Dimetalla-heterocyclic carbenes: the interconversion of chalcocarbonyl and carbido ligands.
Barnett, Harrison J.; Hill, Anthony F.; Chemical communications (Cambridge, England) 56 (2020) 12593–12596; doi:10.1039/d0cc05106c

data_7127189
_publ_section_title
;
 Dimetalla-heterocyclic carbenes: the interconversion of chalcocarbonyl
 and carbido ligands.
;
_journal_issue                   83
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              12593
_journal_page_last               12596
_journal_paper_doi               10.1039/d0cc05106c
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         '2(C51 H44 Cl2 P4 Rh2 S), 2.5(C7 H8)'
_chemical_formula_sum            'C119.5 H108 Cl4 P8 Rh4 S2'
_chemical_formula_weight         2409.37
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2020-02-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-07-01 deposited with the CCDC.	2020-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                71.332(2)
_cell_angle_beta                 72.996(2)
_cell_angle_gamma                79.948(2)
_cell_formula_units_Z            2
_cell_length_a                   16.3139(3)
_cell_length_b                   19.5375(3)
_cell_length_c                   22.4893(4)
_cell_measurement_reflns_used    21994
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      70.7550
_cell_measurement_theta_min      4.2970
_cell_volume                     6468.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.36a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.36a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.36a (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.969
_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    -65.00  35.00   1.00    1.00    --  -36.03  19.00-150.00  100
  2  \w    -53.00  31.00   1.00    1.00    --  -36.03  57.00 -90.00   84
  3  \w   -105.00 -17.00   1.00    1.00    --  -36.03 -38.00  30.00   88
  4  \w     27.00  89.00   1.00    1.00    --   36.03-125.00-180.00   62
  5  \w      6.00  75.00   1.00    1.00    --   36.03 -99.00 -30.00   69
  6  \w     35.00 109.00   1.00    5.00    --  105.15-111.00-120.00   74
  7  \w     36.00 106.00   1.00    5.00    --  105.15 -95.00   0.00   70
  8  \w     38.00 132.00   1.00    5.00    --  105.15 -77.00  60.00   94
  9  \w     37.00 123.00   1.00    5.00    --  105.15 -45.00 150.00   86
 10  \w     87.00 172.00   1.00    5.00    --  105.15  61.00 -60.00   85
 11  \w    103.00 173.00   1.00    5.00    --  105.15  77.00 150.00   70
 12  \w     37.00 123.00   1.00    5.00    --  105.15 -45.00   0.00   86
 13  \w     37.00 123.00   1.00    5.00    --  105.15 -45.00  90.00   86
 14  \w     37.00 123.00   1.00    5.00    --  105.15 -45.00-120.00   86
 15  \w     38.00 132.00   1.00    5.00    --  105.15 -77.00-120.00   94
 16  \w     36.00 174.00   1.00    5.00    --  105.15   0.00 -60.00  138
 17  \w      9.00  42.00   1.00    1.00    --   36.03  78.00 -66.96   33
 18  \w     17.00 105.00   1.00    1.00    --   36.03  38.00 -90.00   88
 19  \w     19.00 103.00   1.00    1.00    --   36.03  57.00-180.00   84
 20  \w      3.00  28.00   1.00    1.00    --   36.03  88.00  14.28   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0512227000
_diffrn_orient_matrix_UB_12      0.0421051000
_diffrn_orient_matrix_UB_13      -0.0503298000
_diffrn_orient_matrix_UB_21      -0.0506092000
_diffrn_orient_matrix_UB_22      -0.0663297000
_diffrn_orient_matrix_UB_23      0.0174645000
_diffrn_orient_matrix_UB_31      -0.0681531000
_diffrn_orient_matrix_UB_32      0.0284704000
_diffrn_orient_matrix_UB_33      0.0524346000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0668
_diffrn_reflns_av_unetI/netI     0.0792
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            48252
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.747
_diffrn_reflns_theta_min         3.553
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.368
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.223
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.36a (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
;
_exptl_crystal_colour            gold
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       plate
_exptl_crystal_F_000             2450
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.082
_refine_diff_density_max         2.232
_refine_diff_density_min         -1.663
_refine_diff_density_rms         0.194
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1235
_refine_ls_number_reflns         24086
_refine_ls_number_restraints     263
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0858
_refine_ls_R_factor_gt           0.0728
_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^)+(0.1310P)^2^+18.2776P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2055
_refine_ls_wR_factor_ref         0.2249
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19891
_reflns_number_total             24086
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc05106c2.cif
_cod_data_source_block           hb_1164-5-1_scale
_cod_depositor_comments
'Adding full bibliography for 7127189--7127192.cif.'
_cod_original_formula_sum        'C119.50 H108 Cl4 P8 Rh4 S2'
_cod_database_code               7127189
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.623
_shelx_estimated_absorpt_t_min   0.185
_reflns_odcompleteness_completeness 99.19
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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
 C220-C226
 1.55 with sigma of 0.02
3. Restrained planarity
 C220, C221, C225, C226
 with sigma of 0.1
4. Rigid bond restraints
 C210, C214, C216, C215, C213, C212, C211
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C222, C220, C221, C225, C224, C223, C226
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
C207 \\sim H20A \\sim H20B \\sim H20C \\sim C204 \\sim H204 \\sim C201 \\sim
C202 \\sim C203 \\sim C205 \\sim H205 \\sim C206 \\sim H206: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C210 \\sim C214 \\sim C216 \\sim C215 \\sim C213 \\sim C212 \\sim C211: within
1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
C222 \\sim H222 \\sim C220 \\sim C221 \\sim C225 \\sim C224 \\sim H224 \\sim
C223 \\sim H223 \\sim C226: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C201) \\sim Ueq, Uanis(C207) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
Uanis(C226) \\sim Ueq, Uanis(C221) \\sim Ueq, Uanis(C220) \\sim Ueq,
Uanis(C222) \\sim Ueq, Uanis(C225) \\sim Ueq, Uanis(C223) \\sim Ueq,
Uanis(C224) \\sim Ueq, : with sigma of 0.05 and sigma for terminal atoms of 0.1
6. Others
 Fixed Sof: C210(0.5) C215(0.5) H215(0.5) C214(0.5) H214(0.5) C213(0.5)
 H213(0.5) C212(0.5) H212(0.5) C211(0.5) H211(0.5) C216(0.5) H21A(0.5)
 H21B(0.5) H21C(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C5(H5A,H5B)
7.b Me refined with everything fixed:
 C216(H21A,H21B,H21C), C226(H22A,H22B,H22C)
7.c Aromatic/amide H refined with riding coordinates:
 C75(H75), C12(H12), C45(H45), C74(H74), C33(H33), C85(H85), C66(H66),
 C76(H76), C52(H52), C72(H72), C46(H46), C63(H63), C86(H86), C16(H16), C54(H54),
  C82(H82), C25(H25), C53(H53), C15(H15), C83(H83), C34(H34), C24(H24),
 C42(H42), C62(H62), C56(H56), C73(H73), C65(H65), C26(H26), C35(H35), C64(H64),
  C43(H43), C23(H23), C84(H84), C22(H22), C14(H14), C55(H55), C32(H32),
 C36(H36), C13(H13), C44(H44), C124(H124), C144(H144), C134(H134), C173(H173),
 C106(H106), C104(H104), C145(H145), C152(H152), C166(H166), C175(H175),
 C174(H174), C163(H163), C126(H126), C115(H115), C146(H146), C176(H176),
 C112(H112), C103(H103), C156(H156), C143(H143), C164(H164), C116(H116),
 C113(H113), C114(H114), C136(H136), C125(H125), C172(H172), C162(H162),
 C155(H155), C142(H142), C122(H122), C135(H135), C133(H133), C102(H102),
 C165(H165), C123(H123), C153(H153), C132(H132), C154(H154), C105(H105),
 C215(H215), C214(H214), C213(H213), C212(H212), C211(H211), C202(H202),
 C203(H203), C204(H204), C205(H205), C206(H206), C221(H221), C225(H225),
 C224(H224), C223(H223), C222(H222)
7.d Fitted hexagon refined as free rotating group:
 C210(C215,C214,C213,C212,C211), C201(C202,C203,C204,C205,C206), C221(C220,
 C225,C224,C223,C222)
7.e Idealised Me refined as rotating group:
 C207(H20A,H20B,H20C)
;
_shelx_res_checksum              59198
_ins_header
;
TITL HB_1164-5-1_scale in P-1 
REM P-1 (#2 in standard setting)
CELL 1.54184  16.313872  19.537451  22.489289  71.3324  72.9963  79.9480
ZERR    3.00   0.000297   0.000342   0.000389   0.0016   0.0016   0.0015
LATT  1
SFAC C H P S Cl Rh
UNIT 300.00 300.00 24.00 6.00 12.00 12.00
TREF
HKLF 4
END
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 1.558
_oxdiff_exptl_absorpt_empirical_full_min 0.663