The energy gap law for NIR-phosphorescent Cr(III) complexes.
Cheng, Yang; Yang, Qingqing; He, Jiang; Zou, Wenjie; Liao, Keyu; Chang, Xiaoyong; Zou, Chao; Lu, Wei; Dalton transactions (Cambridge, England : 2003) 52 (2023) 2561–2565; doi:10.1039/d2dt02872g

data_7711613
_publ_section_title
;
 The energy gap law for NIR-phosphorescent Cr(III) complexes.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2561
_journal_page_last               2565
_journal_paper_doi               10.1039/d2dt02872g
_journal_volume                  52
_journal_year                    2023
_chemical_formula_moiety
'C44 H44 Cr N14, 0.794(F6 P), 0.25(C2 H4 Cl4 F4.938 P0.823), 2.5(C H2 Cl2)'
_chemical_formula_sum            'C47 H50 Cl6 Cr F6 N14 P'
_chemical_formula_weight         1220.68
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-07-19 deposited with the CCDC.	2022-10-26 downloaded from the CCDC.
;
_cell_angle_alpha                73.632(3)
_cell_angle_beta                 88.899(3)
_cell_angle_gamma                76.362(2)
_cell_formula_units_Z            4
_cell_length_a                   16.2168(14)
_cell_length_b                   17.7781(14)
_cell_length_c                   19.4572(16)
_cell_measurement_reflns_used    2548
_cell_measurement_temperature    100
_cell_measurement_theta_max      25
_cell_measurement_theta_min      3
_cell_volume                     5223.8(8)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker PHOTON 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker CMOS area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0735
_diffrn_reflns_av_unetI/netI     0.0963
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            36187
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.717
_diffrn_reflns_theta_min         2.390
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  0.68
_exptl_absorpt_correction_T_min  0.24
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 80145 reflections, Rint = 0.0870
 (44227 with I > 3sig(I), Rint = 0.0735)
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_description       block
_exptl_crystal_F_000             2500
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.946
_refine_diff_density_min         -1.015
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1438
_refine_ls_number_reflns         36187
_refine_ls_number_restraints     152
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1309
_refine_ls_R_factor_gt           0.0816
_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^)+(0.1107P)^2^+5.4782P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1980
_refine_ls_wR_factor_ref         0.2311
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23981
_reflns_number_total             36187
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02872g2.cif
_cod_data_source_block           cxy1732_0m
_cod_depositor_comments
'Adding full bibliography for 7711611--7711615.cif.'
_cod_database_code               7711613
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.783
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.4049(11)
 0.5951(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Cl1-C89 = Cl3-C89 = Cl1-C89A = Cl2-C89A
 1.79 with sigma of 0.02
 Cl8-C92 = Cl8A-C92A = Cl9A-C92A = Cl9-C92
 1.79 with sigma of 0.02
 P2-F7 \\sim P2A-F7A
 with sigma of 0.02
 F11-F12 \\sim F11A-F12A
 with sigma of 0.04
 P2-F11 \\sim P2A-F11A
 with sigma of 0.02
 P2-F8 \\sim P2A-F8A
 with sigma of 0.02
 F8-F11 \\sim F8A-F11A
 with sigma of 0.04
 F9-F11 \\sim F9A-F11A
 with sigma of 0.04
 P2-F9 \\sim P2A-F9A
 with sigma of 0.02
 F10-F11 \\sim F10A-F11A
 with sigma of 0.04
 P2-F10 \\sim P2A-F10A
 with sigma of 0.02
 F7-F11 \\sim F7A-F11A
 with sigma of 0.04
 P2-F12 \\sim P2A-F12A
 with sigma of 0.02
 F10-F12 \\sim F10A-F12A
 with sigma of 0.04
 F8-F10 \\sim F8A-F10A
 with sigma of 0.04
 F8-F12 \\sim F8A-F12A
 with sigma of 0.04
 F9-F10 \\sim F9A-F10A
 with sigma of 0.04
 F9-F12 \\sim F9A-F12A
 with sigma of 0.04
 F7-F8 \\sim F7A-F8A
 with sigma of 0.04
 F7-F9 \\sim F7A-F9A
 with sigma of 0.04
 F7-F10 \\sim F7A-F10A
 with sigma of 0.04
 F7-F12 \\sim F7A-F12A
 with sigma of 0.04
 F8-F9 \\sim F8A-F9A
 with sigma of 0.04
 F3-F6 \\sim F3A-F6A
 with sigma of 0.04
 P1-F1 \\sim P1A-F1A
 with sigma of 0.02
 F4-F6 \\sim F4A-F6A
 with sigma of 0.04
 F1-F3 \\sim F1A-F3A
 with sigma of 0.04
 F1-F5 \\sim F1A-F5A
 with sigma of 0.04
 F3-F5 \\sim F3A-F5A
 with sigma of 0.04
 F1-F4 \\sim F1A-F4A
 with sigma of 0.04
 F4-F5 \\sim F4A-F5A
 with sigma of 0.04
 F2-F3 \\sim F2A-F3A
 with sigma of 0.04
 F5-F6 \\sim F5A-F6A
 with sigma of 0.04
 F2-F4 \\sim F2A-F4A
 with sigma of 0.04
 P1-F2 \\sim P1A-F2A
 with sigma of 0.02
 F2-F5 \\sim F2A-F5A
 with sigma of 0.04
 F1-F6 \\sim F1A-F6A
 with sigma of 0.04
 F2-F6 \\sim F2A-F6A
 with sigma of 0.04
 F3-F4 \\sim F3A-F4A
 with sigma of 0.04
 P1-F3 \\sim P1A-F3A
 with sigma of 0.02
 P1-F4 \\sim P1A-F4A
 with sigma of 0.02
 P1-F5 \\sim P1A-F5A
 with sigma of 0.02
 P1-F6 \\sim P1A-F6A
 with sigma of 0.02
 F1-F2 \\sim F1A-F2A
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C89 \\sim Cl1 \\sim C89A \\sim Cl3 \\sim Cl2: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(Cl1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C92) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F6A) \\sim Ueq, Uanis(P1A) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2A)
\\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(F5A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F8) = Uanis(F8A)
Uanis(F11A) = Uanis(F11)
Uanis(F12) = Uanis(F12A)
Uanis(F9A) = Uanis(F9)
Uanis(P2A) = Uanis(P2)
Uanis(F7) = Uanis(F7A)
Uanis(F10) = Uanis(F10A)
Uanis(F5A) = Uanis(F5)
Uanis(P1) = Uanis(P1A)
Uanis(F6A) = Uanis(F6)
Uanis(F1A) = Uanis(F1)
Uanis(F4) = Uanis(F4A)
Uanis(F2) = Uanis(F2A)
Uanis(F3A) = Uanis(F3)
Uanis(C89) = Uanis(C89A)
Uanis(Cl8) = Uanis(Cl8A)
Uanis(Cl9A) = Uanis(Cl9)
Uanis(C92) = Uanis(C92A)
Uanis(Cl5) = Uanis(Cl5A)
5. Others
 Sof(F8A)=Sof(P2A)=Sof(F7A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(1)
 Sof(P2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(1)
 Sof(F6A)=Sof(P1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=1-FVAR(2)
 Sof(P1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(Cl8A)=Sof(C92A)=Sof(H92C)=Sof(H92D)=Sof(Cl9A)=1-FVAR(3)
 Sof(Cl8)=Sof(Cl9)=Sof(C92)=Sof(H92A)=Sof(H92B)=FVAR(3)
 Sof(H90C)=Sof(H90D)=Sof(Cl5A)=1-FVAR(4)
 Sof(Cl5)=Sof(H90A)=Sof(H90B)=FVAR(4)
 Fixed Sof: Cl2(0.5) Cl3(0.5) C89(0.5) H89A(0.5) H89B(0.5) C89A(0.5) H89C(0.5)
 H89D(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C89(H89A,H89B), C90(H90A,H90B), C90(H90C,H90D), C91(H91A,H91B), C92(H92A,
 H92B), C93(H93A,H93B), C94(H94A,H94B), C89A(H89C,H89D), C92A(H92C,H92D)
6.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C3(H3), C35(H35), C40(H40), C13(H13), C18(H18), C26(H26), C8(H8),
 C4(H4), C22(H22), C19(H19), C30(H30), C43(H43), C44(H44), C14(H14), C36(H36),
 C20(H20), C21(H21), C42(H42), C41(H41), C57(H57), C47(H47), C79(H79), C62(H62),
  C70(H70), C48(H48), C74(H74), C80(H80), C64(H64), C66(H66), C58(H58),
 C84(H84), C69(H69), C88(H88), C87(H87), C63(H63), C65(H65), C52(H52), C86(H86),
  C85(H85)
6.c Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C16(H16A,H16B,H16C), C28(H28A,H28B,H28C), C39(H39A,H39B,
 H39C), C6(H6A,H6B,H6C), C17(H17A,H17B,H17C), C29(H29A,H29B,H29C), C7(H7A,H7B,
 H7C), C72(H72A,H72B,H72C), C60(H60A,H60B,H60C), C82(H82A,H82B,H82C), C50(H50A,
 H50B,H50C), C51(H51A,H51B,H51C), C83(H83A,H83B,H83C), C61(H61A,H61B,H61C),
 C73(H73A,H73B,H73C)
;
_shelx_res_checksum              52843
_olex2_submission_special_instructions 'No special instructions were received'