Mono- versus Bicyclic Carbene Metal Amide Photoemitters: Which Design Leads to the Best Performance?
Chotard, Florian; Sivchik, Vasily; Linnolahti, Mikko; Bochmann, Manfred; Romanov, Alexander S.; Chemistry of Materials  (2020) –; doi:10.1021/acs.chemmater.0c01769

data_4003616
_publ_section_title
;
 Mono- versus Bicyclic Carbene Metal Amide Photoemitters: Which Design
 Leads to the Best Performance?
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.0c01769
_journal_year                    2020
_chemical_formula_moiety         'C40 H49 Cu N2, C H2 Cl2'
_chemical_formula_sum            'C41 H51 Cl2 Cu N2'
_chemical_formula_weight         706.27
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-11-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.4735(4)
_cell_length_b                   10.1510(2)
_cell_length_c                   19.3448(4)
_cell_measurement_reflns_used    16682
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      30.8910
_cell_measurement_theta_min      2.1940
_cell_volume                     3627.62(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_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(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.897
_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     15.00  68.00   0.50   15.10    --    4.95  37.00  30.00  106
  2  \w     -4.00  60.00   0.50   15.10    --    4.95  37.00 -60.00  128
  3  \w    -15.00  26.00   0.50   15.10    --    4.95 -99.00 -90.00   82
  4  \w     -8.00  38.00   0.50   15.10    --    4.95 -99.00 -30.00   92
  5  \w    -54.00  14.00   0.50   15.10    --    4.95 -57.00-180.00  136
  6  \w    -76.00  17.00   0.50   15.10    --   -5.49 -77.00  90.00  186
  7  \w    -60.00  -1.00   0.50   15.10    --    4.95 -57.00 120.00  118
;
_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      -0.0044728000
_diffrn_orient_matrix_UB_12      0.0069207000
_diffrn_orient_matrix_UB_13      0.0362352000
_diffrn_orient_matrix_UB_21      0.0180961000
_diffrn_orient_matrix_UB_22      0.0615790000
_diffrn_orient_matrix_UB_23      -0.0012534000
_diffrn_orient_matrix_UB_31      -0.0335787000
_diffrn_orient_matrix_UB_32      0.0322407000
_diffrn_orient_matrix_UB_33      -0.0054786000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0464
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.897
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            51449
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.848
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.842
_diffrn_reflns_theta_min         2.106
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.781
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61121
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.57a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             1496
_exptl_crystal_size_max          0.666
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.920
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Flack x determined using 3040 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     431
_refine_ls_number_reflns         9681
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0541
_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^)+(0.0919P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1290
_refine_ls_wR_factor_ref         0.1368
_reflns_Friedel_coverage         0.842
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.796
_reflns_number_gt                7639
_reflns_number_total             9681
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c01769_si_003.cif
_cod_data_source_block           vs_c6cucz
_cod_database_code               4003616
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C40H48N2Cu
_chemical_oxdiff_usercomment     'DCM/hexanes, -20 deg, light yellow block'
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.624
_diffrn_oxdiff_digest_frames
;
0167258a8db444ed47c782d3def638bf8d00025cd8b
;
_diffrn_oxdiff_digest_hkl
;
01d8ec4a48da3b31baf602ff3a3c52fd83c3be
;
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 Cl1A-C41A = Cl2A-C41A
 1.7602 with sigma of 0.002
 Cl1-C41 = Cl2-C41
 1.7602 with sigma of 0.002
 Cl1A-Cl2A
 2.9338 with sigma of 0.004
 Cl1-Cl2
 2.9338 with sigma of 0.004
3. Uiso/Uaniso restraints and constraints
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(C41) = Uanis(C41A)
4. Others
 Sof(Cl1A)=Sof(Cl2A)=Sof(C41A)=Sof(H41C)=Sof(H41D)=1-FVAR(1)
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(Cl1)=Sof(Cl2)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C20(H20), C22(H22), C24(H24), C26(H26)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C21(H21A,H21B), C23(H23A,H23B), C25(H25A,H25B),
 C27(H27A,H27B), C28(H28A,H28B), C41(H41A,H41B), C41A(H41C,H41D)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C30(H30), C31(H31), C32(H32), C33(H33), C36(H36),
 C37(H37), C38(H38), C39(H39)
5.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              8234
_shelx_hkl_checksum              87214
_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 1.437
_oxdiff_exptl_absorpt_empirical_full_min 0.447