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

data_7122811
_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 Br6 P4 Rh2'
_chemical_formula_sum            'C51 H44 Br6 P4 Rh2'
_chemical_formula_weight         1466.02
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_symmetry_space_group_name_Hall  'P 4nw 2abw'
_symmetry_space_group_name_H-M   'P 43 21 2'
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3383(2)
_cell_length_b                   15.3383(2)
_cell_length_c                   25.9466(5)
_cell_measurement_reflns_used    11107
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.1750
_cell_measurement_theta_min      4.4670
_cell_volume                     6104.29(16)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -105.00  34.00   1.00    3.00    --  -35.78   0.00-120.00  139
  2  \w     23.00  89.00   1.00    3.00    --   35.78-125.00-180.00   66
  3  \w     23.00  89.00   1.00    3.00    --   35.78-125.00 -30.00   66
  4  \w     19.00 103.00   1.00    3.00    --   35.78  57.00-120.00   84
  5  \w      1.00  75.00   1.00    3.00    --   35.78 -99.00  30.00   74
  6  \w    -33.00  55.00   1.00    3.00    --   35.78 -38.00  30.00   88
  7  \w     91.00 176.00   1.00   30.00    --  108.91  61.00   0.00   85
  8  \w     41.00 136.00   1.00   30.00    --  108.91 -77.00  90.00   95
  9  \w     39.00 113.00   1.00   30.00    --  108.91-111.00  90.00   74
 10  \w     92.00 177.00   1.00   30.00    --  108.91  45.00-180.00   85
 11  \w     40.00 126.00   1.00   30.00    --  108.91 -45.00  30.00   86
 12  \w     39.00 113.00   1.00   30.00    --  108.91-111.00-120.00   74
 13  \w     40.00 126.00   1.00   30.00    --  108.91 -45.00-150.00   86
 14  \w     42.00 127.00   1.00   30.00    --  108.91 -61.00 -60.00   85
 15  \w     39.00 110.00   1.00   30.00    --  108.91 -95.00 -90.00   71
 16  \w     40.00 126.00   1.00   30.00    --  108.91 -45.00 150.00   86
 17  \w     40.00 178.00   1.00   30.00    --  108.91   0.00 150.00  138
 18  \w     19.00  91.00   1.00    3.00    --   35.78  57.00  60.00   72
 19  \w     19.00 103.00   1.00    3.00    --   35.78  57.00 120.00   84
;
_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      -0.0199504000
_diffrn_orient_matrix_UB_12      -0.0954272000
_diffrn_orient_matrix_UB_13      -0.0143181000
_diffrn_orient_matrix_UB_21      0.0024748000
_diffrn_orient_matrix_UB_22      -0.0251091000
_diffrn_orient_matrix_UB_23      0.0574685000
_diffrn_orient_matrix_UB_31      -0.0983951000
_diffrn_orient_matrix_UB_32      0.0187089000
_diffrn_orient_matrix_UB_33      0.0043415000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0930
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            41974
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.586
_diffrn_reflns_theta_max         66.586
_diffrn_reflns_theta_min         4.076
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.192
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56198
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.595
_exptl_crystal_description       prism
_exptl_crystal_F_000             2840
_exptl_crystal_size_max          0.155
_exptl_crystal_size_mid          0.127
_exptl_crystal_size_min          0.067
_refine_diff_density_max         1.856
_refine_diff_density_min         -0.792
_refine_diff_density_rms         0.234
_refine_ls_abs_structure_details
;
 Flack x determined using 1279 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.032(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         5386
_refine_ls_number_restraints     414
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1383
_refine_ls_R_factor_gt           0.0944
_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^)+(0.1859P)^2^+65.9788P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2596
_refine_ls_wR_factor_ref         0.3215
_reflns_Friedel_coverage         0.728
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3779
_reflns_number_total             5386
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc09692a2.cif
_cod_data_source_block           hb_1044-1_scale2
_cod_original_cell_volume        6104.3(2)
_cod_database_code               7122811
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid bond restraints
 C42A, C41A, C46A, C45A, C44A, C43A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C42B, C43B, C44B, C45B, C46B, C41B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C15, C16, C11, C12, C13, C14
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C35B, C36B, C31B, C32B, C33B, C34B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C33A, C32A, C31A, C36A, C35A, C34A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C23B, C22B, C21B, C26B, C25B, C24B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C23A, C24A, C25A, C26A, C21A, C22A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
C42A \\sim C44A \\sim C45A \\sim C46A \\sim C41A \\sim C43A: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C42B \\sim C43B \\sim C44B \\sim C45B \\sim C46B \\sim C41B: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C15 \\sim C16 \\sim C11 \\sim C12 \\sim C13 \\sim C14: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
C36B \\sim C31B \\sim C32B \\sim C33B \\sim C34B \\sim C35B: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C34A \\sim C33A \\sim C32A \\sim C31A \\sim C36A \\sim C35A: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C24B \\sim C25B \\sim C26B \\sim C21B \\sim C22B \\sim C23B: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C23A \\sim C24A \\sim C25A \\sim C26A \\sim C21A \\sim C22A: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C1 \\sim Br1: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(C36B) \\sim Ueq, Uanis(C31B) \\sim Ueq, Uanis(C32B) \\sim Ueq,
Uanis(C33B) \\sim Ueq, Uanis(C34B) \\sim Ueq, Uanis(C35B) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C34A) \\sim Ueq, Uanis(C33A) \\sim Ueq, Uanis(C32A) \\sim Ueq,
Uanis(C31A) \\sim Ueq, Uanis(C36A) \\sim Ueq, Uanis(C35A) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(C35A)=Sof(H35A)=Sof(C34A)=Sof(H34A)=Sof(C33A)=Sof(H33A)=Sof(C32A)=
 Sof(H32A)=Sof(C31A)=Sof(C36A)=Sof(H36A)=1-FVAR(1)
 Sof(C35B)=Sof(H35B)=Sof(C34B)=Sof(H34B)=Sof(C33B)=Sof(H33B)=Sof(C32B)=
 Sof(H32B)=Sof(C31B)=Sof(C36B)=Sof(H36B)=FVAR(1)
 Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(C26A)=Sof(H26A)=Sof(C25A)=Sof(H25A)=
 Sof(C24A)=Sof(H24A)=Sof(C23A)=Sof(H23A)=1-FVAR(2)
 Sof(C24B)=Sof(H24B)=Sof(C23B)=Sof(H23B)=Sof(C22B)=Sof(H22B)=Sof(C21B)=
 Sof(C26B)=Sof(H26B)=Sof(C25B)=Sof(H25B)=FVAR(2)
 Fixed Sof: C43A(0.6) H43A(0.6) C44A(0.6) H44A(0.6) C45A(0.6) H45A(0.6)
 C46A(0.6) H46A(0.6) C41A(0.6) C42A(0.6) H42A(0.6) C44B(0.4) H44B(0.4)
 C45B(0.4) H45B(0.4) C46B(0.4) H46B(0.4) C41B(0.4) C42B(0.4) H42B(0.4)
 C43B(0.4) H43B(0.4)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
5.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C16(H16), C12(H12), C24B(H24B), C23B(H23B),
 C22B(H22B), C26B(H26B), C25B(H25B), C35B(H35B), C34B(H34B), C33B(H33B),
 C32B(H32B), C36B(H36B), C43A(H43A), C44A(H44A), C45A(H45A), C46A(H46A),
 C42A(H42A), C44B(H44B), C45B(H45B), C46B(H46B), C42B(H42B), C43B(H43B),
 C35A(H35A), C34A(H34A), C33A(H33A), C32A(H32A), C36A(H36A), C22A(H22A),
 C26A(H26A), C25A(H25A), C24A(H24A), C23A(H23A)
5.c Fitted hexagon refined as free rotating group:
 C13(C14,C15,C16,C11,C12), C24B(C23B,C22B,C21B,C26B,C25B), C35B(C34B,C33B,C32B,
 C31B,C36B), C43A(C44A,C45A,C46A,C41A,C42A), C44B(C45B,C46B,C41B,C42B,C43B),
 C35A(C34A,C33A,C32A,C31A,C36A), C22A(C21A,C26A,C25A,C24A,C23A)
;
_shelx_res_checksum              10034
_shelx_hkl_checksum              25470
_ins_header
;
TITL HB_1044-1_scale2 in P4(1)2(1)2 
REM P4(1)2(1)2 (#92 in standard setting)
CELL 1.54184  15.338308  15.338308  25.946565  90.0000  90.0000  90.0000
ZERR    5.00   0.000202   0.000202   0.000537   0.0000   0.0000   0.0000
LATT -1
SYMM -x,-y, z+1/2 
SYMM -y+1/2, x+1/2, z+1/4 
SYMM  y+1/2,-x+1/2, z+3/4 
SYMM -x+1/2, y+1/2,-z+1/4 
SYMM  x+1/2,-y+1/2,-z+3/4 
SYMM  y, x,-z 
SYMM -y,-x,-z+1/2 
SFAC C H P Br Rh
UNIT 255.00 220.00 20.00 30.00 10.00
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 1.573
_oxdiff_exptl_absorpt_empirical_full_min 0.686