Chiral Molecular Ruby [Cr(dqp)<sub>2</sub>]<sup>3+</sup> with Long-Lived Circularly Polarized Luminescence.
Jiménez, Juan-Ramón; Doistau, Benjamin; Cruz, Carlos M.; Besnard, Céline; Cuerva, Juan M.; Campaña, Araceli G; Piguet, Claude; Journal of the American Chemical Society 141 (2019) 13244–13252; doi:10.1021/jacs.9b06524

data_4127842
_publ_section_title
;
 Chiral Molecular Ruby [Cr(dqp)<sub>2</sub>]<sup>3+</sup> with Long-Lived
 Circularly Polarized Luminescence.
;
_journal_issue                   33
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13244
_journal_page_last               13252
_journal_paper_doi               10.1021/jacs.9b06524
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C46 H30 Cr N6, 3(F6 P), 2(C3 H6 O), H2 O'
_chemical_formula_sum            'C52 H44 Cr F18 N6 O3 P3'
_chemical_formula_weight         1287.84
_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_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-05-09
_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                   13.45292(10)
_cell_length_b                   17.12816(13)
_cell_length_c                   23.4250(2)
_cell_measurement_reflns_used    42481
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      68.9760
_cell_measurement_theta_min      4.1580
_cell_volume                     5397.68(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4670
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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  39.60   0.60    1.00    --  -38.19  38.00 150.00  181
  2  \w     23.00  95.60   0.60    1.00    --   38.19-125.00  90.00  121
  3  \w     23.00  95.60   0.60    1.00    --   38.19-125.00   0.00  121
  4  \w     57.00 150.00   0.60    1.00    --  100.00 178.00 -60.00  155
  5  \w     57.00 150.00   0.60    1.00    --  100.00 178.00  90.00  155
  6  \w     64.00 178.00   0.60    1.00    --  100.00  77.00 -30.00  190
  7  \w    100.00 178.00   0.60    1.00    --  100.00 111.00  90.00  130
  8  \w    100.00 178.00   0.60    1.00    --  100.00 111.00 -60.00  130
  9  \w    100.00 178.00   0.60    1.00    --  100.00 111.00 150.00  130
 10  \w    100.00 172.60   0.60    1.00    --  100.00 111.00 -90.00  121
 11  \w     83.00 116.60   0.60    1.00    --  100.00 178.00   0.00   56
 12  \w    106.00 169.60   0.60    1.00    --  100.00  61.00-150.00  106
 13  \w    -73.00  -2.80   0.60    1.00    --  -38.19 -77.00  30.00  117
 14  \w    -69.00  40.20   0.60    1.00    --  -38.19  38.00 -90.00  182
 15  \w    -63.00  -6.60   0.60    1.00    --  -38.19 -57.00-150.00   94
 16  \w   -122.00  -2.60   0.60    1.00    --  -38.19 -77.00 150.00  199
 17  \w   -109.00 -67.60   0.60    1.00    --  -38.19 -57.00-150.00   69
 18  \w   -118.00 -78.40   0.60    1.00    --  -38.19 -77.00  30.00   66
 19  \w    -71.00  -3.20   0.60    1.00    --  -38.19 -77.00 -60.00  113
 20  \w    -64.00 -10.60   0.60    1.00    --  -38.19 -77.00-150.00   89
 21  \w    -62.00  -6.80   0.60    1.00    --  -38.19 -57.00  30.00   92
 22  \w   -121.00 -91.00   0.60    1.00    --  -38.19 -77.00-150.00   50
 23  \w    122.00 158.60   0.60    1.00    --  100.00  77.00 120.00   61
 24  \w    151.60 178.00   0.60    1.00    --  100.00  77.00-150.00   44
 25  \w     64.00  89.20   0.60    1.00    --  100.00  77.00   0.00   42
 26  \w     64.00  90.40   0.60    1.00    --  100.00  77.00  60.00   44
 27  \w     64.00 100.00   0.60    1.00    --  100.00  77.00-150.00   60
 28  \w     64.00 115.60   0.60    1.00    --  100.00  77.00 120.00   86
 29  \w     65.00 176.00   0.60    1.00    --  100.00  63.00-110.77  185
 30  \w     19.00 112.00   0.60    1.00    --  100.00-111.00 -90.00  155
 31  \w    134.80 177.40   0.60    1.00    --  100.00 111.00  60.00   71
 32  \w     95.00 123.20   0.60    1.00    --  100.00  77.00  90.00   47
;
_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      0.0799323000
_diffrn_orient_matrix_UB_12      -0.0384449000
_diffrn_orient_matrix_UB_13      0.0377652000
_diffrn_orient_matrix_UB_21      -0.0312547000
_diffrn_orient_matrix_UB_22      0.0524726000
_diffrn_orient_matrix_UB_23      0.0503340000
_diffrn_orient_matrix_UB_31      -0.0757979000
_diffrn_orient_matrix_UB_32      -0.0621427000
_diffrn_orient_matrix_UB_33      0.0191136000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            42188
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.846
_diffrn_reflns_theta_min         3.774
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.598
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.065
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       block
_exptl_crystal_F_000             2612
_exptl_crystal_size_max          0.574
_exptl_crystal_size_mid          0.424
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.607
_refine_diff_density_min         -0.553
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
Flack x determined using 4142 quotients [(I+)-(I-)]/[(I+)+(I-)]:  -0.0016(15)
;
_refine_ls_abs_structure_Flack   0.005(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     822
_refine_ls_number_reflns         9897
_refine_ls_number_restraints     82
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0613P)^2^+2.2304P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.0924
_reflns_Friedel_coverage         0.797
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                9690
_reflns_number_total             9897
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b06524_si_002.cif
_cod_data_source_block           jr215
_cod_database_code               4127842
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C52 H44 Cr1 F18 N6 O3 P3'
_shelx_estimated_absorpt_t_max   0.479
_shelx_estimated_absorpt_t_min   0.232
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.995(5)
 0.005(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
3. Restrained distances
 P2-F40A \\sim P2-F40B \\sim P2-F41A \\sim P2-F41B \\sim P2-F38A \\sim P2-F38B
\\sim P2-F39A \\sim P2-F39B
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O64A \\sim C65A \\sim C66A \\sim C67A \\sim O64B \\sim C65B \\sim C66B \\sim
C67B: within 1A with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 O64B, C65B, C66B, C67B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O64A, C65A, C66A, C67A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O64A)=Sof(C65A)=Sof(C66A)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C67A)=
 Sof(H67A)=Sof(H67B)=Sof(H67C)=1-FVAR(1)
 Sof(O64B)=Sof(C65B)=Sof(C66B)=Sof(H66D)=Sof(H66E)=Sof(H66F)=Sof(C67B)=
 Sof(H67D)=Sof(H67E)=Sof(H67F)=FVAR(1)
 Sof(F38B)=Sof(F39B)=Sof(F40B)=Sof(F41B)=1-FVAR(2)
 Sof(F38A)=Sof(F39A)=Sof(F40A)=Sof(F41A)=FVAR(2)
7.a Riding coordinates:
 C67A(H67A,H67B,H67C)
7.b Free rotating group:
 O64B(C65B,C66B,C67B), OW1(HW1A,HW1B)
7.c Me refined with riding coordinates:
 C66A(H66A,H66B,H66C), C66B(H66D,H66E,H66F), C67B(H67D,H67E,H67F)
7.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C7(H7), C8(H8), C11(H11), C12(H12), C13(H13),
 C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C31(H31), C32(H32),
  C33(H33), C36(H36), C37(H37), C38(H38), C41(H41), C42(H42), C43(H43),
 C46(H46), C47(H47), C48(H48), C51(H51), C52(H52), C53(H53)
7.e Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C), C63(H63A,H63B,H63C)
;
_shelx_res_checksum              98836
_shelx_hkl_checksum              52
_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 1.693
_oxdiff_exptl_absorpt_empirical_full_min 0.684