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_4123902
_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         'C60 H65 N4 O4 P4 Rh, 1(C4 H8 O)'
_chemical_formula_sum            'C64 H73 N4 O5 P4 Rh'
_chemical_formula_weight         1205.05
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_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                 112.6250(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9890(2)
_cell_length_b                   48.2896(9)
_cell_length_c                   12.8422(3)
_cell_measurement_reflns_used    9571
_cell_measurement_temperature    100
_cell_measurement_theta_max      36.005
_cell_measurement_theta_min      2.216
_cell_volume                     5717.9(2)
_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 APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'four-circle KAPPA diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa APEX II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_laue_measured_fraction_full 1.000
_diffrn_reflns_laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       59
_diffrn_reflns_limit_k_min       -59
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            99820
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.687
_diffrn_source                   'sealed tube'
_diffrn_source_type              fine-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.465
_exptl_absorpt_correction_T_max  0.1138
_exptl_absorpt_correction_T_min  0.0657
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0578 before and 0.0526 after correction.
The Ratio of minimum to maximum transmission is 0.5773.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.400
_exptl_crystal_description       block
_exptl_crystal_F_000             2520
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.466
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.459(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1413
_refine_ls_number_reflns         22483
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0250
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0226P)^2^+3.3798P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0578
_refine_ls_wR_factor_ref         0.0582
_reflns_Friedel_coverage         0.975
_reflns_friedel_fraction_full    1.000
_reflns_friedel_fraction_max     1.000
_reflns_number_gt                22083
_reflns_number_total             22483
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b04291_si_007.cif
_cod_data_source_block           a14403_a
_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_database_code               4123902
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.909
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.541(14) 0.459(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Shared sites
{O2SC, C8SB}
{O2SB, C8SC}
4. Restrained distances
 O2SB-C6S = O2SB-C7SB = O2S-C5S = O2S-C8S = O2SC-C5S
 1.45 with sigma of 0.02
 C7S-C6S = C8S-C7S = C8SB-C7SB = C8SB-C5S
 1.54 with sigma of 0.02
 Rh1'-HA = Rh1-H
 1.6 with sigma of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(O2SC) = Uanis(C8SB)
Uanis(O2SB) = Uanis(C8SC)
Uanis(O2S) = Uanis(C6S) = Uanis(C5S) = Uanis(C7S) = Uanis(O2SB) = Uanis(C8SC) =
Uanis(C8SB) = Uanis(O2SC) = Uanis(C8S) = Uanis(C7SB) = Uanis(C7SC)
6. Others
 1*[Sof(O2S)+Sof(H5SA)+Sof(H5SB)+Sof(H6SA)+Sof(H6SB)+Sof(C7S)+Sof(H7SA)+
 Sof(H7SB)+Sof(C8S)+Sof(H8SA)+Sof(H8SB)]+1*[Sof(O2SB)+Sof(H5SC)+Sof(H5SD)+
 Sof(H6SC)+Sof(H6SD)+Sof(C7SB)+Sof(H7SC)+Sof(H7SD)+Sof(C8SB)+Sof(H8SC)+
 Sof(H8SD)]+1*[Sof(O2SC)+Sof(H5SE)+Sof(H5SF)+Sof(H6SE)+Sof(H6SF)+Sof(C7SC)+
 Sof(H7SE)+Sof(H7SF)+Sof(C8SC)+Sof(H8SE)+Sof(H8SF)]=1 with esd of 0.0001
 Sof(O2S)=Sof(H5SA)=Sof(H5SB)=Sof(H6SA)=Sof(H6SB)=Sof(C7S)=Sof(H7SA)=Sof(H7SB)=
 Sof(C8S)=Sof(H8SA)=Sof(H8SB)=FVAR(1)
 Sof(O2SB)=Sof(H5SC)=Sof(H5SD)=Sof(H6SC)=Sof(H6SD)=Sof(C7SB)=Sof(H7SC)=
 Sof(H7SD)=Sof(C8SB)=Sof(H8SC)=Sof(H8SD)=FVAR(2)
 Sof(O2SC)=Sof(H5SE)=Sof(H5SF)=Sof(H6SE)=Sof(H6SF)=Sof(C7SC)=Sof(H7SE)=
 Sof(H7SF)=Sof(C8SC)=Sof(H8SE)=Sof(H8SF)=FVAR(3)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C1'(H1'A,H1'B), C2'(H2'A,H2'B), C3'(H3'A,H3'B),
 C4'(H4'A,H4'B), C5'(H5'A,H5'B), C6'(H6'A,H6'B), C7'(H7'A,H7'B), C8'(H8'A,H8'B),
  C1S(H1SA,H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C5S(H5SA,
 H5SB), C5S(H5SC,H5SD), C5S(H5SE,H5SF), C6S(H6SA,H6SB), C6S(H6SC,H6SD),
 C6S(H6SE,H6SF), C7S(H7SA,H7SB), C8S(H8SA,H8SB), C7SB(H7SC,H7SD), C8SB(H8SC,
 H8SD), C7SC(H7SE,H7SF), C8SC(H8SE,H8SF)
7.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C19(H19), C20(H20), C23(H23), C24(H24), C26(H26), C27(H27), C30(H30), C31(H31),
  C32(H32), C33(H33), C34(H34), C36(H36), C37(H37), C38(H38), C39(H39),
 C40(H40), C42(H42), C43(H43), C45(H45), C46(H46), C49(H49), C50(H50), C52(H52),
  C53(H53), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C10'(H10'),
 C11'(H11'), C12'(H12'), C13'(H13'), C14'(H14'), C16'(H16'), C17'(H17'),
 C19'(H19'), C20'(H20'), C23'(H23'), C24'(H24'), C26'(H26'), C27'(H27'),
 C30'(H30'), C31'(H31'), C32'(H32'), C33'(H33'), C34'(H34'), C36'(H36'),
 C37'(H37'), C38'(H38'), C39'(H39'), C40'(H40'), C42'(H42'), C43'(H43'),
 C45'(H45'), C46'(H46'), C49'(H49'), C50'(H50'), C52'(H52'), C53'(H53'),
 C56'(H56'), C57'(H57'), C58'(H58'), C59'(H59'), C60'(H60')
7.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C28(H28A,H28B,H28C), C47(H47A,H47B,H47C), C54(H54A,H54B,
 H54C), C21'(H21D,H21E,H21F), C28'(H28D,H28E,H28F), C47'(H47D,H47E,H47F),
 C54'(H54D,H54E,H54F)
;
_shelx_res_checksum              85449
_shelx_hkl_checksum              27540
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'