Halogenation of A-Frame μ-Carbido Complexes: Synthesis of η2-Halocarbynes
Hill, Anthony; Barnett, Harrison J.; Chemical Communications  (2019) –; doi:10.1039/C8CC09692A

data_7122812
_publ_section_title
;
 Halogenation of A-Frame \m-Carbido Complexes: Synthesis of
 \h2-Halocarbynes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C8CC09692A
_journal_year                    2019
_chemical_formula_moiety         'C51 H44 Cl6 P4 Rh2, C H Cl3'
_chemical_formula_sum            'C52 H45 Cl9 P4 Rh2'
_chemical_formula_weight         1318.63
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-01-07 deposited with the CCDC.
2019-01-11 downloaded from the CCDC.
;
_cell_angle_alpha                81.467(4)
_cell_angle_beta                 76.544(3)
_cell_angle_gamma                69.731(4)
_cell_formula_units_Z            2
_cell_length_a                   10.9452(5)
_cell_length_b                   14.1036(7)
_cell_length_c                   23.4931(8)
_cell_measurement_reflns_used    15083
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      28.7160
_cell_measurement_theta_min      3.6730
_cell_volume                     3299.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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 0.997
_diffrn_measured_fraction_theta_max 0.892
_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     -1.00  83.00   1.00    6.00    --   15.57  57.00 120.00   84
  2  \w     -1.00  83.00   1.00    6.00    --   15.57  57.00-150.00   84
  3  \w    -52.00  32.00   1.00    6.00    --   15.57 -57.00-150.00   84
  4  \w     -1.00  83.00   1.00    6.00    --   15.57  57.00  60.00   84
  5  \w    -11.00  83.00   1.00    6.00    --   15.57  77.00 -30.00   94
  6  \w     -8.00  62.00   1.00    6.00    --   15.57-113.00  52.00   70
  7  \w     35.00  88.00   1.00    6.00    --   15.57 178.00  30.00   53
  8  \w     -3.00  85.00   1.00    6.00    --   15.57  38.00 -60.00   88
  9  \w     35.00  88.00   1.00    6.00    --   15.57 178.00-150.00   53
 10  \w    -20.00  55.00   1.00    6.00    --   15.57 -99.00 -60.00   75
 11  \w    -20.00  55.00   1.00    6.00    --   15.57 -99.00 120.00   75
 12  \w    -52.00  32.00   1.00    6.00    --   15.57 -57.00 -30.00   84
 13  \w    -63.00 -13.00   1.00    6.00    --  -16.67 113.00 143.00   50
 14  \w    -20.00   5.00   1.00    6.00    --   15.57 -99.00-180.00   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      0.0263631000
_diffrn_orient_matrix_UB_12      -0.0534916000
_diffrn_orient_matrix_UB_13      0.0044309000
_diffrn_orient_matrix_UB_21      0.0288519000
_diffrn_orient_matrix_UB_22      -0.0028817000
_diffrn_orient_matrix_UB_23      -0.0302985000
_diffrn_orient_matrix_UB_31      0.0586059000
_diffrn_orient_matrix_UB_32      0.0045247000
_diffrn_orient_matrix_UB_33      0.0056102000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1221
_diffrn_reflns_av_unetI/netI     0.1092
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.892
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            70868
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.376
_diffrn_reflns_theta_min         3.247
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.991
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57347
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_description       plate
_exptl_crystal_F_000             1320
_exptl_crystal_size_max          0.885
_exptl_crystal_size_mid          0.414
_exptl_crystal_size_min          0.291
_refine_diff_density_max         1.840
_refine_diff_density_min         -1.007
_refine_diff_density_rms         0.152
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         16210
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.1193
_refine_ls_R_factor_gt           0.0798
_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^)+(0.0992P)^2^+1.6737P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1969
_refine_ls_wR_factor_ref         0.2233
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9963
_reflns_number_total             16210
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc09692a2.cif
_cod_data_source_block           hb_1042-1_scale
_cod_database_code               7122812
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid bond restraints
 C71, C72, C73, C74, C75, C76
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C74)
\\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C76) \\sim Ueq: with sigma of 0.05 and
sigma for terminal atoms of 0.1
4.a Ternary CH refined with riding coordinates:
 C101(H101)
4.b Secondary CH2 refined with riding coordinates:
 C91(H91A,H91B), C92(H92A,H92B)
4.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C13(H13), C14(H14), C15(H15), C16(H16), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
  C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C52(H52), C53(H53),
 C54(H54), C55(H55), C56(H56), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66),
  C76(H76), C72(H72), C73(H73), C74(H74), C75(H75), C82(H82), C83(H83),
 C84(H84), C85(H85), C86(H86)
4.d Fitted hexagon refined as free rotating group:
 C76(C71,C72,C73,C74,C75)
;
_shelx_res_checksum              1857
_shelx_hkl_checksum              84867
_shelx_fab_checksum              40575
_ins_header
;
TITL HB_1042-1_scale in P-1 
REM P-1 (#2 in standard setting)
CELL 0.71073  10.945233  14.103607  23.493092  81.4672  76.5435  69.7312
ZERR    3.00   0.000484   0.000703   0.000826   0.0035   0.0034   0.0043
LATT  1
SFAC C H P Cl Rh
UNIT 150.00 120.00 12.00 18.00 6.00
TREF
HKLF 4
END
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.877
_oxdiff_exptl_absorpt_empirical_full_min 0.356