A Significant but Constrained Geometry Pt→Al Interaction: Fixation of CO2 and CS2, Activation of H2 and PhCONH2.
Devillard, Marc; Declercq, Richard; Nicolas, Emmanuel; Ehlers, Andreas W.; Backs, Jana; Saffon-Merceron, Nathalie; Bouhadir, Ghenwa; Slootweg, J. Chris; Uhl, Werner; Bourissou, Didier; Journal of the American Chemical Society 138 (2016) 4917–4926; doi:10.1021/jacs.6b01320

data_4130214
_publ_section_title
;
 A Significant but Constrained Geometry Pt\\rightarrow Al Interaction:
 Fixation of CO2 and CS2, Activation of H2 and PhCONH2.
;
_journal_issue                   14
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4917
_journal_page_last               4926
_journal_paper_doi               10.1021/jacs.6b01320
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         '2(C53 H61 Al O2 P2 Pt), 0.5(C4 H8 O)'
_chemical_formula_sum            'C108 H126 Al2 O4.5 P4 Pt2'
_chemical_formula_weight         2064.10
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2016-01-12
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                97.690(2)
_cell_angle_beta                 92.244(2)
_cell_angle_gamma                108.259(2)
_cell_formula_units_Z            2
_cell_length_a                   12.5062(9)
_cell_length_b                   18.9753(13)
_cell_length_c                   21.5190(14)
_cell_measurement_reflns_used    9890
_cell_measurement_temperature    193(2)
_cell_measurement_theta_max      22.72
_cell_measurement_theta_min      3.22
_cell_volume                     4788.0(6)
_computing_cell_refinement       'SAINT v8.34A (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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      193.02
_diffrn_measured_fraction_theta_full 0.934
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0769
_diffrn_reflns_av_unetI/netI     0.0573
_diffrn_reflns_Laue_measured_fraction_full 0.934
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            92035
_diffrn_reflns_point_group_measured_fraction_full 0.934
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.713
_diffrn_reflns_theta_min         5.101
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.056
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6484
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/3 (Bruker,2014/3) was used for absorption correction. wR2(int) was 0.1088 before and 0.0641 after correction. The Ratio of minimum to maximum transmission is 0.8696. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.432
_exptl_crystal_description       plate
_exptl_crystal_F_000             2104
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.554
_refine_diff_density_min         -2.291
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1194
_refine_ls_number_reflns         16171
_refine_ls_number_restraints     152
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0478
_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^)+(0.0291P)^2^+34.4305P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1076
_refine_ls_wR_factor_ref         0.1163
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12610
_reflns_number_total             16171
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b01320_si_002.cif
_cod_data_source_block           3
_cod_original_formula_sum        'C108 H126 Al2 O4.50 P4 Pt2'
_cod_database_code               4130214
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.888
_shelx_estimated_absorpt_t_min   0.566
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C108, C107, O5, C110, C109
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C78, C79, C80, C78', C79', C80'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C74, C75, C76, C74', C75', C76'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C108 \\sim C107 \\sim O5 \\sim C110 \\sim C109: within 1.7A with sigma of 0.04
and sigma for terminal atoms of 0.08
C73 \\sim C74 \\sim C75 \\sim C76 \\sim C74' \\sim C75' \\sim C76': within 1.7A
with sigma of 0.005 and sigma for terminal atoms of 0.01
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C78' \\sim C79' \\sim C80': within 1.7A
with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Same fragment restrains
{C109, C110, O5, C107, C108} sigma for 1-2: 0.02, 1-3: 0.04
as
{C108, C107, O5, C110, C109}
5. Others
 Sof(C74')=Sof(H74D)=Sof(H74E)=Sof(H74F)=Sof(C75')=Sof(H75D)=Sof(H75E)=
 Sof(H75F)=Sof(C76')=Sof(H76D)=Sof(H76E)=Sof(H76F)=1-FVAR(1)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(1)
 Sof(C78')=Sof(H78D)=Sof(H78E)=Sof(H78F)=Sof(C79')=Sof(H79D)=Sof(H79E)=
 Sof(H79F)=Sof(C80')=Sof(H80D)=Sof(H80E)=Sof(H80F)=1-FVAR(2)
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=FVAR(2)
 Fixed Sof: C108(0.5) H10A(0.5) H10B(0.5) C107(0.5) H10C(0.5) H10D(0.5)
 O5(0.5) C110(0.5) H11A(0.5) H11B(0.5) C109(0.5) H10E(0.5) H10F(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C108(H10A,H10B), C107(H10C,H10D), C110(H11A,H11B), C109(H10E,H10F)
6.b Aromatic/amide H refined with riding coordinates:
 C100(H100), C106(H106), C105(H105), C104(H104), C103(H103), C102(H102),
 C86(H86), C84(H84), C95(H95), C93(H93), C71(H71), C70(H70), C69(H69), C68(H68),
  C67(H67), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65), C59(H59),
 C58(H58), C57(H57), C56(H56), C55(H55), C52(H52), C47(H47), C49(H49), C53(H53),
  C51(H51), C50(H50), C42(H42), C40(H40), C31(H31), C33(H33), C14(H14),
 C15(H15), C16(H16), C17(H17), C18(H18), C6(H6), C5(H5), C4(H4), C3(H3), C2(H2),
  C8(H8), C9(H9), C10(H10), C11(H11), C12(H12)
6.c Idealised Me refined as rotating group:
 C90(H90A,H90B,H90C), C89(H89A,H89B,H89C), C88(H88A,H88B,H88C), C99(H99A,H99B,
 H99C), C98(H98A,H98B,H98C), C97(H97A,H97B,H97C), C78(H78A,H78B,H78C), C79(H79A,
 H79B,H79C), C80(H80A,H80B,H80C), C78'(H78D,H78E,H78F), C79'(H79D,H79E,H79F),
 C80'(H80D,H80E,H80F), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,
 H76C), C74'(H74D,H74E,H74F), C75'(H75D,H75E,H75F), C76'(H76D,H76E,H76F),
 C46(H46A,H46B,H46C), C45(H45A,H45B,H45C), C44(H44A,H44B,H44C), C35(H35A,H35B,
 H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C27(H27A,H27B,H27C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C),
 C22(H22A,H22B,H22C)
;
_shelx_res_checksum              41687
_shelx_hkl_checksum              67394
_olex2_submission_special_instructions 'No special instructions were received'