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_4511984
_publ_contact_author_name
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;
_publ_section_title
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 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
'C56 H54 N2 O4 P4 Rh, 2.125(C4 H8 O), C F3 O3 S'
_chemical_formula_sum            'C65.5 H70.875 F3 N2 O9.125 P4 Rh S'
_chemical_formula_weight         1347.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2013-06-04
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_audit_update_record
;
2013-06-04 # Formatted by publCIF
;
_cell_angle_alpha                90
_cell_angle_beta                 91.499(4)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   12.4663(14)
_cell_length_b                   47.636(5)
_cell_length_c                   42.394(5)
_cell_measurement_reflns_used    9680
_cell_measurement_temperature    140(2)
_cell_measurement_theta_max      29.550
_cell_measurement_theta_min      2.442
_cell_volume                     25167(5)
_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
;
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
;
_diffrn_ambient_temperature      140.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.989
_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  0.0578
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       58
_diffrn_reflns_limit_k_min       -65
_diffrn_reflns_limit_l_max       58
_diffrn_reflns_limit_l_min       -52
_diffrn_reflns_number            388331
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.582
_diffrn_reflns_theta_min         1.504
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.474
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9305
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0632 before and 0.0544 after correction.
The Ratio of minimum to maximum transmission is 0.9305.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_description       block
_exptl_crystal_F_000             11182
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.177
_refine_diff_density_min         -1.162
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3117
_refine_ls_number_reflns         69881
_refine_ls_number_restraints     158
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0966
_refine_ls_R_factor_gt           0.0598
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0291P)^2^+54.6024P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1118
_refine_ls_wR_factor_ref         0.1237
_reflns_Friedel_coverage         0.000
_reflns_number_gt                49235
_reflns_number_total             69881
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs5009199_si_002.cif
_cod_data_source_block           '[Rh(PNGlyP)2]OTf'
_cod_original_cell_volume        25166(5)
_cod_original_formula_sum        'C65.50 H70.875 F3 N2 O9.125 P4 Rh S'
_cod_database_code               4511984
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 C243-C242 \\sim C244-C241
 with sigma of 0.02
 S1-O26 \\sim S1A-O27A \\sim S1A-O25A \\sim S1A-O26A \\sim S1-O27 \\sim S1-O25
 with sigma of 0.02
 S1-C1S \\sim S1A-C1SA
 with sigma of 0.02
 F3-C1S \\sim F1-C1S \\sim F2A-C1SA \\sim F2-C1S \\sim F1A-C1SA \\sim F3A-C1SA
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1TA \\sim C1T: within 1.7A with sigma of 0.04 
C4UA \\sim C2UA \\sim C3UA: within 1.7A with sigma of 0.01 
C244 \\sim C243: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C2VA \\sim C3VA \\sim C1VA \\sim C4VA: within 1.7A with sigma of 0.01 
C4VA \\sim C3VA \\sim C2VA \\sim C1VA: within 1.7A with sigma of 0.01 
S4 \\sim S4A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C1S \\sim C1SA: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C3U \\sim C4U \\sim C1U \\sim C2U: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C4U \\sim C2U \\sim C3U: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C242) = Uanis(C241)
Uanis(C4TA) = Uanis(C4TB)
Uanis(O37A) = Uanis(O36)
Uanis(S1) = Uanis(S1A)
Uanis(O25A) = Uanis(O25)
Uanis(O27) = Uanis(O27A)
Uanis(O26) = Uanis(O26A)
Uanis(F2A) = Uanis(F2)
Uanis(F1A) = Uanis(F1)
Uanis(O38) = Uanis(O38A)
Uanis(O24A) = Uanis(O24)
4. Others
 Fixed Sof: C1T(0.36862) H1TA(0.36862) H1TB(0.36862) C1TA(0.63138)
 H1TC(0.63138) H1TD(0.63138) H22G(0.36862) H22H(0.36862) H22I(0.63138)
 H22J(0.63138) H22K(0.36862) H22L(0.36862) H22M(0.63138) H22N(0.63138)
 C241(0.5) H24C(0.5) H24D(0.5) C242(0.5) H24E(0.5) H24F(0.5) C243(0.5)
 H24G(0.5) H24H(0.5) C244(0.5) H24I(0.5) H24J(0.5) O21(0.5) O24(0.55532)
 C4U(0.55532) H4UA(0.55532) H4UB(0.55532) C3U(0.12835) H3UA(0.12835)
 H3UB(0.12835) C2U(0.55532) H2UA(0.55532) H2UB(0.55532) C1U(0.55532)
 H1UA(0.55532) H1UB(0.55532) C3VT(0.42697) H3VA(0.42697) H3VB(0.42697)
 O24A(0.44468) C1UA(0.44468) H1UC(0.44468) H1UD(0.44468) C2UA(0.44468)
 H2UC(0.44468) H2UD(0.44468) C3UA(0.44468) H3UC(0.44468) H3UD(0.44468)
 C4UA(0.44468) H4UC(0.44468) H4UD(0.44468) C1O(0.5) H1OA(0.5) H1OB(0.5)
 C1M(0.5) H1MA(0.5) H1MB(0.5) C1N(0.5) H1NA(0.5) H1NB(0.5) O1D(0.5) C1P(0.5)
 H1PA(0.5) H1PB(0.5) C237(0.5) H23O(0.5) H23P(0.5) C238(0.5) H23Q(0.5)
 H23R(0.5) C239(0.5) H23S(0.5) H23T(0.5) C240(0.5) H24K(0.5) H24L(0.5) O20(0.5)
 O38A(0.39282) C1VA(0.39282) H1VA(0.39282) H1VB(0.39282) C2VA(0.39282)
 H2VA(0.39282) H2VB(0.39282) C3VA(0.39282) H3VC(0.39282) H3VD(0.39282)
 C4VA(0.39282) H4VA(0.39282) H4VB(0.39282) S4A(0.28248) O36A(0.28248)
 O35A(0.28248) O37A(0.28248) C4TA(0.28248) F12A(0.28248) F10A(0.28248)
 F11A(0.28248) S4(0.71752) O37(0.71752) O35(0.71752) O36(0.71752) C4TB(0.71752)
 F10(0.71752) F11(0.71752) F12(0.71752) O38(0.60718) C4V(0.60718) H4VC(0.60718)
 H4VD(0.60718) C3V(0.60718) H3VE(0.60718) H3VF(0.60718) C2V(0.60718)
 H2VC(0.60718) H2VD(0.60718) C1V(0.60718) H1VC(0.60718) H1VD(0.60718)
 C1S(0.61809) O25(0.61809) O26(0.61809) O27(0.61809) F1(0.61809) F2(0.61809)
 F3(0.61809) S1(0.61809) C1SA(0.38191) O25A(0.38191) O26A(0.38191)
 O27A(0.38191) F1A(0.38191) F2A(0.38191) F3A(0.38191) S1A(0.38191)
5.a Free rotating group:
 O24(C4U,C3U,C2U,C1U,C3VT), O24A(C1UA,C2UA,C3UA,C4UA,C1O,C1M,C1N,O1D,C1P,C237,
 C238,C239,C240,O20), O38A(C1VA,C2VA,C3VA,C4VA,S4A,O36A,O35A,O37A,C4TA,F12A,
 F10A,F11A,S4,O37,O35,O36,C4TB,F10,F11,F12), O38(C4V,C3V,C2V,C1V,C245,C246,C247,
 C248,O22,C259,O32,O33,O34,F7,F8,F9,S3,C1S,O25,O26,O27,F1,F2,F3,S1,C258,O29,O30,
 O31,F4,F5,F6,S2,C1SA,O25A,O26A,O27A,F1A,F2A,F3A,S1A)
5.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C53(H53A,H53B), C54(H54A,
 H54B), C55(H55A,H55B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
 C109(H10A,H10B), C110(H11A,H11B), C111(H11C,H11D), C137(H13A,H13B), C138(H13C,
 H13D), C139(H13E,H13F), C165(H16A,H16B), C166(H16C,H16D), C167(H16E,H16F),
 C193(H19A,H19B), C194(H19C,H19D), C195(H19E,H19F), C221(H22A,H22B), C222(H22C,
 H22D), C223(H22E,H22F), C1T(H1TA,H1TB), C1TA(H1TC,H1TD), C225(H22G,H22H),
 C225(H22I,H22J), C227(H22K,H22L), C227(H22M,H22N), C228(H22O,H22P), C249(H24A,
 H24B), C250(H25C,H25D), C251(H25E,H25F), C252(H25G,H25H), C229(H22Q,H22R),
 C230(H23A,H23B), C231(H23C,H23D), C232(H23E,H23F), C233(H23G,H23H), C234(H23I,
 H23J), C235(H23K,H23L), C236(H23M,H23N), C241(H24C,H24D), C242(H24E,H24F),
 C243(H24G,H24H), C244(H24I,H24J), C4U(H4UA,H4UB), C3U(H3UA,H3UB), C2U(H2UA,
 H2UB), C1U(H1UA,H1UB), C3VT(H3VA,H3VB), C1UA(H1UC,H1UD), C2UA(H2UC,H2UD),
 C3UA(H3UC,H3UD), C4UA(H4UC,H4UD), C1O(H1OA,H1OB), C1M(H1MA,H1MB), C1N(H1NA,
 H1NB), C1P(H1PA,H1PB), C237(H23O,H23P), C238(H23Q,H23R), C239(H23S,H23T),
 C240(H24K,H24L), C1VA(H1VA,H1VB), C2VA(H2VA,H2VB), C3VA(H3VC,H3VD), C4VA(H4VA,
 H4VB), C4V(H4VC,H4VD), C3V(H3VE,H3VF), C2V(H2VC,H2VD), C1V(H1VC,H1VD),
 C245(H24M,H24N), C246(H24O,H24P), C247(H24Q,H24R), C248(H24S,H24T)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C30(H30), C31(H31), C32(H32), C33(H33),
 C34(H34), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42), C43(H43),
  C44(H44), C45(H45), C46(H46), C48(H48), C49(H49), C50(H50), C51(H51),
 C52(H52), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C64(H64), C65(H65),
  C66(H66), C67(H67), C68(H68), C70(H70), C71(H71), C72(H72), C73(H73),
 C74(H74), C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C86(H86), C87(H87),
  C88(H88), C89(H89), C90(H90), C92(H92), C93(H93), C94(H94), C95(H95),
 C96(H96), C98(H98), C99(H99), C100(H100), C101(H101), C102(H102), C104(H104),
 C105(H105), C106(H106), C107(H107), C108(H108), C114(H114), C115(H115),
 C116(H116), C117(H117), C118(H118), C120(H120), C121(H121), C122(H122),
 C123(H123), C124(H124), C126(H126), C127(H127), C128(H128), C129(H129),
 C130(H130), C132(H132), C133(H133), C134(H134), C135(H135), C136(H136),
 C142(H142), C143(H143), C144(H144), C145(H145), C146(H146), C148(H148),
 C149(H149), C150(H150), C151(H151), C152(H152), C154(H154), C155(H155),
 C156(H156), C157(H157), C158(H158), C160(H160), C161(H161), C162(H162),
 C163(H163), C164(H164), C170(H170), C171(H171), C172(H172), C173(H173),
 C174(H174), C176(H176), C177(H177), C178(H178), C179(H179), C180(H180),
 C182(H182), C183(H183), C184(H184), C185(H185), C186(H186), C188(H188),
 C189(H189), C190(H190), C191(H191), C192(H192), C198(H198), C199(H199),
 C200(H200), C201(H201), C202(H202), C204(H204), C205(H205), C206(H206),
 C207(H207), C208(H208), C210(H210), C211(H211), C212(H212), C213(H213),
 C214(H214), C216(H216), C217(H217), C218(H218), C219(H219), C220(H220)
5.d Idealised tetrahedral OH refined as rotating group:
 O2(H2A), O4(H4A), O6(H6A), O8(H8A), O10(H10C), O12(H12A), O14(H14A), O16(H16G)
;
_shelx_hkl_checksum              75916
_shelx_res_checksum              72879
_shelxl_version_number           2013-2