Synthesis, Structural Characterization, and Gas-Phase Unimolecular Reactivity of Bis(diphenylphosphino)amino Copper Hydride Nanoclusters [Cu<sub>3</sub>(X)(μ<sub>3</sub>-H)((PPh<sub>2</sub>)<sub>2</sub>NH)<sub>3</sub>](BF<sub>4</sub>), Where X = μ<sub>2</sub>-Cl and μ<sub>3</sub>-BH<sub>4</sub>.
Li, Jiaye; White, Jonathan M.; Mulder, Roger J.; Reid, Gavin E.; Donnelly, Paul S.; O'Hair, Richard A J; Inorganic chemistry 55 (2016) 9858–9868; doi:10.1021/acs.inorgchem.6b01696

data_4348817
_publ_section_title
;
 Synthesis, Structural Characterization, and Gas-Phase Unimolecular
 Reactivity of Bis(diphenylphosphino)amino Copper Hydride Nanoclusters
 [Cu<sub>3</sub>(X)(\m<sub>3</sub>-H)((PPh<sub>2</sub>)<sub>2</sub>NH)<sub>3</sub>](BF<sub>4</sub>),
 Where X = \m<sub>2</sub>-Cl and \m<sub>3</sub>-BH<sub>4</sub>.
;
_journal_issue                   19
_journal_name_full               'Inorganic chemistry'
_journal_page_first              9858
_journal_page_last               9868
_journal_paper_doi               10.1021/acs.inorgchem.6b01696
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C72 H68 B Cu3 N3 P6, B F4'
_chemical_formula_sum            'C72 H68 B2 Cu3 F4 N3 P6'
_chemical_formula_weight         1449.35
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-05
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.774(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.4210(4)
_cell_length_b                   22.4885(3)
_cell_length_c                   21.3690(4)
_cell_measurement_reflns_used    13579
_cell_measurement_temperature    292.56(10)
_cell_measurement_theta_max      76.4200
_cell_measurement_theta_min      3.3020
_cell_volume                     8101.2(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      292.56(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
  1 omega  -49.00   14.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -40.6044   37.0000    0.0000 63

  2 omega  -96.00   -2.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -40.6044  125.0000  -30.0000 94

  3 omega -104.00   -7.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -40.6044  -77.0000 -150.0000 97

  4 omega -115.00  -13.00   1.0000    1.2500
omega____ theta____ kappa____ phi______ frames
    -      -40.6044  -57.0000   90.0000 102

  5 omega   36.00  109.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000 -180.0000 73

  6 omega   43.00  147.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000 -120.0000 104

  7 omega   82.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000   60.0000 96

  8 omega  101.00  155.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000  120.0000 54

  9 omega   91.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -30.0000 87

 10 omega   63.00  150.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000 -120.0000 87

 11 omega   52.00   88.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  150.0000 36

 12 omega   39.00   98.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   30.0000 59

 13 omega   39.00  124.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -129.0000  114.5885 85

 14 omega   35.00   84.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000 -120.0000 49
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0112416000
_diffrn_orient_matrix_UB_12      -0.0672381000
_diffrn_orient_matrix_UB_13      0.0067017000
_diffrn_orient_matrix_UB_21      -0.0678771000
_diffrn_orient_matrix_UB_22      -0.0005212000
_diffrn_orient_matrix_UB_23      -0.0718434000
_diffrn_orient_matrix_UB_31      0.0601646000
_diffrn_orient_matrix_UB_32      -0.0132037000
_diffrn_orient_matrix_UB_33      -0.0315517000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            51047
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.828
_diffrn_reflns_theta_min         2.995
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.410
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88701
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.188
_exptl_crystal_description       block
_exptl_crystal_F_000             2976
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.939
_refine_diff_density_min         -0.433
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     725
_refine_ls_number_reflns         16820
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0427
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0613P)^2^+2.2575P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1125
_refine_ls_wR_factor_ref         0.1209
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13268
_reflns_number_total             16820
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b01696_si_002.cif
_cod_data_source_block           lij21xl-b3
_cod_original_cell_volume        8101.1(3)
_cod_database_code               4348817
_chemical_oxdiff_formula         'Cu3 N3 P3 F4 B4 H20 C20'
_chemical_oxdiff_usercomment     'colorless block'
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2. Others
 Sof(F2)=Sof(F7)=Sof(F1)=Sof(F4)=1-FVAR(1)
 Sof(F6)=Sof(F5)=Sof(F8)=Sof(F3)=FVAR(1)
 Fixed X: H1D(0.0098)
 Fixed Y: H1D(1.0377)
 Fixed Z: H1D(0.3412)
3.a Aromatic/amide H refined with riding coordinates:
 N3(H3), N1(H1), N2(H2), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
 C42(H42), C41(H41), C40(H40), C39(H39), C38(H38), C8(H8), C9(H9), C10(H10),
 C11(H11), C12(H12), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C30(H30),
  C29(H29), C28(H28), C27(H27), C26(H26), C1(H1A), C6(H6), C5(H5), C4(H4),
 C3(H3A), C18(H18), C17(H17), C16(H16), C15(H15), C14(H14), C59(H59), C58(H58),
 C57(H57), C56(H56), C60(H60), C67(H67), C1AA(H1AA), C4AA(H4AA), C68(H68),
 C51(H51), C50(H50), C54(H54), C53(H53), C52(H52), C66(H66), C65(H65), C64(H64),
  C63(H63), C62(H62), C46(H46), C45(H45), C44(H44), C48(H48), C47(H47)
3.b Fitted hexagon refined as free rotating group:
 C31(C32,C33,C34,C35,C36), C42(C41,C40,C39,C38,C37), C8(C9,C10,C11,C12,C7),
 C20(C21,C22,C23,C24,C19), C30(C29,C28,C27,C26,C25), C1(C6,C5,C4,C3,C2),
 C18(C17,C16,C15,C14,C13), C59(C58,C57,C56,C55,C60), C67(C1AA,C4AA,C68,C6AA,
 C5AA), C51(C50,C49,C54,C53,C52), C66(C65,C64,C63,C62,C61), C46(C45,C44,C43,C48,
 C47)
;
_shelx_res_checksum              93581
_shelx_hkl_checksum              169
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'