87132
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'