Electropolymerizable N-heterocyclic carbene complexes of Rh and Ir with enantiotropic polymorphic phases.
Wang, Weiran; Lynch, Vincent M.; Guo, Hongyu; Datta, Anwesha; Jones, Richard A.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 2264–2272; doi:10.1039/c9dt04844h

data_7703409
_publ_section_title
;
 Electropolymerizable N-heterocyclic carbene complexes of Rh and Ir with
 enantiotropic polymorphic phases.
;
_journal_issue                   7
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2264
_journal_page_last               2272
_journal_paper_doi               10.1039/c9dt04844h
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         '1(C23 H24 I Ir N2 S3)'
_chemical_formula_sum            'C23 H24 I Ir N2 S3'
_chemical_formula_weight         743.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yab'
_space_group_name_H-M_alt        'P 1 21/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-11-05 deposited with the CCDC.	2020-01-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.303(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.1194(3)
_cell_length_b                   9.17930(10)
_cell_length_c                   23.3012(4)
_cell_measurement_reflns_used    18523
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      75.6560
_cell_measurement_theta_min      3.9680
_cell_volume                     4738.04(13)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      100.01(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2940
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.905
_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    -69.00  32.00   1.00    5.50    --  -41.34  57.00 120.00  101
  2  \w   -117.00  -9.00   1.00    5.50    --  -41.34 -77.00 -30.00  108
  3  \w      9.00 117.00   1.00    5.50    --   41.34  77.00 -30.00  108
  4  \w     36.00 113.00   1.00   18.00    --  112.00-111.00-120.00   77
  5  \w     84.00 178.00   1.00   18.00    --  112.00  30.00 150.00   94
  6  \w     36.00 145.00   1.00   18.00    --  112.00 -77.00 -60.00  109
  7  \w     36.00 113.00   1.00   18.00    --  112.00-111.00-180.00   77
  8  \w     79.00 178.00   1.00   18.00    --  112.00  77.00  30.00   99
  9  \w     84.00 178.00   1.00   18.00    --  112.00  30.00   0.00   94
 10  \w     79.00 178.00   1.00   18.00    --  112.00  77.00  60.00   99
 11  \w   -113.00 -13.00   1.00    5.50    --  -41.34 -57.00-150.00  100
 12  \w   -113.00 -13.00   1.00    5.50    --  -41.34 -57.00 120.00  100
 13  \w     84.00 178.00   1.00   18.00    --  112.00  30.00 -90.00   94
 14  \w     83.00 178.00   1.00   18.00    --  112.00  61.00 -60.00   95
 15  \w     36.00 104.00   1.00   18.00    --  112.00-111.00 120.00   68
 16  \w     79.00 178.00   1.00   18.00    --  112.00  77.00 150.00   99
 17  \w     79.00 178.00   1.00   18.00    --  112.00  77.00  90.00   99
 18  \w     79.00 178.00   1.00   18.00    --  112.00  77.00-180.00   99
 19  \w   -113.00 -52.00   1.00    5.50    --  -41.34 -57.00  30.00   61
 20  \w    -92.00  -2.00   1.00    5.50    --  -41.34 125.00-150.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0224874000
_diffrn_orient_matrix_UB_12      0.1579853000
_diffrn_orient_matrix_UB_13      0.0002894000
_diffrn_orient_matrix_UB_21      0.0154107000
_diffrn_orient_matrix_UB_22      0.0106286000
_diffrn_orient_matrix_UB_23      0.0681381000
_diffrn_orient_matrix_UB_31      0.0666291000
_diffrn_orient_matrix_UB_32      -0.0556954000
_diffrn_orient_matrix_UB_33      0.0138720000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0496
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.905
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            50416
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.905
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         87.803
_diffrn_reflns_theta_min         3.697
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    23.713
_exptl_absorpt_correction_T_max  0.506
_exptl_absorpt_correction_T_min  0.158
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            orange
_exptl_crystal_density_diffrn    2.085
_exptl_crystal_description       prism
_exptl_crystal_F_000             2832
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.054
_refine_diff_density_max         1.719
_refine_diff_density_min         -1.247
_refine_diff_density_rms         0.168
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     647
_refine_ls_number_reflns         9777
_refine_ls_number_restraints     618
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0554
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0548P)^2^+24.7690P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1130
_refine_ls_wR_factor_ref         0.1250
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7777
_reflns_number_total             9777
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt04844h2.cif
_cod_data_source_block           ir_100k_p21a
_cod_depositor_comments
'Adding full bibliography for 7703409--7703412.cif.'
_cod_original_cell_volume        4738.03(13)
_cod_database_code               7703409
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         C23H20N2S3IrI
_shelx_estimated_absorpt_t_max   0.361
_shelx_estimated_absorpt_t_min   0.149
_reflns_odcompleteness_completeness 99.67
_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
 S1-C4 \\sim S1A-C4
 with sigma of 0.02
 S1-C1 \\sim S1A-C1A
 with sigma of 0.02
 C3-C4 \\sim C3A-C4
 with sigma of 0.02
 C3-C2 \\sim C3A-C2A
 with sigma of 0.02
 C2-C1 \\sim C2A-C1A
 with sigma of 0.02
 S1-C2 \\sim S1A-C2A
 with sigma of 0.04
 C3-C1 \\sim C3A-C1A
 with sigma of 0.04
 C4-C2 \\sim C4-C2A
 with sigma of 0.04
 C4-C1 \\sim C4-C1A
 with sigma of 0.04
 Ir2-C43 \\sim Ir2A-C43
 with sigma of 0.02
 Ir2-C37 \\sim Ir2A-C37
 with sigma of 0.02
 Ir2-C42 \\sim Ir2A-C42
 with sigma of 0.02
 Ir2-C39 \\sim Ir2A-C39
 with sigma of 0.02
 Ir2-C46 \\sim Ir2A-C46
 with sigma of 0.02
 C32-C35 \\sim C32-C35A
 with sigma of 0.04
 I2-C43 \\sim I2A-C43
 with sigma of 0.04
 I2-C37 \\sim I2A-C37
 with sigma of 0.04
 I2-C42 \\sim I2A-C42
 with sigma of 0.04
 I2-C39 \\sim I2A-C39
 with sigma of 0.04
 I2-C46 \\sim I2A-C46
 with sigma of 0.04
 Ir2-I2 \\sim Ir2A-I2A
 with sigma of 0.02
 I1-C16 \\sim I1A-C16
 with sigma of 0.04
 I1-C14 \\sim I1A-C14
 with sigma of 0.04
 I1-C23 \\sim I1A-C23
 with sigma of 0.04
 I1-C19 \\sim I1A-C19
 with sigma of 0.04
 I1-C20 \\sim I1A-C20
 with sigma of 0.04
 Ir1-I1 \\sim Ir1A-I1A
 with sigma of 0.02
 Ir1-C16 \\sim Ir1A-C16
 with sigma of 0.02
 Ir1-C14 \\sim Ir1A-C14
 with sigma of 0.02
 Ir1-C23 \\sim Ir1A-C23
 with sigma of 0.02
 Ir1-C19 \\sim Ir1A-C19
 with sigma of 0.02
 Ir1-C20 \\sim Ir1A-C20
 with sigma of 0.02
 C23-C22 \\sim C23-C22A
 with sigma of 0.02
 C20-C22 \\sim C20-C22A
 with sigma of 0.04
 C20-C21 \\sim C20-C21A
 with sigma of 0.02
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C23-C21 \\sim C23-C21A
 with sigma of 0.04
 C42-C41 \\sim C42-C41A
 with sigma of 0.02
 C39-C41 \\sim C39-C41A
 with sigma of 0.04
 C43-C44 \\sim C43-C44A
 with sigma of 0.02
 C45-C46 \\sim C45A-C46
 with sigma of 0.02
 C45-C44 \\sim C45A-C44A
 with sigma of 0.02
 C43-C45 \\sim C43-C45A
 with sigma of 0.04
 C46-C44 \\sim C46-C44A
 with sigma of 0.04
 C39-C40 \\sim C39-C40A
 with sigma of 0.02
 C41-C40 \\sim C41A-C40A
 with sigma of 0.02
 C42-C40 \\sim C42-C40A
 with sigma of 0.04
 C16-C17 \\sim C16-C17A
 with sigma of 0.02
 C19-C18 \\sim C19-C18A
 with sigma of 0.02
 C18-C17 \\sim C18A-C17A
 with sigma of 0.02
 C16-C18 \\sim C16-C18A
 with sigma of 0.04
 C19-C17 \\sim C19-C17A
 with sigma of 0.04
 S6-C32 \\sim S6A-C32
 with sigma of 0.02
 C33-C32 \\sim C33A-C32
 with sigma of 0.02
 S6-C35 \\sim S6A-C35A
 with sigma of 0.02
 C33-C34 \\sim C33A-C34A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 S6-C34 \\sim S6A-C34A
 with sigma of 0.04
 C33-C35 \\sim C33A-C35A
 with sigma of 0.04
 C32-C34 \\sim C32-C34A
 with sigma of 0.04
3. Restrained planarity
 C4, C3, C2, C1, S1
 with sigma of 0.1
 C4, C3A, C2A, C1A, S1A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C4 \\sim C3 \\sim C2 \\sim C1 \\sim S1: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C4 \\sim C3A \\sim C2A \\sim C1A \\sim S1A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Ir2 \\sim C37 \\sim I2 \\sim C42 \\sim C43 \\sim C39 \\sim C46: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Ir2A \\sim C37 \\sim I2A \\sim C42 \\sim C43 \\sim C39 \\sim C46: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C14 \\sim Ir1A \\sim I1A \\sim C16 \\sim C23 \\sim C19 \\sim C20: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C14 \\sim Ir1 \\sim I1 \\sim C16 \\sim C23 \\sim C19 \\sim C20: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C23 \\sim C22A \\sim C21A \\sim C20: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C23 \\sim C22 \\sim C21 \\sim C20: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C43 \\sim C44 \\sim C45 \\sim C46: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C43 \\sim C44A \\sim C45A \\sim C46: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C39 \\sim C40 \\sim C41 \\sim C42: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C39 \\sim C40A \\sim C41A \\sim C42: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C19 \\sim C18A \\sim C17A \\sim C16: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C19 \\sim C18 \\sim C17 \\sim C16: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(S1) = Uanis(S1A)
Uanis(C2A) = Uanis(C1)
Uanis(C2) = Uanis(C1A)
Uanis(C3) = Uanis(C3A)
Uanis(Ir2A) = Uanis(Ir2)
Uanis(C35A) = Uanis(C35)
Uanis(C21) = Uanis(C21A)
Uanis(C22A) = Uanis(C22)
Uanis(C41) = Uanis(C41A)
Uanis(C40) = Uanis(C40A)
Uanis(C34A) = Uanis(C34)
Uanis(C33) = Uanis(C33A)
Uanis(S6) = Uanis(S6A)
5. Rigid body (RIGU) restrains
 C4, C3, C2, C1, S1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4, C3A, C2A, C1A, S1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Ir2, C37, I2, C42, C43, C39, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Ir2A, C37, I2A, C42, C43, C39, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, Ir1A, I1A, C16, C23, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, Ir1, I1, C16, C23, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, C22A, C21A, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, C22, C21, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45A, C44A, C43, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C43, C44, C45, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, C40, C41, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, C40A, C41A, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C18A, C17A, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C18, C17, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Ir2(0.80491) Ir1(0.4251) I1(0.4251) I2(0.80491) S6(0.89078)
 S1(0.87918) H16(0.4251) H16A(0.5749) C3(0.87918) H3(0.87918) C33(0.89078)
 H33(0.89078) H43(0.80491) H43A(0.19509) H23(0.4251) H23A(0.5749) H19(0.4251)
 H19A(0.5749) C45(0.59278) H45A(0.59278) H45B(0.59278) C18(0.73923)
 H18A(0.73923) H18B(0.73923) H42(0.80491) H42A(0.19509) C34(0.89078)
 H34(0.89078) H20(0.4251) H20A(0.5749) H39(0.80491) H39A(0.19509) C2(0.87918)
 H2(0.87918) C1(0.87918) H1(0.87918) H46(0.80491) H46A(0.19509) C35(0.89078)
 H35(0.89078) C44(0.59278) H44A(0.59278) H44B(0.59278) C17(0.73923)
 H17A(0.73923) H17B(0.73923) C22(0.73923) H22A(0.73923) H22B(0.73923)
 C21(0.73923) H21A(0.73923) H21B(0.73923) C41(0.59278) H41A(0.59278)
 H41B(0.59278) C40(0.59278) H40A(0.59278) H40B(0.59278) S1A(0.12082)
 C1A(0.12082) H1A(0.12082) C2A(0.12082) H2A(0.12082) C3A(0.12082) H3A(0.12082)
 C33A(0.10922) H33A(0.10922) C34A(0.10922) H34A(0.10922) C35A(0.10922)
 H35A(0.10922) S6A(0.10922) Ir2A(0.19509) I2A(0.19509) C40A(0.40722)
 H40C(0.40722) H40D(0.40722) C41A(0.40722) H41C(0.40722) H41D(0.40722)
 Ir1A(0.5749) I1A(0.5749) C22A(0.26077) H22C(0.26077) H22D(0.26077)
 C21A(0.26077) H21C(0.26077) H21D(0.26077) C44A(0.40722) H44C(0.40722)
 H44D(0.40722) C45A(0.40722) H45C(0.40722) H45D(0.40722) C17A(0.26077)
 H17C(0.26077) H17D(0.26077) C18A(0.26077) H18C(0.26077) H18D(0.26077)
7.a Ternary CH refined with riding coordinates:
 C16(H16), C16(H16A), C43(H43), C43(H43A), C23(H23), C23(H23A), C19(H19),
 C19(H19A), C42(H42), C42(H42A), C20(H20), C20(H20A), C39(H39), C39(H39A),
 C46(H46), C46(H46A)
7.b Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B), C18(H18A,H18B), C44(H44A,H44B), C17(H17A,H17B), C22(H22A,
 H22B), C21(H21A,H21B), C41(H41A,H41B), C40(H40A,H40B), C40A(H40C,H40D),
 C41A(H41C,H41D), C22A(H22C,H22D), C21A(H21C,H21D), C44A(H44C,H44D), C45A(H45C,
 H45D), C17A(H17C,H17D), C18A(H18C,H18D)
7.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C3(H3), C26(H26), C33(H33), C11(H11), C25(H25), C24(H24), C34(H34),
 C12(H12), C2(H2), C1(H1), C35(H35), C1A(H1A), C2A(H2A), C3A(H3A), C33A(H33A),
 C34A(H34A), C35A(H35A)
7.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C38(H38A,H38B,H38C), C36(H36A,H36B,H36C), C15(H15A,H15B,
 H15C)
;
_shelx_res_checksum              7440
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.476
_oxdiff_exptl_absorpt_empirical_full_min 0.711