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_7121028
_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_formula_moiety         'C32 H32 Cl2 N2 Ni P2, 2(C4 H8 O)'
_chemical_formula_sum            'C40 H48 Cl2 N2 Ni O2 P2'
_chemical_formula_weight         780.35
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-08-14
_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                 90.593(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.2751(11)
_cell_length_b                   11.6325(7)
_cell_length_c                   18.6817(12)
_cell_measurement_reflns_used    9843
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      38.65
_cell_measurement_theta_min      2.36
_cell_volume                     3753.9(4)
_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 0.984
_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_R_equivalents  0.0442
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            379989
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         38.883
_diffrn_reflns_theta_min         2.358
_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    0.782
_exptl_absorpt_correction_T_max  0.7476
_exptl_absorpt_correction_T_min  0.7039
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0746 before and 0.0532 after correction.
The Ratio of minimum to maximum transmission is 0.9415.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1640
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.774
_refine_diff_density_min         -0.776
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     538
_refine_ls_number_reflns         21322
_refine_ls_number_restraints     177
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0351P)^2^+1.5892P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0754
_refine_ls_wR_factor_ref         0.0831
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17363
_reflns_number_total             21322
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc09003j2.cif
_cod_data_source_block           p17270_a
_cod_depositor_comments
'Adding full bibliography for 7121026--7121028.cif.'
_cod_database_code               7121028
_shelxl_version_number           2014-2
_shelx_estimated_absorpt_t_max   0.879
_shelx_estimated_absorpt_t_min   0.817
_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. Restrained distances
 O1B-C33B \\sim O1A-C33A \\sim O1A-C36A \\sim O1B-C36B
 with sigma of 0.02
 C33B-C34B \\sim C34A-C33A \\sim C35B-C36B \\sim C36A-C35A
 with sigma of 0.02
 C35B-C34B \\sim C34A-C35A
 with sigma of 0.02
3. Rigid bond restraints
 O1B, C33B, C34B, C35B, C36B, O1A, C33A, C34A, C35A, C36A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O1B \\sim C33B \\sim C34B \\sim C35B \\sim C36B \\sim O1A \\sim C33A \\sim C34A
\\sim C35A \\sim C36A: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
5. Others
 Sof(O1A)=Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=
 Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=1-FVAR(1)
 Sof(O1B)=Sof(C33B)=Sof(H33A)=Sof(H33B)=Sof(C34B)=Sof(H34A)=Sof(H34B)=
 Sof(C35B)=Sof(H35A)=Sof(H35B)=Sof(C36B)=Sof(H36A)=Sof(H36B)=FVAR(1)
 Sof(O2A)=Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=
 Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(H40C)=Sof(H40D)=1-FVAR(2)
 Sof(O2B)=Sof(C37B)=Sof(H37A)=Sof(H37B)=Sof(C38B)=Sof(H38A)=Sof(H38B)=
 Sof(C39B)=Sof(H39A)=Sof(H39B)=Sof(C40B)=Sof(H40A)=Sof(H40B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C8(H8), C17(H17), C24(H24)
6.b Secondary CH2 refined with riding coordinates:
 C33B(H33A,H33B), C34B(H34A,H34B), C35B(H35A,H35B), C36B(H36A,H36B), C37B(H37A,
 H37B), C38B(H38A,H38B), C39B(H39A,H39B), C40B(H40A,H40B), C33A(H33C,H33D),
 C34A(H34C,H34D), C35A(H35C,H35D), C36A(H36C,H36D), C37A(H37C,H37D), C38A(H38C,
 H38D), C39A(H39C,H39D), C40A(H40C,H40D)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13),
 C19(H19), C20(H20), C21(H21), C22(H22), C26(H26), C27(H27), C28(H28), C29(H29)
6.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C)
;
_shelx_res_checksum              49768
_olex2_submission_special_instructions 'No special instructions were received'