Cluster transformation of [Cu3(μ3-H)(μ3-BH4)((PPh2)2NH)3](BF4) to [Cu3(μ3-H)(μ2,μ1-S2CH)((PPh2)2NH)3](BF4) via reaction with CS2. X-ray structural characterisation and reactivity of cationic clusters explored by multistage mass spectrometry and computational studies
Ma, Howard Z.; Li, Jiaye; Canty, Allan J.; O'Hair, Richard A. J.; Dalton Trans.  (2017) –; doi:10.1039/C7DT03510A

data_7044509
_publ_section_title
;
 Cluster transformation of [Cu3(\m3-H)(\m3-BH4)((PPh2)2NH)3](BF4) to
 [Cu3(\m3-H)(\m2,\m1-S2CH)((PPh2)2NH)3](BF4) via reaction with CS2. X-ray
 structural characterisation and reactivity of cationic clusters explored
 by multistage mass spectrometry and computational studies
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT03510A
_journal_year                    2017
_chemical_formula_moiety
'C73 H65 Cu3 N3 P6 S2, C0.94 H2 Cl2, C H1.93 Cl2, B F4.05, C2 H3 N'
_chemical_formula_sum            'C76.94 H71.88 B Cl4 Cu3 F4.05 N4 P6 S2'
_chemical_formula_weight         1722.57
_chemical_name_common            Cu3CS2H
_chemical_name_systematic        Cu3CS2H
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-09-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-09-05 deposited with the CCDC.
2017-10-10 downloaded from the CCDC.
;
_cell_angle_alpha                79.962(3)
_cell_angle_beta                 84.904(3)
_cell_angle_gamma                84.146(3)
_cell_formula_units_Z            2
_cell_length_a                   14.5606(5)
_cell_length_b                   15.3131(5)
_cell_length_c                   18.0023(8)
_cell_measurement_reflns_used    8657
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      76.8380
_cell_measurement_theta_min      4.0200
_cell_volume                     3921.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43i (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43i (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43i (Rigaku OD, 2015)'
_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      N~2~
_diffrn_ambient_temperature      130.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -50.00  35.00   1.00    1.00    --  -40.81  38.00  30.00   85
  2  \w      7.00  40.00   1.00    1.00    --   40.81  77.00-120.00   33
  3  \w     94.00 120.00   1.00    1.00    --   40.81  77.00-120.00   26
  4  \w    139.00 178.00   1.00    1.77    --  113.00  45.00 -90.00   39
  5  \w    120.00 177.00   1.00    1.77    --  113.00 111.00 -90.00   57
  6  \w     91.00 131.00   1.00    1.77    --  113.00  45.00 -90.00   40
  7  \w     86.00 178.00   1.00    1.77    --  113.00  45.00   0.00   92
  8  \w     82.00 177.00   1.00    1.77    --  113.00  30.00 -30.00   95
  9  \w     71.00 109.00   1.00    1.77    --  113.00 -94.00-180.00   38
 10  \w     56.00 116.00   1.00    1.77    --  113.00-111.00 -60.00   60
 11  \w     41.00 143.00   1.00    1.77    --  113.00 -61.00 -90.00  102
 12  \w     30.00  57.00   1.00    1.77    --  113.00 -94.00-180.00   27
 13  \w     23.00  98.00   1.00    1.00    --   40.81-125.00 120.00   75
 14  \w     48.00 135.00   1.00    1.77    --  113.00 -61.00 150.00   87
 15  \w     41.00 116.00   1.00    1.77    --  113.00-111.00 150.00   75
 16  \w     35.00  86.00   1.00    1.77    --  113.00 -30.00 150.00   51
 17  \w     58.00 150.00   1.00    1.77    --  113.00 178.00 150.00   92
 18  \w     58.00 150.00   1.00    1.77    --  113.00 178.00-180.00   92
 19  \w    -48.00  28.00   1.00    1.00    --  -40.81  38.00-180.00   76
 20  \w   -115.00 -11.00   1.00    1.00    --  -40.81 -57.00-120.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0797524000
_diffrn_orient_matrix_UB_12      0.0514336000
_diffrn_orient_matrix_UB_13      -0.0425260000
_diffrn_orient_matrix_UB_21      0.0417854000
_diffrn_orient_matrix_UB_22      0.0001025000
_diffrn_orient_matrix_UB_23      0.0756564000
_diffrn_orient_matrix_UB_31      0.0571442000
_diffrn_orient_matrix_UB_32      -0.0887402000
_diffrn_orient_matrix_UB_33      -0.0077643000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0377
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            31062
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.091
_diffrn_reflns_theta_min         3.529
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.299
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75944
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43i (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orangish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.459
_exptl_crystal_description       block
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.489
_refine_diff_density_min         -0.706
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     818
_refine_ls_number_reflns         16161
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0487
_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^)+(0.0417P)^2^+6.9716P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1261
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12572
_reflns_number_total             16161
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt03510a2.cif
_cod_data_source_block           lijcu3cs2_orange_20170407
_cod_database_code               7044509
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C H N P Cu B F'
_chemical_oxdiff_usercomment     'orange block'
_reflns_odcompleteness_completeness 98.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     75.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Cl5) = Uanis(Cl7)
Uanis(F98) = Uanis(F97) = Uanis(F95) = Uanis(F99)
3. Others
 Sof(F97A)=1-FVAR(1)
 Sof(F97)=FVAR(1)
 Sof(F95A)=1-FVAR(2)
 Sof(F95)=FVAR(2)
 Sof(H77C)=Sof(H77D)=Sof(Cl6)=1-FVAR(3)
 Sof(Cl7)=FVAR(3)
 Sof(Cl4)=1-FVAR(4)
 Sof(Cl5)=Sof(H77A)=Sof(H77B)=FVAR(4)
 Sof(H76C)=Sof(H76D)=Sof(Cl1)=1-FVAR(5)
 Sof(Cl2)=Sof(H76A)=Sof(H76B)=FVAR(5)
 Fixed X: H75(0.6387)
 Fixed Y: H75(0.5574)
 Fixed Z: H75(0.504399)
4.a Riding coordinates:
 N2(H2)
4.b Secondary CH2 refined with riding coordinates:
 C76(H76A,H76B), C76(H76C,H76D), C77(H77A,H77B), C77(H77C,H77D)
4.c Aromatic/amide H refined with riding coordinates:
 C36(H36), C35(H35), C34(H34), C33(H33), C32(H32), C2(H2A), C3(H3A), C4(H4),
 C5(H5), C6(H6), C15(H15), C16(H16), C17(H17), C18(H18), C14(H14), C56(H56),
 C57(H57), C58(H58), C59(H59), C60(H60), C46(H46), C45(H45), C44(H44), C48(H48),
  C47(H47), C69(H69), C70(H70), C71(H71), C72(H72), C68(H68), C9(H9), C10(H10),
 C11(H11), C12(H12), C8(H8), C24(H24), C23(H23), C22(H22), C21(H21), C20(H20),
 C40(H40), C41(H41), C42(H42), C38(H38), C39(H39), C64(H64), C63(H63), C62(H62),
  C66(H66), C65(H65), C52(H52), C51(H51), C50(H50), C54(H54), C53(H53),
 C27(H27), C28(H28), C29(H29), C30(H30), C26(H26)
4.d Fitted hexagon refined as free rotating group:
 C31(C36,C35,C34,C33,C32), C2(C3,C4,C5,C6,C1), C15(C16,C17,C18,C13,C14),
 C56(C57,C58,C59,C60,C55), C46(C45,C44,C43,C48,C47), C69(C70,C71,C72,C67,C68),
 C9(C10,C11,C12,C7,C8), C24(C23,C22,C21,C20,C19), C40(C41,C42,C37,C38,C39),
 C64(C63,C62,C61,C66,C65), C52(C51,C50,C49,C54,C53), C27(C28,C29,C30,C25,C26)
4.e Idealised Me refined as rotating group:
 C74(H74A,H74B,H74C)
;
_shelx_res_checksum              59798
_olex2_date_sample_data_collection 2017-04-07
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.775
_oxdiff_exptl_absorpt_empirical_full_min 0.741