Cationic Copper Hydride Clusters Arising from Oxidation of (Ph<sub>3</sub>P)<sub>6</sub>Cu<sub>6</sub>H<sub>6</sub>.
Liu, Shuo; Eberhart, Michael S.; Norton, Jack R.; Yin, Xiaodong; Neary, Michelle C.; Paley, Daniel W.; Journal of the American Chemical Society 139 (2017) 7685–7688; doi:10.1021/jacs.7b02183

data_4131257
_publ_section_title
;
 Cationic Copper Hydride Clusters Arising from Oxidation of
 (Ph<sub>3</sub>P)<sub>6</sub>Cu<sub>6</sub>H<sub>6</sub>.
;
_journal_issue                   23
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7685
_journal_page_last               7688
_journal_paper_doi               10.1021/jacs.7b02183
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C108 H90 Cu6 P6, 0.9(C F3 O3 S), 0.1(F6 P)'
_chemical_formula_sum            'C108.9 H90 Cu6 F3.3 O2.71 P6.1 S0.9'
_chemical_formula_weight         2103.54
_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
_audit_creation_date             2016-12-09
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3368 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                114.492(5)
_cell_angle_beta                 98.338(5)
_cell_angle_gamma                92.257(5)
_cell_formula_units_Z            4
_cell_length_a                   15.0213(10)
_cell_length_b                   25.1312(12)
_cell_length_c                   28.3846(14)
_cell_measurement_reflns_used    6585
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      69.6060
_cell_measurement_theta_min      3.7160
_cell_volume                     9588.9(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.958
_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    -63.00  31.00   1.00    5.00    --  -36.47  77.00   0.00   94
  2  \w   -109.00 -35.00   1.00    5.00    --  -36.47-178.00  90.00   74
  3  \w   -109.00 -35.00   1.00    5.00    --  -36.47-178.00-150.00   74
  4  \w    -53.00  31.00   1.00    5.00    --  -36.47  57.00 -90.00   84
  5  \w   -106.00 -17.00   1.00    5.00    --  -36.47 -37.00  30.00   89
  6  \w   -104.00 -10.00   1.00    5.00    --  -36.47 -77.00   0.00   94
  7  \w    -63.00  31.00   1.00    5.00    --  -36.47  77.00 120.00   94
  8  \w      1.00  75.00   1.00    5.00    --   36.47 -99.00-120.00   74
  9  \w      1.00  75.00   1.00    5.00    --   36.47 -99.00-180.00   74
 10  \w      1.00  75.00   1.00    5.00    --   36.47 -99.00 -30.00   74
 11  \w     55.00 109.00   1.00    5.00    --   36.47-178.00 -60.00   54
 12  \w     94.00 178.00   1.00   25.00    --  111.00  45.00 120.00   84
 13  \w     88.00 178.00   1.00   25.00    --  111.00  71.00 138.00   90
 14  \w     41.00 116.00   1.00   25.00    --  111.00-111.00   0.00   75
 15  \w     43.00 128.00   1.00   25.00    --  111.00 -45.00 120.00   85
 16  \w     43.00 138.00   1.00   25.00    --  111.00 -77.00  30.00   95
 17  \w     43.00 128.00   1.00   25.00    --  111.00 -45.00 -30.00   85
 18  \w     42.00 109.00   1.00   25.00    --  111.00 -94.00  30.00   67
 19  \w     41.00 132.00   1.00   25.00    --  111.00 -30.00-180.00   91
 20  \w     42.00 109.00   1.00   25.00    --  111.00 -94.00 -90.00   67
 21  \w     41.00 116.00   1.00   25.00    --  111.00-111.00-150.00   75
 22  \w    100.00 174.00   1.00   25.00    --  111.00 111.00 -30.00   74
 23  \w     46.00 107.00   1.00   25.00    --  111.00-111.00 150.00   61
 24  \w     51.00 122.00   1.00   25.00    --  111.00 -77.00-150.00   71
 25  \w     42.00 107.00   1.00   25.00    --  111.00   0.00  90.00   65
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1024139000
_diffrn_orient_matrix_UB_12      -0.0019995000
_diffrn_orient_matrix_UB_13      0.0140827000
_diffrn_orient_matrix_UB_21      -0.0159685000
_diffrn_orient_matrix_UB_22      -0.0137443000
_diffrn_orient_matrix_UB_23      0.0463951000
_diffrn_orient_matrix_UB_31      -0.0115542000
_diffrn_orient_matrix_UB_32      -0.0663387000
_diffrn_orient_matrix_UB_33      -0.0363571000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1250
_diffrn_reflns_av_unetI/netI     0.2122
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            87462
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.093
_diffrn_reflns_theta_min         3.383
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.057
_exptl_absorpt_correction_T_max  0.968
_exptl_absorpt_correction_T_min  0.689
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
'CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.457
_exptl_crystal_description       plate
_exptl_crystal_F_000             4298
_exptl_crystal_size_max          0.219
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.011
_refine_diff_density_max         1.083
_refine_diff_density_min         -0.705
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2567
_refine_ls_number_reflns         36769
_refine_ls_number_restraints     695
_refine_ls_restrained_S_all      0.991
_refine_ls_R_factor_all          0.2022
_refine_ls_R_factor_gt           0.0983
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0890P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2187
_refine_ls_wR_factor_ref         0.2908
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15811
_reflns_number_total             36769
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b02183_si_001.cif
_cod_data_source_block           Cu6L6H5
_cod_original_formula_sum        'C108.90 H90 Cu6 F3.30 O2.71 P6.10 S0.90'
_cod_database_code               4131257
_chemical_oxdiff_formula         'Cu6 P6 C100 H100 S O3 F3'
_reflns_odcompleteness_completeness 94.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.83
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 S1_1-C1_1
 S1_2-C1_2
 S1_3-C1_3
 S1_4-C1_4
 1.851 with sigma of 0.02
 S1_1-O1_1 = S1_1-O2_1 = S1_1-O3_1
 S1_2-O1_2 = S1_2-O2_2 = S1_2-O3_2
 S1_3-O1_3 = S1_3-O2_3 = S1_3-O3_3
 S1_4-O1_4 = S1_4-O2_4 = S1_4-O3_4
 1.445 with sigma of 0.02
 C1_1-F1_1 = C1_1-F2_1 = C1_1-F3_1
 C1_2-F1_2 = C1_2-F2_2 = C1_2-F3_2
 C1_3-F1_3 = C1_3-F2_3 = C1_3-F3_3
 C1_4-F1_4 = C1_4-F2_4 = C1_4-F3_4
 1.338 with sigma of 0.02
 S1_1-F1_1 = S1_1-F2_1 = S1_1-F3_1
 S1_2-F1_2 = S1_2-F2_2 = S1_2-F3_2
 S1_3-F1_3 = S1_3-F2_3 = S1_3-F3_3
 S1_4-F1_4 = S1_4-F2_4 = S1_4-F3_4
 2.658 with sigma of 0.04
 C1_1-O1_1 = C1_1-O2_1 = C1_1-O3_1
 C1_2-O1_2 = C1_2-O2_2 = C1_2-O3_2
 C1_3-O1_3 = C1_3-O2_3 = C1_3-O3_3
 C1_4-O1_4 = C1_4-O2_4 = C1_4-O3_4
 2.581 with sigma of 0.04
 O1_1-O2_1 = O1_1-O3_1 = O2_1-O3_1
 O1_2-O2_2 = O1_2-O3_2 = O2_2-O3_2
 O1_3-O2_3 = O1_3-O3_3 = O2_3-O3_3
 O1_4-O2_4 = O1_4-O3_4 = O2_4-O3_4
 2.445 with sigma of 0.04
 F1_1-F2_1 = F1_1-F3_1 = F2_1-F3_1
 F1_2-F2_2 = F1_2-F3_2 = F2_2-F3_2
 F1_3-F2_3 = F1_3-F3_3 = F2_3-F3_3
 F1_4-F2_4 = F1_4-F3_4 = F2_4-F3_4
 2.151 with sigma of 0.04
 P1_22-C1_3
 0.86 with sigma of 0.02
 P1_22-S1_3
 0.96 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.01 and sigma
for terminal atoms of 0.02
: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 P1, C23, C24, C25, C26, C27, C28, C23B, C24B, C25B, C26B, C27B, C28B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1_1, O1_1, O2_1, O3_1, C1_1, F1_1, F2_1, F3_1
 S1_2, O1_2, O2_2, O3_2, C1_2, F1_2, F2_2, F3_2
 S1_3, O1_3, O2_3, O3_3, C1_3, F1_3, F2_3, F3_3
 S1_4, O1_4, O2_4, O3_4, C1_4, F1_4, F2_4, F3_4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{Cu1, P1, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23B,
C24B, C25B, C26B, C27B, C28B} sigma for 1-2: 0.02, 1-3: 0.04
{Cu1, P1, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23B,
C28B, C27B, C26B, C25B, C24B} sigma for 1-2: 0.02, 1-3: 0.04
as
{Cu1, P1, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24,
C25, C26, C27, C28}
6. Others
 1*[Sof(S1)+Sof(O1)+Sof(O2)+Sof(O3)+Sof(C1)+Sof(F1)+Sof(F2)+Sof(F3)]+1*
 [Sof(S1)+Sof(O1)+Sof(O2)+Sof(O3)+Sof(C1)+Sof(F1)+Sof(F2)+Sof(F3)]+1*[Sof(P1)+
 Sof(F2)+Sof(F3)+Sof(F4)+Sof(Q1)+Sof(Q2)+Sof(Q3)+Sof(Q4)+Sof(Q5)+Sof(Q6)+
 Sof(Q7)+Sof(Q8)+Sof(Q9)+Sof(Q10)+Sof(Q11)+Sof(Q12)+Sof(Q13)+Sof(Q14)+Sof(Q15)+
 Sof(Q16)+Sof(Q17)+Sof(Q18)+Sof(Q19)+Sof(Q20)+Sof(Q21)+Sof(Q22)+Sof(Q23)+
 Sof(Q24)+Sof(Q25)+Sof(Q26)+Sof(Q27)+Sof(Q28)+Sof(Q29)+Sof(Q30)+Sof(Q31)+
 Sof(Q32)+Sof(Q33)+Sof(Q34)+Sof(Q35)+Sof(Q36)+Sof(Q37)+Sof(Q38)+Sof(Q39)+
 Sof(Q40)+Sof(Q41)+Sof(Q42)+Sof(Q43)+Sof(Q44)+Sof(Q45)+Sof(Q46)+Sof(Q47)+
 Sof(Q48)+Sof(Q49)+Sof(Q50)+Sof(Q51)+Sof(Q52)+Sof(Q53)+Sof(Q54)+Sof(Q55)+
 Sof(Q56)+Sof(Q57)+Sof(Q58)+Sof(Q59)+Sof(Q60)+Sof(Q61)+Sof(Q62)+Sof(Q63)+
 Sof(Q64)+Sof(Q65)+Sof(Q66)+Sof(Q67)+Sof(Q68)+Sof(Q69)+Sof(Q70)+Sof(Q71)+
 Sof(Q72)+Sof(Q73)+Sof(Q74)+Sof(Q75)+Sof(Q76)+Sof(Q77)+Sof(Q78)+Sof(Q79)+
 Sof(Q80)]=1 with esd of 0.01
 Sof(P1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=1-FVAR(1)
 Sof(S1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(C1)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(S1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(C1)=Sof(F1)=Sof(F2)=Sof(F3)=0.5*FVAR(3)
 1(DFIX)=1(DFIX)=FVAR(3)
 1(DFIX)=1(DFIX)=1.414*FVAR(4)
 Sof(C23B)=Sof(C24B)=Sof(H24B)=Sof(C25B)=Sof(H25B)=Sof(C26B)=Sof(H26B)=
 Sof(C27B)=Sof(H27B)=Sof(C28B)=Sof(H28B)=1-FVAR(4)
 Sof(C23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=
 Sof(H27)=Sof(C28)=Sof(H28)=FVAR(4)
 Sof(S1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(C1)=Sof(F1)=Sof(F2)=Sof(F3)=0.5*FVAR(6)
 Sof(P1)=0.5*FVAR(7)
 Sof(F2)=Sof(F3)=Sof(F4)=Sof(Q1)=Sof(Q2)=Sof(Q3)=Sof(Q4)=Sof(Q5)=Sof(Q6)=
 Sof(Q7)=Sof(Q8)=Sof(Q9)=Sof(Q10)=Sof(Q11)=Sof(Q12)=Sof(Q13)=Sof(Q14)=Sof(Q15)=
 Sof(Q16)=Sof(Q17)=Sof(Q18)=Sof(Q19)=Sof(Q20)=Sof(Q21)=Sof(Q22)=Sof(Q23)=
 Sof(Q24)=Sof(Q25)=Sof(Q26)=Sof(Q27)=Sof(Q28)=Sof(Q29)=Sof(Q30)=Sof(Q31)=
 Sof(Q32)=Sof(Q33)=Sof(Q34)=Sof(Q35)=Sof(Q36)=Sof(Q37)=Sof(Q38)=Sof(Q39)=
 Sof(Q40)=Sof(Q41)=Sof(Q42)=Sof(Q43)=Sof(Q44)=Sof(Q45)=Sof(Q46)=Sof(Q47)=
 Sof(Q48)=Sof(Q49)=Sof(Q50)=Sof(Q51)=Sof(Q52)=Sof(Q53)=Sof(Q54)=Sof(Q55)=
 Sof(Q56)=Sof(Q57)=Sof(Q58)=Sof(Q59)=Sof(Q60)=Sof(Q61)=Sof(Q62)=Sof(Q63)=
 Sof(Q64)=Sof(Q65)=Sof(Q66)=Sof(Q67)=Sof(Q68)=Sof(Q69)=Sof(Q70)=Sof(Q71)=
 Sof(Q72)=Sof(Q73)=Sof(Q74)=Sof(Q75)=Sof(Q76)=Sof(Q77)=Sof(Q78)=Sof(Q79)=
 Sof(Q80)=FVAR(6)
 Fixed Sof: S1(0.5) O1(0.5) O2(0.5) O3(0.5) C1(0.5) F1(0.5) F2(0.5) F3(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C24B(H24B), C25B(H25B), C26B(H26B), C27B(H27B), C28B(H28B), C32(H32),
 C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41),
  C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C52(H52),
 C53(H53), C54(H54), C55(H55), C56(H56), C58(H58), C59(H59), C60(H60), C61(H61),
  C62(H62), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C72(H72),
 C73(H73), C74(H74), C75(H75), C76(H76), C78(H78), C79(H79), C80(H80), C81(H81),
  C82(H82), C84(H84), C85(H85), C86(H86), C87(H87), C88(H88), C92(H92),
 C93(H93), C94(H94), C95(H95), C96(H96), C98(H98), C99(H99), C100(H100),
 C101(H101), C102(H102), C104(H104), C105(H105), C106(H106), C107(H107),
 C108(H108), C112(H112), C113(H113), C114(H114), C115(H115), C116(H116),
 C118(H118), C119(H119), C120(H120), C121(H121), C122(H122), C124(H124),
 C125(H125), C126(H126), C127(H127), C128(H128), C132(H132), C133(H133),
 C134(H134), C135(H135), C136(H136), C138(H138), C139(H139), C140(H140),
 C141(H141), C142(H142), C144(H144), C145(H145), C146(H146), C147(H147),
 C148(H148), C152(H152), C153(H153), C154(H154), C155(H155), C156(H156),
 C158(H158), C159(H159), C160(H160), C161(H161), C162(H162), C164(H164),
 C165(H165), C166(H166), C167(H167), C168(H168), C172(H172), C173(H173),
 C174(H174), C175(H175), C176(H176), C178(H178), C179(H179), C180(H180),
 C181(H181), C182(H182), C184(H184), C185(H185), C186(H186), C187(H187),
 C188(H188), C192(H192), C193(H193), C194(H194), C195(H195), C196(H196),
 C198(H198), C199(H199), C200(H200), C201(H201), C202(H202), C204(H204),
 C205(H205), C206(H206), C207(H207), C208(H208), C212(H212), C213(H213),
 C214(H214), C215(H215), C216(H216), C218(H218), C219(H219), C220(H220),
 C221(H221), C222(H222), C224(H224), C225(H225), C226(H226), C227(H227),
 C228(H228), C232(H232), C233(H233), C234(H234), C235(H235), C236(H236),
 C238(H238), C239(H239), C240(H240), C241(H241), C242(H242), C244(H244),
 C245(H245), C246(H246), C247(H247), C248(H248)
;
_shelx_res_checksum              25839
_shelx_hkl_checksum              33883
_shelx_shelxl_version_number     2016/6
_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 1.712
_oxdiff_exptl_absorpt_empirical_full_min 0.655