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_4130933
_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 B1 F24, C33 H56 D4  P2 Rh1'
_chemical_formula_sum            'C65 H68 B D4 F24 P2 Rh'
_chemical_formula_weight         1488.93
_chemical_melting_point          ?
_chemical_name_systematic        exoD4-2
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     geom
_cell_angle_alpha                90
_cell_angle_beta                 91.7138(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.0579(2)
_cell_length_b                   17.9828(2)
_cell_length_c                   19.5453(2)
_cell_measurement_reflns_used    14453
_cell_measurement_temperature    150
_cell_measurement_theta_max      76
_cell_measurement_theta_min      3
_cell_volume                     6695.46(12)
_computing_data_collection       'MAATEL/ANSTO control program'
_computing_data_reduction
'argonne_boxes (Wilkinson et al., 1988) & LaueG (Piltz, 2011)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.804
_diffrn_measured_fraction_theta_max 0.804
_diffrn_measurement_details      '19 images, exposure time 200 minutes'
_diffrn_measurement_device       'Laue image-plate diffractometer'
_diffrn_measurement_device_type  KOALA
_diffrn_measurement_method       Laue
_diffrn_radiation_probe          neutron
_diffrn_radiation_type           neutron
_diffrn_radiation_wavelength     0.85
_diffrn_reflns_av_R_equivalents  0.7426
_diffrn_reflns_av_unetI/netI     0.4108
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            3257
_diffrn_reflns_reduction_process 'LaueG (Piltz, 2011)'
_diffrn_reflns_resolution_max    0.83
_diffrn_reflns_theta_full        44.89
_diffrn_reflns_theta_max         44.99
_diffrn_source                   'nuclear reactor'
_diffrn_source_details           'thermal neutrons, supermirror guides'
_diffrn_source_type
'OPAL reactor, ANSTO, Lucas Heights, Australia'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.0
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.477
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       rod
_exptl_crystal_F_000             1504
_exptl_crystal_size_max          1.0
_exptl_crystal_size_mid          1.0
_exptl_crystal_size_min          0.5
_refine_diff_density_max         1.34
_refine_diff_density_min         -1.34
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   1.3622
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     685
_refine_ls_number_reflns         1843
_refine_ls_number_restraints     288
_refine_ls_R_factor_all          0.2447
_refine_ls_R_factor_gt           0.1676
_refine_ls_shift/su_max          0.0057637
_refine_ls_shift/su_mean         0.0003248
_refine_ls_structure_factor_coef F
_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: 
 19.8 9.26 13.7 11.0 4.31 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.2549
_refine_ls_wR_factor_gt          0.1392
_refine_ls_wR_factor_ref         0.1312
_reflns_number_gt                2158
_reflns_number_total             3257
_reflns_threshold_expression     >2sigma(I)
_oxford_refine_ls_r_factor_ref   0.1482
_oxford_refine_ls_scale          0.358(4)
_oxford_reflns_number_all        3224
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_oxford_structure_analysis_title
'1 in C:\Users\Mark\OneDrive\Chem At 5:41 on '
_cod_data_source_file            ja6b07968_si_003.cif
_cod_data_source_block           exoD42
_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/n 1 '
_cod_original_formula_sum        'C65 H68 B1 D4 F24 P2 Rh1'
_cod_database_code               4130933
_iucr_refine_instructions_details_constraints
;
BLOCK 
CONT SCALE 
CONT FIRST (X'S,U[ISO]) UNTIL LAST 
END                                                                             
;
_iucr_refine_instructions_details_restraints
;
NO 
PLANAR  C(34) UNTIL C(39) 
PLANAR C(42) UNTIL C(47) 
PLANAR C(50) UNTIL C(55) 
PLANAR C(58) UNTIL C(63) 
DIST 0.0,.01 = MEAN  C(34) TO C(35)  C(34) TO C(39) 
CONT C(42) TO C(43)  C(42) TO C(47)  C(50) TO C(51)  C(50) TO C(55) 
CONT C(58) TO C(59)  C(58) TO C(63) 
DIST 0.0,.01 = MEAN  C(34) TO C(36)  C(34) TO C(38) 
CONT C(42) TO C(44)  C(42) TO C(46) C(50) TO C(52)  C(50) TO C(54) 
CONT C(58) TO C(60)  C(58) TO C(62) 
DIST 0.0,.01 = MEAN  C(35) TO C(36)  C(39) TO C(38) 
CONT C(43) TO C(44)  C(47) TO C(46) C(51) TO C(52)  C(55) TO C(54) 
CONT C(59) TO C(60)  C(63) TO C(62) 
DIST 0.0,.01 = MEAN  C(35) TO C(37)  C(39) TO C(37) 
CONT C(43) TO C(45)  C(47) TO C(45) C(51) TO C(53)  C(55) TO C(53) 
CONT C(59) TO C(61)  C(63) TO C(61) 
DIST 0.0,.01 = MEAN  C(36) TO C(37)  C(38) TO C(37) 
CONT C(44) TO C(45)  C(46) TO C(45) C(52) TO C(53)  C(54) TO C(53) 
CONT C(60) TO C(61)  C(62) TO C(61) 
DIST 0.0, 0.01 = MEAN C(35) TO H(351) C(37) TO H(371) C(39) TO H(391) 
CONT C(43) TO H(431) C(45) TO H(451) C(47) TO H(471) 
CONT C(51) TO H(511) C(53) TO H(531) C(55) TO H(551) 
CONT C(59) TO H(591) C(61) TO H(611) C(63) TO H(631) 
DIST 0.0,.01 = MEAN  C(8) TO C(9)  C(8) TO C(13) 
CONT C(14) TO C(15)  C(14) TO C(19) C(23) TO C(22)  C(22) TO C(27) 
CONT  C(28) TO C(29)  C(28) TO C(33) C(9) TO C(10)  C(13) TO C(12) 
CONT C(15) TO C(16)  C(19) TO C(18) C(23) TO C(24)  C(26) TO C(27) 
CONT C(29) TO C(30)  C(33) TO C(32) C(10) TO C(11)  C(12) TO C(11) 
CONT C(16) TO C(17)  C(18) TO C(17) C(25) TO C(24)  C(25) TO C(26) 
CONT C(30) TO C(31)  C(32) TO C(31) 
DIST 0.0,.01 = MEAN  C(8) TO C(10)  C(8) TO C(12) 
CONT C(14) TO C(16)  C(14) TO C(18) C(22) TO C(24)  C(22) TO C(26) 
CONT C(28) TO C(30)  C(28) TO C(32)  C(9) TO C(11)  C(13) TO C(11) 
CONT C(15) TO C(17)  C(19) TO C(17) C(23) TO C(25)  C(27) TO C(25) 
CONT C(29) TO C(31)  C(33) TO C(31) 
DIST 0.0, 0.02 = MEAN  C(13) TO H(131) C(13) TO H(132) C(10) TO H(102) 
CONT C(8) TO H(81)  C(9) TO H(91) C(9) TO H(92) C(10) TO H(101) 
CONT C(11) TO H(111) C(11) TO H(112) C(12) TO H(121) C(12) TO H(122) 
CONT C(14) TO H(141) C(15) TO H(151) C(15) TO H(152) C(16) TO H(161) 
CONT C(17) TO H(171) C(17) TO H(172) C(18) TO H(181) C(18) TO H(182) 
CONT C(19) TO H(192) C(16) TO H(162) C(19) TO H(191) 
CONT C(22) TO H(221) C(23) TO H(231) C(23) TO H(232) C(24) TO H(241) 
CONT C(25) TO H(251) C(25) TO H(252) C(26) TO H(261) C(26) TO H(262) 
CONT C(27) TO H(272) C(24) TO H(242) 
CONT C(28) TO H(281) C(29) TO H(291) C(29) TO H(292) C(30) TO H(301) 
CONT C(31) TO H(311) C(31) TO H(312) C(32) TO H(321) C(32) TO H(322) 
CONT C(33) TO H(332) C(30) TO H(302) C(33) TO H(331) 
SAME C(44) C(48) F(71) F(80) F(91) AND 
CONT C(44) C(48) F(80) F(91) F(71) AND 
CONT C(44) C(48) F(91) F(71) F(80) AND 
CONT C(44) C(48) F(70) F(81) F(90) AND 
CONT C(44) C(48) F(81) F(90) F(70) AND 
CONT C(44) C(48) F(90) F(70) F(81) 
SAME C(54) C(57) F(160) F(171) F(180) AND 
CONT C(54) C(57) F(171) F(180) F(160) AND 
CONT C(54) C(57) F(180) F(160) F(171) AND 
CONT C(54) C(57) F(161) F(170) F(181) AND 
CONT C(54) C(57) F(170) F(181) F(161) AND 
CONT C(54) C(57) F(181) F(161) F(170) 
DELU 0.01 F(171) C(57) 
SIMU 0.01 C(171) C(57) 
DELU 0.01 B(1) C(34) 
SIMU 0.01 B(1) C(34) 
DELU 0.01 B(1) C(42) 
SIMU 0.01 B(1) C(42) 
DELU 0.01 B(1) C(50) 
SIMU 0.01 B(1) C(50) 
DELU 0.01 B(1) C(58) 
SIMU 0.01 B(1) C(58) 
DELU 0.01 F(170) C(57) 
SIMU 0.01 C(170) C(57) 
DELU 0.01 C(55) C(54) 
SIMU 0.01 C(55) C(54) 
DELU 0.01 C(55) C(50) 
SIMU 0.01 C(55) C(50) 
DELU 0.01 C(21) P(2) 
SIMU 0.01 C(21) P(2) 
REM   THERMSIM   END (DO NOT REMOVE THIS LINE) 
REM   SHIFTLIMIT   START (DO NOT REMOVE THIS LINE) 
REM   SHIFTLIMIT   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;