Versatile heteroleptic bis-terdentate Cr(iii) chromophores displaying room temperature millisecond excited state lifetimes.
Jiménez, Juan-Ramón; Doistau, Benjamin; Besnard, Céline; Piguet, Claude; Chemical communications (Cambridge, England) 54 (2018) 13228–13231; doi:10.1039/c8cc07671e

data_7122546
_publ_section_title
;
 Versatile heteroleptic bis-terdentate Cr(iii) chromophores displaying
 room temperature millisecond excited state lifetimes.
;
_journal_issue                   94
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              13228
_journal_page_last               13231
_journal_paper_doi               10.1039/c8cc07671e
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety
'C35 H32 Cr N8 O2, C F3 O3 S, 2(F6 P), 3(C2 H3 N)'
_chemical_formula_sum            'C42 H41 Cr F15 N11 O5 P2 S'
_chemical_formula_weight         1210.86
_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             2018-09-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-20 deposited with the CCDC.
2018-11-02 downloaded from the CCDC.
;
_cell_angle_alpha                74.089(5)
_cell_angle_beta                 75.790(5)
_cell_angle_gamma                69.487(6)
_cell_formula_units_Z            2
_cell_length_a                   11.9089(6)
_cell_length_b                   12.6435(8)
_cell_length_c                   19.9341(10)
_cell_measurement_reflns_used    7429
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      68.3040
_cell_measurement_theta_min      3.8030
_cell_volume                     2666.0(3)
_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      180.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4670
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.982
_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    -33.00  -6.00   1.00    1.00    --  -38.13 125.00  90.00   27
  2  \w    -89.00 -12.00   1.00    1.00    --  -38.13 125.00 150.00   77
  3  \w   -113.00  -6.00   1.00    1.00    --  -38.13 -57.00  30.00  107
  4  \w     11.00 109.00   1.00    1.00    --   38.13  57.00 150.00   98
  5  \w    -38.00  68.00   1.00    1.00    --   38.13 -77.00 -60.00  106
  6  \w     87.00 136.00   1.00    2.50    --  100.00 -77.00  90.00   49
  7  \w    127.00 164.00   1.00    2.50    --  100.00  45.00-120.00   37
  8  \w     23.00  54.00   1.00    2.50    --  100.00 -45.00-150.00   31
  9  \w     65.00 178.00   1.00    2.50    --  100.00  30.00-150.00  113
 10  \w     69.00 159.00   1.00    2.50    --  100.00  45.00 -60.00   90
 11  \w     83.00 113.00   1.00    2.50    --  100.00-111.00-150.00   30
 12  \w     16.00  77.00   1.00    2.50    --  100.00 -77.00  90.00   61
 13  \w    102.00 166.00   1.00    2.50    --  100.00 111.00 120.00   64
 14  \w    126.00 151.00   1.00    2.50    --  100.00 178.00 120.00   25
 15  \w     61.00 113.00   1.00    2.50    --  100.00-111.00   0.00   52
 16  \w     33.00 113.00   1.00    2.50    --  100.00-111.00  90.00   80
 17  \w     27.00  54.00   1.00    2.50    --  100.00-111.00   0.00   27
 18  \w     17.00  75.00   1.00    2.50    --  100.00 -94.00 150.00   58
 19  \w     56.00 101.00   1.00    2.50    --  100.00-111.00 -60.00   45
 20  \w    109.00 175.00   1.00    2.50    --  100.00 111.00 150.00   66
 21  \w     24.00  84.00   1.00    2.50    --  100.00 -94.00-120.00   60
 22  \w    103.00 130.00   1.00    2.50    --  100.00 111.00-120.00   27
 23  \w     79.00 123.00   1.00    2.50    --  100.00 -45.00-150.00   44
 24  \w     78.00 111.00   1.00    2.50    --  100.00  61.00-180.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0263372000
_diffrn_orient_matrix_UB_12      -0.1311019000
_diffrn_orient_matrix_UB_13      0.0096616000
_diffrn_orient_matrix_UB_21      0.0600911000
_diffrn_orient_matrix_UB_22      -0.0209200000
_diffrn_orient_matrix_UB_23      0.0645993000
_diffrn_orient_matrix_UB_31      -0.1237430000
_diffrn_orient_matrix_UB_32      0.0076495000
_diffrn_orient_matrix_UB_33      0.0487270000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            20526
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.915
_diffrn_reflns_theta_min         3.816
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.655
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.241
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.508
_exptl_crystal_description       plate
_exptl_crystal_F_000             1230
_exptl_crystal_size_max          0.463
_exptl_crystal_size_mid          0.231
_exptl_crystal_size_min          0.023
_refine_diff_density_max         0.955
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     805
_refine_ls_number_reflns         9722
_refine_ls_number_restraints     485
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0686
_refine_ls_R_factor_gt           0.0556
_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^)+(0.0975P)^2^+1.5066P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1555
_refine_ls_wR_factor_ref         0.1695
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7857
_reflns_number_total             9722
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc07671e2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7122544--7122546.cif.'
_cod_database_code               7122546
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C42 H41 Cr1 F15 N11 O5 P2 S1'
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C37A-C36A = C37B-C36B
 1.5 with sigma of 0.02
 O34B-C33B = O34A-C33A
 1.2 with sigma of 0.02
 O35B-C36B = O35A-C36A
 1.45 with sigma of 0.01
 O35A-C37A
 2.375 with sigma of 0.04
 C37B-O35B
 2.375 with sigma of 0.04
 O35B-C33B = O35A-C33A
 1.34 with sigma of 0.01
 P2A-F7A \\sim P2A-F8A \\sim P2A-F9A \\sim P2A-F10A \\sim P2A-F11A \\sim
P2A-F12A
 with sigma of 0.02
 F12A-F9A \\sim F12A-F11A \\sim F12A-F10A \\sim F12A-F8A \\sim F8A-F9A \\sim
F9A-F11A \\sim F11A-F10A
 \\sim F10A-F8A \\sim F7A-F8A \\sim F7A-F10A \\sim F7A-F11A \\sim F7A-F9A \\sim
F9A-F8A \\sim F8A-F10A ~
 F10A-F11A \\sim F11A-F9A
 with sigma of 0.04
 F7B-F8B \\sim F7B-F10B \\sim F7B-F11B \\sim F7B-F9B \\sim F9B-F8B \\sim
F8B-F10B \\sim F10B-F11B ~
 F11B-F9B \\sim F12B-F9B \\sim F12B-F11B \\sim F12B-F10B \\sim F12B-F8B \\sim
F8B-F9B \\sim F9B-F11B ~
 F11B-F10B \\sim F10B-F8B
 with sigma of 0.04
 P2B-F7B \\sim P2B-F8B \\sim P2B-F9B \\sim P2B-F12B \\sim P2B-F11B \\sim
P2B-F10B
 with sigma of 0.02
 C33A-C25 \\sim C33B-C25
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O34A \\sim O34B \\sim C33B \\sim C33A \\sim O35A \\sim O35B \\sim C36A \\sim
C36B \\sim C37B \\sim C37A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Uanis(F11B) = Uanis(F11A)
4. Rigid body (RIGU) restrains
 P2B, F7B, F8B, F9B, F10B, F11B, F12B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P2A, F7A, F8A, F9A, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O34A, O35A, C25, C33A, C36A, C37A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O34B, O35B, C25, C33B, C36B, C37B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O34B)=Sof(O35B)=Sof(C33B)=Sof(C36B)=Sof(H36A)=Sof(H36B)=Sof(C37B)=
 Sof(H37A)=Sof(H37B)=Sof(H37C)=1-FVAR(1)
 Sof(O34A)=Sof(O35A)=Sof(C33A)=Sof(C36A)=Sof(H27A)=Sof(H27B)=Sof(C37A)=
 Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(P2B)=Sof(F7B)=Sof(F8B)=Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(2)
 Sof(P2A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C36A(H27A,H27B), C36B(H36A,H36B)
6.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C1(H1), C26(H26), C2(H2), C3(H3), C31(H31), C4(H4), C8(H8), C9(H9),
 C10(H10), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20),
  C21(H21), C24(H24), C29(H29), C30(H30)
6.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C12(H12A,H12B,H12C), C37A(H28A,H28B,H28C), C37B(H37A,H37B,
 H37C), C42(H42A,H42B,H42C), C48(H48A,H48B,H48C), C45(H45A,H45B,H45C)
;
_shelx_res_checksum              78260
_shelx_hkl_checksum              20873
_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 1.649
_oxdiff_exptl_absorpt_empirical_full_min 0.775