The Influence of the Second and Outer Coordination Spheres on Rh(diphosphine)2 CO2 Hydrogenation Catalysts
Bays, John Timothy; Priyadarshani, Nilusha; Jeletic, Matthew S.; Hulley, Elliot B.; Miller, Deanna L.; Linehan, John C.; Shaw, Wendy J.; ACS Catalysis  (2014) 140903144432009–; doi:10.1021/cs5009199

data_4511983
_publ_contact_author_name
;
;
_publ_section_title
;
 The Influence of the Second and Outer Coordination Spheres on
 Rh(diphosphine)2 CO2 Hydrogenation Catalysts
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_journal_name_full               'ACS Catalysis'
_journal_page_first              140903144432009
_journal_paper_doi               10.1021/cs5009199
_journal_year                    2014
_chemical_formula_moiety         'C54 H52 P4 Rh, C F3 O3 S, C4 H8 O'
_chemical_formula_sum            'C59 H60 F3 O4 P4 Rh S'
_chemical_formula_weight         1148.92
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-11-11
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.4290(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.7463(5)
_cell_length_b                   15.5086(7)
_cell_length_c                   13.5727(6)
_cell_measurement_reflns_used    9333
_cell_measurement_temperature    100
_cell_measurement_theta_max      32.013
_cell_measurement_theta_min      2.630
_cell_volume                     2530.23(19)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
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O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            63838
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.017
_diffrn_reflns_theta_min         1.900
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.566
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9152
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0799 before and 0.0446 after correction.
The Ratio of minimum to maximum transmission is 0.9152.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.508
_exptl_crystal_description       prism
_exptl_crystal_F_000             1188
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.568
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         8769
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0287
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0287P)^2^+1.5685P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0650
_refine_ls_wR_factor_ref         0.0696
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7375
_reflns_number_total             8769
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs5009199_si_002.cif
_cod_data_source_block           '[Rh(dppp)2]OTf'
_cod_database_code               4511983
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C56-F3
 1.322 with sigma of 0.02
 C56-F2
 1.322 with sigma of 0.02
 F1-C56
 1.322 with sigma of 0.02
 S1-C56
 1.814 with sigma of 0.02
 S1-O2
 1.433 with sigma of 0.02
 S1-O3
 1.433 with sigma of 0.02
 S1-O1
 1.433 with sigma of 0.02
 O4-C81 \\sim O4-C84
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(S1) = Uanis(S2)
Uanis(O1) = Uanis(O7)
Uanis(O2) = Uanis(O5)
Uanis(O6) = Uanis(O3)
Uanis(C56) = Uanis(C1I)
Uanis(F2) = Uanis(F8)
Uanis(F1) = Uanis(F7)
Uanis(F3) = Uanis(F9)
4. Others
 Sof(S2)=Sof(O5)=Sof(O6)=Sof(O7)=Sof(C1I)=Sof(F7)=Sof(F8)=Sof(F9)=0.5*(1-
 FVAR(2))
 Sof(S1)=Sof(O2)=Sof(O3)=Sof(O1)=Sof(F3)=Sof(F1)=Sof(F2)=Sof(C56)=0.5*FVAR(2)
 Fixed Sof: O4(0.5) C84(0.5) H84A(0.5) H84B(0.5) C81(0.5) H81A(0.5) H81B(0.5)
 C82(0.5) H82A(0.5) H82B(0.5) C83(0.5) H83A(0.5) H83B(0.5)
5.a Free rotating group:
 S2(O5,O6,O7,C1I,F7,F8,F9)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C9(H9A,H9B), C1B(H1BA,H1BB), C84(H84A,H84B), C81(H81A,H81B),
 C82(H82A,H82B), C83(H83A,H83B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C6(H6), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12), C14(H14),
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C1A(H1A), C1C(H1C), C1D(H1D),
  C1E(H1E), C1F(H1F), C1G(H1G), C1H(H1H)
;
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.925
_shelx_hkl_checksum              73279
_shelx_res_checksum              30914
_shelxl_version_number           2013-2