Mild electrochemical synthesis of metal phosphides with dibenzo-7-phosphanorbornadiene derivatives: mechanistic insights and application to proton reduction in water.
Shida, Naoki; Buss, Joshua A.; Agapie, Theodor; Chemical communications (Cambridge, England) 54 (2018) 767–770; doi:10.1039/c7cc09003j

data_7121026
_publ_section_title
;
 Mild electrochemical synthesis of metal phosphides with
 dibenzo-7-phosphanorbornadiene derivatives: mechanistic insights and
 application to proton reduction in water.
;
_journal_issue                   7
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              767
_journal_page_last               770
_journal_paper_doi               10.1039/c7cc09003j
_journal_volume                  54
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C56 H40 Cl4 Ni P4, 2.5(C7 H8), 0.5(C5 H12)'
_chemical_formula_sum            'C76 H66 Cl4 Ni P4'
_chemical_formula_weight         1303.67
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-08-19
_audit_creation_method
;
Olex2 1.2
(compiled Aug 10 2017 17:28:52 for OlexSys, GUI svn.r5375),
SHELXL-2016,
and manual edit
;
_audit_update_record
;
2017-10-05 deposited with the CCDC.
2017-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.332(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3354(8)
_cell_length_b                   26.2108(16)
_cell_length_c                   16.4415(10)
_cell_measurement_reflns_used    9490
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      35.55
_cell_measurement_theta_min      2.66
_cell_volume                     6430.6(6)
_computing_cell_refinement       'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_data_collection       'BIS V6.2.1/2016-03-01'
_computing_data_reduction        'SAINT V8.38A (Bruker-AXS, 2016)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0689
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            60598
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.778
_diffrn_reflns_theta_min         2.258
_diffrn_source                   'I\mS HB micro-focus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatech I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.612
_exptl_absorpt_correction_T_max  0.9729
_exptl_absorpt_correction_T_min  0.8997
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0864 before and 0.0699 after correction. The Ratio of minimum to maximum transmission is 0.9136. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.347
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2712
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.210
_refine_diff_density_min         -1.348
_refine_diff_density_rms         0.115
_refine_ls_abs_structure_details
;
 Flack x determined using 21733 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1539
_refine_ls_number_reflns         60598
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0709
_refine_ls_R_factor_gt           0.0571
_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^)+(0.0532P)^2^+6.6014P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1283
_refine_ls_wR_factor_ref         0.1373
_reflns_Friedel_coverage         0.933
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.934
_reflns_number_gt                53170
_reflns_number_total             60598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc09003j2.cif
_cod_data_source_block           p17268hm
_cod_depositor_comments
;

2018-02-12
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel

 Adding full bibliography for 7121026--7121028.cif.
;
_cod_original_formula_moiety     '2(C56 H40 Cl4 Ni P4), 5(C7 H8), C5 H12'
_cod_original_formula_sum        'C152 H132 Cl8 Ni2 P8'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     2607.35
_cod_database_code               7121026
_shelxl_version_number           2014-2
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.893
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6276(7)
 0.3724(7)
2. 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
3.a Ternary CH refined with riding coordinates:
 C1(H1), C8(H8), C15(H15), C22(H22), C29(H29), C36(H36), C43(H43), C50(H50),
 C57(H57), C64(H64), C71(H71), C78(H78), C85(H85), C92(H92), C99(H99),
 C106(H106)
3.b Secondary CH2 refined with riding coordinates:
 C149(H14D,H14E), C150(H15A,H15B), C151(H15C,H15D)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13),
 C17(H17), C18(H18), C19(H19), C20(H20), C24(H24), C25(H25), C26(H26), C27(H27),
  C31(H31), C32(H32), C33(H33), C34(H34), C38(H38), C39(H39), C40(H40),
 C41(H41), C45(H45), C46(H46), C47(H47), C48(H48), C52(H52), C53(H53), C54(H54),
  C55(H55), C59(H59), C60(H60), C61(H61), C62(H62), C66(H66), C67(H67),
 C68(H68), C69(H69), C73(H73), C74(H74), C75(H75), C76(H76), C80(H80), C81(H81),
  C82(H82), C83(H83), C87(H87), C88(H88), C89(H89), C90(H90), C94(H94),
 C95(H95), C96(H96), C97(H97), C101(H101), C102(H102), C103(H103), C104(H104),
 C108(H108), C109(H109), C110(H110), C111(H111), C115(H115), C116(H116),
 C117(H117), C118(H118), C119(H119), C122(H122), C123(H123), C124(H124),
 C125(H125), C126(H126), C129(H129), C130(H130), C131(H131), C132(H132),
 C133(H133), C136(H136), C137(H137), C138(H138), C139(H139), C140(H140),
 C143(H143), C144(H144), C145(H145), C146(H146), C147(H147)
3.d Idealised Me refined as rotating group:
 C113(H11A,H11B,H11C), C120(H12A,H12B,H12C), C127(H12D,H12E,H12F), C134(H13A,
 H13B,H13C), C141(H14F,H14G,H14H), C148(H14A,H14B,H14C), C152(H15E,H15F,H15G)
;
_shelx_res_checksum              89246
_olex2_submission_special_instructions 'No special instructions were received'