Metal-Organic Frameworks Stabilize Mono(phosphine)-Metal Complexes for Broad-Scope Catalytic Reactions.
Sawano, Takahiro; Lin, Zekai; Boures, Dean; An, Bing; Wang, Cheng; Lin, Wenbin; Journal of the American Chemical Society 138 (2016) 9783–9786; doi:10.1021/jacs.6b06239

data_4130735
_publ_section_title
;
 Metal-Organic Frameworks Stabilize Mono(phosphine)-Metal Complexes for
 Broad-Scope Catalytic Reactions.
;
_journal_issue                   31
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9783
_journal_page_last               9786
_journal_paper_doi               10.1021/jacs.6b06239
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         '0.01(C184 H128 Cl4 O34 P4 Rh4 Zr6)'
_chemical_formula_sum
'C2.48 H1.71 Cl0.05 O0.45 P0.05 Rh0.05 Zr0.08'
_chemical_formula_weight         55.09
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-04-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                109.155(9)
_cell_angle_beta                 103.794(9)
_cell_angle_gamma                99.700(10)
_cell_formula_units_Z            75
_cell_length_a                   18.126(14)
_cell_length_b                   20.015(15)
_cell_length_c                   21.790(16)
_cell_measurement_reflns_used    775
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      7.4549
_cell_measurement_theta_min      2.2323
_cell_volume                     6985(9)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.046
_diffrn_measured_fraction_theta_max 0.928
_diffrn_measurement_device_type  'synchrotron, beamline 15-ID, APEX2 detector'
_diffrn_measurement_method       'phi scans'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.41328
_diffrn_reflns_av_R_equivalents  0.1223
_diffrn_reflns_av_unetI/netI     0.1373
_diffrn_reflns_Laue_measured_fraction_full 0.046
_diffrn_reflns_Laue_measured_fraction_max 0.928
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            23017
_diffrn_reflns_point_group_measured_fraction_full 0.046
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         9.251
_diffrn_reflns_theta_min         0.650
_diffrn_source                   'synchrotron radiation'
_exptl_absorpt_coefficient_mu    0.650
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    0.982
_exptl_crystal_description       needle
_exptl_crystal_F_000             2064
_refine_diff_density_max         2.156
_refine_diff_density_min         -1.273
_refine_diff_density_rms         0.146
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         6396
_refine_ls_number_restraints     450
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.1636
_refine_ls_R_factor_gt           0.1189
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3042
_refine_ls_wR_factor_ref         0.3358
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3699
_reflns_number_total             6396
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b06239_si_001.cif
_cod_data_source_block           p-1_a
_cod_database_code               4130735
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {C52,H52,C48,H48} of C51, All C(H,H) groups
 At 1.5 times of:
  All C(O) groups
2. Restrained distances
 C74-C79
 1.6 with sigma of 0.02
 C74-C71
 1.6 with sigma of 0.02
 C79-C80
 1.55 with sigma of 0.02
 C71-C02X
 1.55 with sigma of 0.02
 C72-C73
 1.6 with sigma of 0.02
 O1-C2
 1.32 with sigma of 0.02
 C2-O39
 1.32 with sigma of 0.02
 O1-O39
 2.23 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(O15) = Uanis(O16) = Uanis(Zr2)
Uanis(O7) = Uanis(O8)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Ternary CH refined with riding coordinates:
 C02X(H02X), C039(H039), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69),
 C71(H71), C72(H72), C73(H73), C79(H79), C80(H80)
6.b Secondary CH2 refined with riding coordinates:
 C70(H70A,H70B), C74(H74A,H74B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C4(H4), C02O(H02O), C02U(H02U), C03A(H03A),
 C03M(H03M), C9(H9), C10(H10), C11(H11), C12(H12), C025(H025), C02Q(H02Q),
 C038(H038), C028(H028), C17(H17), C18(H18), C16(H16), C15(H15), C24(H24),
 C22(H22), C21(H21), C25(H25), C28(H28), C29(H29), C31(H31), C32(H32), C36(H36),
  C37(H37), C34(H34), C35(H35), C42(H42), C46(H46), C44(H44), C43(H43),
 C52(H52), C48(H48), C49(H49), C50(H50), C54(H54), C56(H56), C57(H57), C55(H55),
  C60(H60), C61(H61), C63(H63), C64(H64)
6.d Fitted hexagon refined as free rotating group:
 C1AA(C3,C5,C7,C6,C4), C02K(C02O,C02U,C02V,C03A,C03M), C016(C025,C02Q,C02R,
 C038,C028), C17(C18,C19,C16,C15,C14), C24(C23,C22,C21,C20,C25), C36(C37,C38,
 C34,C35,C33), C41(C42,C46,C45,C44,C43), C51(C52,C48,C47,C49,C50), C53(C54,C56,
 C58,C57,C55)
;
_shelx_res_checksum              95776
_shelx_hkl_checksum              87801
_olex2_submission_special_instructions 'No special instructions were received'