Rhodium-Stabilized Diarylcarbenes Behaving as Donor/Acceptor Carbenes
Lee, Maizie; Ren, Zhi; Musaev, Djamaladdin G.; Davies, Huw M. L.; ACS Catalysis  (2020) 6240–6247; doi:10.1021/acscatal.0c01131

data_4517678
_publ_section_title
;
 Rhodium-Stabilized Diarylcarbenes Behaving as Donor/Acceptor Carbenes
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              6240
_journal_page_last               6247
_journal_paper_doi               10.1021/acscatal.0c01131
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H18'
_chemical_formula_sum            'C21 H18'
_chemical_formula_weight         270.377
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_Int_Tables_number      19
_audit_creation_date             2020-01-15
_audit_creation_method
;
Olex2 1.3-alpha
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.76988(7)
_cell_length_b                   11.91662(14)
_cell_length_c                   21.9056(2)
_cell_measurement_reflns_used    14976
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.5770
_cell_measurement_theta_min      4.2140
_cell_volume                     1506.17(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3-alpha (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 1.0000
_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     85.00 171.00   0.50    1.00    --   98.78  57.00  90.00  172
  2  \w    124.00 150.00   0.50    1.00    --   98.78  70.00 -62.00   52
  3  \w     85.00 165.00   0.50    1.00    --   98.78  57.00-150.00  160
  4  \w    -11.00  64.00   0.50    0.25    --   47.95 -72.00 -68.00  150
  5  \w     35.00  63.00   0.50    1.00    --   98.78 -57.00-180.00   56
  6  \w     30.00  55.00   0.50    6.59    --   98.78 -38.00-180.00   50
  7  \w     39.00  66.00   0.50    6.59    --   98.78 -57.00-150.00   54
  8  \w     34.00  78.00   0.50    6.59    --   98.78 -72.00 -68.00   88
  9  \w     26.00  68.00   0.50    6.59    --   98.78 -57.00  60.00   84
 10  \w     34.00  96.00   0.50    3.99    --   47.95-125.00 -90.00  124
 11  \w   -159.00-112.00   0.50    6.59    --  -86.25 -80.00  51.00   94
 12  \w   -145.00-115.00   0.50    6.59    --  -86.25 -99.00  30.00   60
 13  \w   -100.00 -75.00   0.50    6.59    --  -86.25 -80.00  51.00   50
 14  \w    -49.00 -14.00   0.50    6.59    --  -86.25  38.00 120.00   70
 15  \w    -77.00 -19.00   0.50    3.99    --  -47.95 125.00  60.00  116
 16  \w    -13.00  13.00   0.50    3.99    --  -47.95  80.00 175.00   52
 17  \w    -53.00  12.00   0.50    3.99    --  -47.95  38.00 -90.00  130
 18  \w   -109.00 -57.00   0.50    3.99    --  -47.95 -38.00 -30.00  104
 19  \w     33.00  61.00   0.50    3.99    --   47.95  57.00 -60.00   56
 20  \w     78.00 118.00   0.50    3.99    --   47.95  57.00 -60.00   80
 21  \w   -140.00 -90.00   0.50    6.59    --  -86.25 -38.00 -90.00  100
 22  \w   -159.00 -73.00   0.50    6.59    --  -86.25 -38.00 -60.00  172
 23  \w   -129.00 -88.00   0.50    6.59    --  -86.25 -99.00 -30.00   82
 24  \w    -96.00 -71.00   0.50    6.59    --  -86.25 -57.00-120.00   50
 25  \w   -159.00-125.00   0.50    6.59    --  -86.25 -57.00-120.00   68
 26  \w     81.00 106.00   0.50    6.59    --   98.78 -99.00-180.00   50
 27  \w     31.00  73.00   0.50    6.59    --   98.78 -77.00  60.00   84
 28  \w     33.00  62.00   0.50    6.59    --   98.78 -99.00-180.00   58
 29  \w     28.00  54.00   0.50    6.59    --   98.78 -38.00 -30.00   52
 30  \w     86.00 111.00   0.50    6.59    --   98.78  38.00 150.00   50
 31  \w     29.00  75.00   0.50    6.59    --   98.78 -77.00   0.00   92
 32  \w     75.00 102.00   0.50    6.59    --   98.78-125.00-150.00   54
 33  \w     29.00  55.00   0.50    6.59    --   98.78 -38.00   0.00   52
 34  \w    131.00 169.00   0.50    6.59    --   98.78  38.00 150.00   76
 35  \w     35.00 112.00   0.50    6.59    --   98.78-125.00-180.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2140975000
_diffrn_orient_matrix_UB_12      0.0443292000
_diffrn_orient_matrix_UB_13      -0.0344049000
_diffrn_orient_matrix_UB_21      -0.0116103000
_diffrn_orient_matrix_UB_22      -0.1012518000
_diffrn_orient_matrix_UB_23      -0.0436365000
_diffrn_orient_matrix_UB_31      -0.1591005000
_diffrn_orient_matrix_UB_32      0.0670737000
_diffrn_orient_matrix_UB_33      -0.0430987000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0163
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 1.0000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            16056
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 1.0000
_diffrn_reflns_theta_full        65.0807
_diffrn_reflns_theta_max         65.08
_diffrn_reflns_theta_min         4.04
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.505
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.488
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.192
_exptl_crystal_description       needle
_exptl_crystal_F_000             577.542
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.525
_exptl_crystal_size_mid          0.215
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.2629
_refine_diff_density_min         -0.2242
_refine_diff_density_rms         0.0278
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   -0.14(4)
_refine_ls_d_res_high            0.8501
_refine_ls_d_res_low             10.9528
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0842
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     354
_refine_ls_number_reflns         2565
_refine_ls_number_restraints     264
_refine_ls_restrained_S_all      1.0248
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0267
_refine_ls_shift/su_max          0.0009
_refine_ls_shift/su_mean         0.0002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0271P)^2^+0.3759P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0665
_refine_ls_wR_factor_ref         0.0667
_reflns_Friedel_coverage         1.000
_reflns_limit_h_max              6
_reflns_limit_h_min              -6
_reflns_limit_k_max              14
_reflns_limit_k_min              -13
_reflns_limit_l_max              25
_reflns_limit_l_min              -25
_reflns_number_gt                2523
_reflns_number_total             2565
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs0c01131_si_002.cif
_cod_data_source_block           cyclopropane-triyltribenzene
_cod_depositor_comments
'Adding full bibliography for 4517677--4517678.cif.'
_cod_original_sg_symbol_Hall     ' P 2ac 2ab'
_cod_database_code               4517678
_chemical_oxdiff_formula         'C84  H72  '
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.14(4)
 -0.14(4)
2. Restrained distances
 C3-H3b = C3-H3a = C2-H2
 0.99 with sigma of 0.02
3. Restrained planarity
 C4, C5, C6, C7, C8, C9
 with sigma of 0.002
4. Rigid body (RIGU) restrains
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 C4, C1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C5, H5, C6, H6, C7, H7
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C10, C11, C12, C13, C14, C15, H15, H13, H14, H12, H5, H11
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C2, C16, C17, C18, C19, C20, C21, H21, H17, H20, H18, H19
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C7, H7, C8, H8, C9, H9
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C3, H3a, H3b, C2, H2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id cyclopropane-triyltribenzene
_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 1.258
_oxdiff_exptl_absorpt_empirical_full_min 0.706