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

data_7122809
_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 Cl2 P4 Rh2, 1.27(C H2 Cl2)'
_chemical_formula_sum            'C52.24 H46.48 Cl4.48 P4 Rh2'
_chemical_formula_weight         1162.77
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_symmetry_space_group_name_Hall  'P 4w'
_symmetry_space_group_name_H-M   'P 41'
_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                   21.2680(4)
_cell_length_b                   21.2680(4)
_cell_length_c                   14.3108(4)
_cell_measurement_reflns_used    20494
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      27.4270
_cell_measurement_theta_min      3.5610
_cell_volume                     6473.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3744
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -20.00  30.00   1.00   20.00    --  -11.22 -99.00-180.00   50
  2  \w    -20.00  30.00   1.00   20.00    --  -11.22 -99.00   0.00   50
  3  \w   -100.00 -35.00   1.00   20.00    --  -11.22-178.00-180.00   65
  4  \w   -100.00 -35.00   1.00   20.00    --  -11.22-178.00  30.00   65
  5  \w    -14.00  29.00   1.00   20.00    --  -11.22 -99.00 120.00   43
  6  \w    -27.00  61.00   1.00   20.00    --   11.46  19.00  60.00   88
  7  \w    -27.00  84.00   1.00   20.00    --   11.46   0.00 150.00  111
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0148418000
_diffrn_orient_matrix_UB_12      0.0294072000
_diffrn_orient_matrix_UB_13      0.0076706000
_diffrn_orient_matrix_UB_21      0.0298760000
_diffrn_orient_matrix_UB_22      -0.0146118000
_diffrn_orient_matrix_UB_23      -0.0039951000
_diffrn_orient_matrix_UB_31      -0.0001100000
_diffrn_orient_matrix_UB_32      0.0058027000
_diffrn_orient_matrix_UB_33      -0.0487904000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0581
_diffrn_reflns_av_unetI/netI     0.0484
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            80627
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.364
_diffrn_reflns_theta_min         3.347
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.821
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75972
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.193
_exptl_crystal_description       needle
_exptl_crystal_F_000             2344
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.207
_exptl_crystal_size_min          0.146
_refine_diff_density_max         1.276
_refine_diff_density_min         -0.691
_refine_diff_density_rms         0.136
_refine_ls_abs_structure_details
;
 Flack x determined using 4519 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.018(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     587
_refine_ls_number_reflns         13162
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0833
_refine_ls_R_factor_gt           0.0594
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1024P)^2^+14.7233P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1562
_refine_ls_wR_factor_ref         0.1815
_reflns_Friedel_coverage         0.914
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                10739
_reflns_number_total             13162
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc09692a2.cif
_cod_data_source_block           hb_1008_3_scale
_cod_original_cell_volume        6473.2(3)
_cod_database_code               7122809
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.71
_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. Uiso/Uaniso restraints and constraints
Cl13 \\sim Cl14 \\sim C102: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C55) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C56) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
3. Others
 Sof(Cl13)=Sof(Cl14)=Sof(C102)=Sof(H10C)=Sof(H10D)=FVAR(1)
 Fixed Sof: Cl11(0.65759) Cl12(0.65759) C101(0.65759) H10A(0.65759)
 H10B(0.65759)
4.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C101(H10A,H10B), C102(H10C,H10D)
4.b Aromatic/amide H refined with riding coordinates:
 C12(H12), 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),
  C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C82(H82), C83(H83),
 C84(H84), C85(H85), C86(H86)
;
_shelx_res_checksum              74223
_shelx_hkl_checksum              32163
_ins_header
;
TITL HB_1008_3_scale in P4(1) 
REM P4(1) (#76 in standard setting)
CELL 0.71073  21.267992  21.267992  14.310824  90.0000  90.0000  90.0000
ZERR    6.00   0.000432   0.000432   0.000375   0.0000   0.0000   0.0000
LATT -1
SYMM -x,-y, z+1/2 
SYMM -y, x, z+1/4 
SYMM  y,-x, z+3/4 
SFAC C H P Cl Rh
UNIT 306.00 264.00 24.00 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:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.175
_oxdiff_exptl_absorpt_empirical_full_min 0.805