Solid–State Molecular Organometallic Chemistry. Single–Crystal to Single–Crystal Reactivity and Catalysis with Light Hydrocarbon Substrates.
Chadwick, Fredrick M.; McKay, Alasdair I.; Martinez-Martinez, Antonio J.; Rees, Nick; Kraemer, Tobias; Macgregor, Stuart Alan; Weller, Andrew; Chem. Sci.  (2017) –; doi:10.1039/C7SC01491K

data_1546507
_publ_section_title
;
 Solid--State Molecular Organometallic Chemistry. Single--Crystal to
 Single--Crystal Reactivity and Catalysis with Light Hydrocarbon
 Substrates.
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC01491K
_journal_year                    2017
_chemical_formula_moiety         'C32 H12 B F24, C32 H60 P2 Rh'
_chemical_formula_sum            'C64 H72 B F24 P2 Rh'
_chemical_formula_weight         1472.87
_chemical_melting_point          ?
_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             2017-03-11
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2017-03-23 deposited with the CCDC.
2017-07-06 downloaded from the CCDC.
;
_cell_angle_alpha                98.549(2)
_cell_angle_beta                 102.097(2)
_cell_angle_gamma                94.411(2)
_cell_formula_units_Z            2
_cell_length_a                   13.4908(4)
_cell_length_b                   14.2693(4)
_cell_length_c                   18.1051(4)
_cell_measurement_reflns_used    15864
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.2720
_cell_measurement_theta_min      4.3210
_cell_volume                     3348.94(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (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      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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    -36.00 -11.00   1.00    1.00    --  -41.65  37.00 -60.00   25
  2  \w    -46.00  30.00   1.00    1.00    --  -41.65  37.00-120.00   76
  3  \w    -48.00  15.00   1.00    1.00    --  -41.65  37.00-180.00   63
  4  \w    -66.00  29.00   1.00    1.00    --  -41.65  57.00  90.00   95
  5  \w     54.00  96.00   1.00    1.00    --   41.65-125.00-120.00   42
  6  \w   -109.00 -18.00   1.00    1.00    --  -41.65 -57.00 -60.00   91
  7  \w     52.00 104.00   1.00    2.00    --  111.00 -77.00-150.00   52
  8  \w    116.00 141.00   1.00    2.00    --  111.00 -77.00-150.00   25
  9  \w    130.00 155.00   1.00    2.00    --  111.00 -15.00-120.00   25
 10  \w    102.00 140.00   1.00    2.00    --  111.00 -77.00 -30.00   38
 11  \w     94.00 121.00   1.00    2.00    --  111.00 -77.00 -90.00   27
 12  \w     94.00 120.00   1.00    2.00    --  111.00-125.00 -90.00   26
 13  \w     81.00 121.00   1.00    2.00    --  111.00-125.00 -30.00   40
 14  \w     72.00 121.00   1.00    2.00    --  111.00-125.00  60.00   49
 15  \w     61.00 114.00   1.00    2.00    --  111.00 -61.00  90.00   53
 16  \w     47.00  74.00   1.00    2.00    --  111.00 -30.00 -30.00   27
 17  \w     42.00  99.00   1.00    2.00    --  111.00 -45.00 -90.00   57
 18  \w     66.00 104.00   1.00    2.00    --  111.00 -94.00 -60.00   38
 19  \w     60.00  86.00   1.00    2.00    --  111.00 -30.00-150.00   26
 20  \w     70.00  97.00   1.00    2.00    --  111.00 -45.00-180.00   27
 21  \w     67.00 149.00   1.00    2.00    --  111.00  15.00-150.00   82
 22  \w     87.00 178.00   1.00    2.00    --  111.00  30.00 -90.00   91
 23  \w    101.00 158.00   1.00    2.00    --  111.00 125.00-180.00   57
 24  \w     40.00 125.00   1.00    2.00    --  111.00 -15.00-120.00   85
 25  \w     53.00 120.00   1.00    2.00    --  111.00-125.00-150.00   67
 26  \w     53.00  78.00   1.00    2.00    --  111.00 -77.00 -30.00   25
 27  \w     37.00  72.00   1.00    2.00    --  111.00 -77.00 -90.00   35
 28  \w     40.00  90.00   1.00    2.00    --  111.00 -45.00 -30.00   50
 29  \w     40.00  97.00   1.00    2.00    --  111.00 -45.00  90.00   57
 30  \w     49.00  81.00   1.00    2.00    --  111.00 -30.00 150.00   32
 31  \w     43.00  86.00   1.00    2.00    --  111.00 -94.00  90.00   43
 32  \w     44.00 116.00   1.00    2.00    --  111.00-125.00 150.00   72
 33  \w     36.00  65.00   1.00    2.00    --  111.00 -30.00  30.00   29
 34  \w     34.00  86.00   1.00    2.00    --  111.00 -94.00-150.00   52
 35  \w     41.00  97.00   1.00    2.00    --  111.00-125.00-180.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1102203000
_diffrn_orient_matrix_UB_12      -0.0255535000
_diffrn_orient_matrix_UB_13      0.0203133000
_diffrn_orient_matrix_UB_21      -0.0404716000
_diffrn_orient_matrix_UB_22      -0.1008828000
_diffrn_orient_matrix_UB_23      0.0084490000
_diffrn_orient_matrix_UB_31      -0.0050152000
_diffrn_orient_matrix_UB_32      -0.0352133000
_diffrn_orient_matrix_UB_33      -0.0855078000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0305
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            36956
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.225
_diffrn_reflns_theta_min         3.736
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.455
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90995
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (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    1.461
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1504
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.22
_refine_diff_density_max         2.248
_refine_diff_density_min         -0.938
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1028
_refine_ls_number_reflns         13869
_refine_ls_number_restraints     612
_refine_ls_restrained_S_all      1.168
_refine_ls_R_factor_all          0.0610
_refine_ls_R_factor_gt           0.0552
_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^)+(0.0711P)^2^+6.1386P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1417
_refine_ls_wR_factor_ref         0.1475
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12456
_reflns_number_total             13869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01491k3.cif
_cod_data_source_block           1bispropene
_cod_depositor_comments
;
The following automatic conversions were performed:

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

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

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_database_code               1546507
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Rh1 B1 F24 P2 C64 H72'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1-F3 \\sim F1-F2 \\sim F3-F2 \\sim F1A-F2A \\sim F1A-F3A \\sim F2A-F3A
 with sigma of 0.04
 C39-F1 \\sim C39-F3 \\sim C39-F2 \\sim C39-F1A \\sim C39-F2A \\sim C39-F3A
 with sigma of 0.02
 F4-F5 \\sim F4-F6 \\sim F5-F6 \\sim F5A-F6A \\sim F5A-F4A \\sim F6A-F4A
 with sigma of 0.04
 C37-C40 \\sim F4-C40 \\sim F5-C40 \\sim F6-C40 \\sim F5A-C40 \\sim F6A-C40
 with sigma of 0.02
 F9-F7 \\sim F9-F8 \\sim F7-F8 \\sim F9A-F7A \\sim F9A-F8A \\sim F7A-F8A
 with sigma of 0.04
 C47-F9 \\sim C47-C43 \\sim C47-F7 \\sim C47-F8 \\sim C47-F9A \\sim C47-F7A
\\sim C47-F8A
 with sigma of 0.02
 F12-F10 \\sim F12-F11 \\sim F10-F11 \\sim F11A-F12A \\sim F11A-F10A \\sim
F12A-F10A
 with sigma of 0.04
 C48-F12 \\sim C48-F10 \\sim C48-F11 \\sim C48-F11A \\sim C48-F12A \\sim
C48-F10A
 with sigma of 0.02
 F16-F18 \\sim F16-F17 \\sim F18-F17 \\sim F16A-F17A \\sim F16A-F18A \\sim
F17A-F18A
 with sigma of 0.04
 C56-C53 \\sim C56-F16 \\sim C56-F18 \\sim C56-F17 \\sim C56-F16A \\sim
C56-F17A \\sim C56-F18A
 with sigma of 0.02
 C2-C1 \\sim C2A-C1A
 with sigma of 0.02
 C3-C2 \\sim C3A-C2A
 with sigma of 0.02
 C1A-C3A \\sim C1-C3
 with sigma of 0.04
 C5A-C4A \\sim C5-C4
 with sigma of 0.02
 C6A-C5A \\sim C6-C5
 with sigma of 0.02
 C4-C6 \\sim C4A-C6A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C39 \\sim F3A \\sim F1A \\sim F2A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C39 \\sim F1 \\sim F2 \\sim F3: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C40 \\sim F6 \\sim F4 \\sim F5: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C40 \\sim F5A \\sim F6A \\sim F4A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C47 \\sim F8 \\sim F9 \\sim F7: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C47 \\sim F9A \\sim F7A \\sim F8A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C48 \\sim F11 \\sim F12 \\sim F10: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C48 \\sim F11A \\sim F12A \\sim F10A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C56 \\sim F18 \\sim F17 \\sim F16: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C56 \\sim F16A \\sim F18A \\sim F17A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C1 \\sim C2 \\sim C3: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
C1A \\sim C2A \\sim C3A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C4 \\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
C4A \\sim C5A \\sim C6A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
4. Rigid body (RIGU) restrains
 C39, F1A, F3A, F2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, F1, F2, F3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, F6, F4, F5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, F5A, F6A, F4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, F7, F8, F9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, F9A, F7A, F8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C48, F11, F12, F10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C48, F11A, F10A, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C56, F18, F17, F16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C56, F16A, F17A, F18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C2A, C3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C2, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4, C5, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4A, C5A, C6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F3)=Sof(F2)=FVAR(1)
 Sof(F5A)=Sof(F6A)=Sof(F4A)=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(F9A)=Sof(F7A)=Sof(F8A)=1-FVAR(3)
 Sof(F9)=Sof(F7)=Sof(F8)=FVAR(3)
 Sof(F11A)=Sof(F12A)=Sof(F10A)=1-FVAR(4)
 Sof(F12)=Sof(F10)=Sof(F11)=FVAR(4)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(5)
 Sof(F16)=Sof(F18)=Sof(F17)=FVAR(5)
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=
 Sof(C2A)=Sof(H2A)=Sof(C5A)=Sof(H5A)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C1A)=
 Sof(H1AA)=Sof(H1AB)=1-FVAR(6)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5)=Sof(C2)=
 Sof(H2)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=
 FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C21(H21), C7(H7), C27(H27), C13(H13)
6.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C28(H28A,H28B), C24(H24A,H24B), C10(H10A,H10B), C32(H32A,
 H32B), C19(H19A,H19B), C22(H22A,H22B), C12(H12A,H12B), C8(H8A,H8B), C25(H25A,
 H25B), C20(H20A,H20B), C23(H23A,H23B), C29(H29A,H29B), C11(H11A,H11B),
 C18(H18A,H18B), C9(H9A,H9B), C15(H15A,H15B), C30(H30A,H30B), C14(H14A,H14B),
 C17(H17A,H17B), C31(H31A,H31B), C16(H16A,H16B)
6.c Aromatic/amide H refined with riding coordinates:
 C46(H46), C62(H62), C60(H60), C50(H50), C58(H58), C38(H38), C42(H42),
 C36(H36), C44(H44), C54(H54), C34(H34), C52(H52), C5(H5), C2(H2), C2A(H2A),
 C5A(H5A)
6.d X=CH2 refined with riding coordinates:
 C1(H1A,H1B), C4(H4A,H4B), C4A(H4AA,H4AB), C1A(H1AA,H1AB)
6.e Idealised Me refined as rotating group:
 C3A(H3AA,H3AB,H3AC), C6A(H6AA,H6AB,H6AC), C3(H3A,H3B,H3C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              77996
_ins_header
;
TITL 120aim17 in P-1 
REM P-1 (#2 in standard setting)
CELL 1.54184  13.490822  14.269291  18.105092  98.5495 102.0969  94.4108
ZERR    2.00   0.000360   0.000397   0.000361   0.0020   0.0020   0.0022
LATT  1
SFAC C H B F P Rh
UNIT 128.00 144.00 2.00 48.00 4.00 2.00
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 1.134
_oxdiff_exptl_absorpt_empirical_full_min 0.912