Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange.
Chadwick, F. Mark; Krämer, Tobias; Gutmann, Torsten; Rees, Nicholas H.; Thompson, Amber L.; Edwards, Alison J.; Buntkowsky, Gerd; Macgregor, Stuart A.; Weller, Andrew S.; Journal of the American Chemical Society 138 (2016) 13369–13378; doi:10.1021/jacs.6b07968

data_4130935
_publ_section_title
;
 Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by
 Solid/Gas Single-Crystal to Single-Crystal H/D Exchange.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13369
_journal_page_last               13378
_journal_paper_doi               10.1021/jacs.6b07968
_journal_volume                  138
_journal_year                    2016
_chemical_compound_source        SYN
_chemical_formula_moiety         'C32 H12 B F24, C33 H60 P2 Rh'
_chemical_formula_sum            'C65 H72 B F24 P2 Rh'
_chemical_formula_weight         1484.90
_chemical_melting_point          ?
_chemical_name_systematic        H8-2-290K
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 134.55(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.100(2)
_cell_length_b                   18.2890(9)
_cell_length_c                   27.926(3)
_cell_measurement_reflns_used    8040
_cell_measurement_temperature    290
_cell_measurement_theta_max      74
_cell_measurement_theta_min      3
_cell_volume                     6952(3)
_computing_cell_refinement       'CrysAlis, (Oxford Diffraction, 2002)'
_computing_data_collection       'SuperNova, (Oxford Diffraction, 2010)'
_computing_data_reduction        'CrysAlis, (Oxford Diffraction, 2002)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      290
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Oxford Diffraction SuperNova'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54180
_diffrn_reflns_av_R_equivalents  0.024
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            28825
_diffrn_reflns_theta_full        67.395
_diffrn_reflns_theta_max         74.060
_diffrn_reflns_theta_min         3.168
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.334
_exptl_absorpt_correction_T_max  0.72
_exptl_absorpt_correction_T_min  0.49
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlis, (Oxford Diffraction, 2002)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3032
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.100
_refine_diff_density_max         1.52
_refine_diff_density_min         -0.90
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.8662
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1027
_refine_ls_number_reflns         13636
_refine_ls_number_restraints     1596
_refine_ls_R_factor_all          0.0776
_refine_ls_R_factor_gt           0.0637
_refine_ls_shift/su_max          0.0688383
_refine_ls_shift/su_mean         0.0008943
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 0.216E+04 0.361E+04 0.215E+04 848. 177. 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1879
_refine_ls_wR_factor_gt          0.1632
_refine_ls_wR_factor_ref         0.1876
_reflns_limit_h_max              16
_reflns_limit_h_min              -23
_reflns_limit_k_max              22
_reflns_limit_k_min              0
_reflns_limit_l_max              34
_reflns_limit_l_min              0
_reflns_number_gt                10950
_reflns_number_total             13701
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   3.76
_oxford_diffrn_Wilson_scale      0.67
_oxford_refine_ls_r_factor_ref   0.0775
_oxford_refine_ls_scale          1.399(6)
_oxford_reflns_number_all        13644
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_oxford_structure_analysis_title 'C:\Users\ASWGroup\Desktop\Crysta At 10:53 on'
_iucr_refine_instructions_details_constraints
;
BLOCK SCALE X'S, U'S 
RIDE C   (   1,X'S) H   (  12,X'S) H   (  11,X'S) 
RIDE C   (   2,X'S) H   (  22,X'S) H   (  21,X'S) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H   (  42,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  52,X'S) H   (  51,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) 
RIDE C   (   7,X'S) H   (  72,X'S) H   (  71,X'S) 
RIDE C   (   8,X'S) H   (  81,X'S) 
RIDE C   (   9,X'S) H   (  92,X'S) H   (  91,X'S) 
RIDE C   (  10,X'S) H   ( 102,X'S) H   ( 101,X'S) 
RIDE C   (  11,X'S) H   ( 112,X'S) H   ( 111,X'S) 
RIDE C   (  12,X'S) H   ( 122,X'S) H   ( 121,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) H   ( 132,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 152,X'S) H   ( 151,X'S) 
RIDE C   (  16,X'S) H   ( 162,X'S) H   ( 161,X'S) 
RIDE C   (  17,X'S) H   ( 172,X'S) H   ( 171,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) H   ( 182,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) H   ( 192,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) H   ( 202,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) H   ( 212,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) H   ( 232,X'S) 
RIDE C   (  24,X'S) H   ( 242,X'S) H   ( 241,X'S) 
RIDE C   (  25,X'S) H   ( 252,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 262,X'S) H   ( 261,X'S) 
RIDE C   (  27,X'S) H   ( 272,X'S) H   ( 271,X'S) 
RIDE C   (  28,X'S) H   ( 281,X'S) 
RIDE C   (  29,X'S) H   ( 292,X'S) H   ( 291,X'S) 
RIDE C   (  30,X'S) H   ( 302,X'S) H   ( 301,X'S) 
RIDE C   (  31,X'S) H   ( 312,X'S) H   ( 311,X'S) 
RIDE C   (  32,X'S) H   ( 322,X'S) H   ( 321,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) H   ( 332,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) 
RIDE C   (  47,X'S) H   ( 471,X'S) 
RIDE C   (  51,X'S) H   ( 511,X'S) 
RIDE C   (  53,X'S) H   ( 531,X'S) 
RIDE C   (  55,X'S) H   ( 551,X'S) 
RIDE C   (  59,X'S) H   ( 591,X'S) 
RIDE C   (  61,X'S) H   ( 611,X'S) 
RIDE C   (  63,X'S) H   ( 631,X'S) 
END                                                                             
;
_iucr_refine_instructions_details_restraints
;
NO 
SAME C(38) C(41) F(40) F(50) F(60) AND 
CONT C(38) C(41) F(50) F(60) F(40) AND 
CONT C(38) C(41) F(60) F(40) F(50) AND 
CONT C(38) C(41) F(41) F(51) F(61) AND 
CONT C(38) C(41) F(51) F(61) F(41) AND 
CONT C(38) C(41) F(61) F(41) F(51) 
DELU 0.015 C(38) C(41) F(40) F(50) F(60) AND 
CONT C(38) C(41) F(50) F(60) F(40) AND 
CONT C(38) C(41) F(60) F(40) F(50) AND 
CONT C(38) C(41) F(41) F(51) F(61) AND 
CONT C(38) C(41) F(51) F(61) F(41) AND 
CONT C(38) C(41) F(61) F(41) F(51) 
SIMU 0.015 C(38) C(41) F(40) F(50) F(60) AND 
CONT C(38) C(41) F(50) F(60) F(40) AND 
CONT C(38) C(41) F(60) F(40) F(50) AND 
CONT C(38) C(41) F(41) F(51) F(61) AND 
CONT C(38) C(41) F(51) F(61) F(41) AND 
CONT C(38) C(41) F(61) F(41) F(51) 
SAME C(44) C(48) F(70) F(80) F(91) AND 
CONT C(44) C(48) F(80) F(91) F(70) AND 
CONT C(44) C(48) F(91) F(70) F(80) AND 
CONT C(44) C(48) F(71) F(81) F(90) AND 
CONT C(44) C(48) F(81) F(90) F(71) AND 
CONT C(44) C(48) F(90) F(71) F(81) 
DELU 0.015 C(44) C(48) F(70) F(80) F(91) AND 
CONT C(44) C(48) F(80) F(91) F(70) AND 
CONT C(44) C(48) F(91) F(70) F(80) AND 
CONT C(44) C(48) F(71) F(81) F(90) AND 
CONT C(44) C(48) F(81) F(90) F(71) AND 
CONT C(44) C(48) F(90) F(71) F(81) 
SIMU 0.015 C(44) C(48) F(70) F(80) F(91) AND 
CONT C(44) C(48) F(80) F(91) F(70) AND 
CONT C(44) C(48) F(91) F(70) F(80) AND 
CONT C(44) C(48) F(71) F(81) F(90) AND 
CONT C(44) C(48) F(81) F(90) F(71) AND 
CONT C(44) C(48) F(90) F(71) F(81) 
SAME C(46) C(49) F(101) F(111) F(120) AND 
CONT C(46) C(49) F(111) F(120) F(101) AND 
CONT C(46) C(49) F(120) F(101) F(111) AND 
CONT C(46) C(49) F(100) F(110) F(121) AND 
CONT C(46) C(49) F(110) F(121) F(100) AND 
CONT C(46) C(49) F(121) F(100) F(110) 
DELU 0.015 C(46) C(49) F(101) F(111) F(120) AND 
CONT C(46) C(49) F(111) F(120) F(101) AND 
CONT C(46) C(49) F(120) F(101) F(111) AND 
CONT C(46) C(49) F(100) F(110) F(121) AND 
CONT C(46) C(49) F(110) F(121) F(100) AND 
CONT C(46) C(49) F(121) F(100) F(110) 
SIMU 0.015 C(46) C(49) F(101) F(111) F(120) AND 
CONT C(46) C(49) F(111) F(120) F(101) AND 
CONT C(46) C(49) F(120) F(101) F(111) AND 
CONT C(46) C(49) F(100) F(110) F(121) AND 
CONT C(46) C(49) F(110) F(121) F(100) AND 
CONT C(46) C(49) F(121) F(100) F(110) 
SAME C(54) C(57) F(161) F(171) F(180) AND 
CONT C(54) C(57) F(171) F(180) F(161) AND 
CONT C(54) C(57) F(180) F(161) F(171) AND 
CONT C(54) C(57) F(160) F(170) F(181) AND 
CONT C(54) C(57) F(170) F(181) F(160) AND 
CONT C(54) C(57) F(181) F(160) F(170) 
DELU 0.015 C(54) C(57) F(161) F(171) F(180) AND 
CONT C(54) C(57) F(171) F(180) F(161) AND 
CONT C(54) C(57) F(180) F(161) F(171) AND 
CONT C(54) C(57) F(160) F(170) F(181) AND 
CONT C(54) C(57) F(170) F(181) F(160) AND 
CONT C(54) C(57) F(181) F(160) F(170) 
SIMU 0.015 C(54) C(57) F(161) F(171) F(180) AND 
CONT C(54) C(57) F(171) F(180) F(161) AND 
CONT C(54) C(57) F(180) F(161) F(171) AND 
CONT C(54) C(57) F(160) F(170) F(181) AND 
CONT C(54) C(57) F(170) F(181) F(160) AND 
CONT C(54) C(57) F(181) F(160) F(170) 
SAME C(52) C(56) F(131) F(141) F(151) AND 
CONT C(52) C(56) F(141) F(151) F(131) AND 
CONT C(52) C(56) F(151) F(131) F(141) AND 
CONT C(52) C(56) F(130) F(140) F(150) AND 
CONT C(52) C(56) F(140) F(150) F(130) AND 
CONT C(52) C(56) F(150) F(130) F(140) 
DELU 0.015 C(52) C(56) F(131) F(141) F(151) AND 
CONT C(52) C(56) F(141) F(151) F(131) AND 
CONT C(52) C(56) F(151) F(131) F(141) AND 
CONT C(52) C(56) F(130) F(140) F(150) AND 
CONT C(52) C(56) F(140) F(150) F(130) AND 
CONT C(52) C(56) F(150) F(130) F(140) 
SIMU 0.015 C(52) C(56) F(131) F(141) F(151) AND 
CONT C(52) C(56) F(141) F(151) F(131) AND 
CONT C(52) C(56) F(151) F(131) F(141) AND 
CONT C(52) C(56) F(130) F(140) F(150) AND 
CONT C(52) C(56) F(140) F(150) F(130) AND 
CONT C(52) C(56) F(150) F(130) F(140) 
SAME C(62) C(65) F(221) F(231) F(241) AND 
CONT C(62) C(65) F(231) F(241) F(221) AND 
CONT C(62) C(65) F(241) F(221) F(231) AND 
CONT C(62) C(65) F(220) F(230) F(240) AND 
CONT C(62) C(65) F(230) F(240) F(220) AND 
CONT C(62) C(65) F(240) F(220) F(230) 
DELU 0.015 C(62) C(65) F(221) F(231) F(241) AND 
CONT C(62) C(65) F(231) F(241) F(221) AND 
CONT C(62) C(65) F(241) F(221) F(231) AND 
CONT C(62) C(65) F(220) F(230) F(240) AND 
CONT C(62) C(65) F(230) F(240) F(220) AND 
CONT C(62) C(65) F(240) F(220) F(230) 
SIMU 0.015 C(62) C(65) F(221) F(231) F(241) AND 
CONT C(62) C(65) F(231) F(241) F(221) AND 
CONT C(62) C(65) F(241) F(221) F(231) AND 
CONT C(62) C(65) F(220) F(230) F(240) AND 
CONT C(62) C(65) F(230) F(240) F(220) AND 
CONT C(62) C(65) F(240) F(220) F(230) 
SAME C(60) C(64) F(190) F(201) F(210) AND 
CONT C(60) C(64) F(201) F(210) F(190) AND 
CONT C(60) C(64) F(210) F(190) F(201) AND 
CONT C(60) C(64) F(191) F(200) F(211) AND 
CONT C(60) C(64) F(200) F(211) F(191) AND 
CONT C(60) C(64) F(211) F(191) F(200) 
DELU 0.015 C(60) C(64) F(190) F(201) F(210) AND 
CONT C(60) C(64) F(201) F(210) F(190) AND 
CONT C(60) C(64) F(210) F(190) F(201) AND 
CONT C(60) C(64) F(191) F(200) F(211) AND 
CONT C(60) C(64) F(200) F(211) F(191) AND 
CONT C(60) C(64) F(211) F(191) F(200) 
SIMU 0.015 C(60) C(64) F(190) F(201) F(210) AND 
CONT C(60) C(64) F(201) F(210) F(190) AND 
CONT C(60) C(64) F(210) F(190) F(201) AND 
CONT C(60) C(64) F(191) F(200) F(211) AND 
CONT C(60) C(64) F(200) F(211) F(191) AND 
CONT C(60) C(64) F(211) F(191) F(200) 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;
_cod_data_source_file            ja6b07968_si_003.cif
_cod_data_source_block           H82290K
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_original_sg_symbol_H-M      'P 1 21/c 1 '
_cod_original_formula_sum        'C65 H72 B1 F24 P2 Rh1'
_cod_database_code               4130935