Reduction of (pddi)Cr reveals redox noninnocence <i>via</i> C-C bond formation amidst competing electrophilicity: [(cpta)CrMe<sub><i>n</i></sub>]<sup>-</sup> (<i>n</i> = 0, 1) and [(pta)Cr]<sup/>.
D'Arpino, Alexander A; Wolczanski, Peter T.; MacMillan, Samantha N.; Cundari, Thomas R.; Krumov, Mihail R.; Chemical communications (Cambridge, England) 60 (2024) 6785–6788; doi:10.1039/d4cc01690d

data_7133137
_publ_section_title
;
 Reduction of (pddi)Cr reveals redox noninnocence <i>via</i> C-C bond
 formation amidst competing electrophilicity:
 [(cpta)CrMe<sub><i>n</i></sub>]<sup>-</sup> (<i>n</i> = 0, 1) and
 [(pta)Cr]<sup/>.
;
_journal_issue                   53
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6785
_journal_page_last               6788
_journal_paper_doi               10.1039/d4cc01690d
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C41 H52 Cr N4, C16 H32 Li O4, C4 H8 O'
_chemical_formula_sum            'C61 H92 Cr Li N4 O5'
_chemical_formula_weight         1020.32
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2023-06-02
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-04-05 deposited with the CCDC.	2024-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                69.5230(10)
_cell_angle_beta                 76.2320(10)
_cell_angle_gamma                65.5100(10)
_cell_formula_units_Z            2
_cell_length_a                   12.36550(10)
_cell_length_b                   14.1523(2)
_cell_length_c                   19.2237(3)
_cell_measurement_reflns_used    34425
_cell_measurement_temperature    100
_cell_measurement_theta_max      79.6410
_cell_measurement_theta_min      2.4570
_cell_volume                     2850.94(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -67.00  11.00   0.50    1.07    --  -48.20  97.00-100.00  156
  2  \w     -6.00  44.00   0.50    1.07    --   48.20 -97.00 151.00  100
  3  \w   -147.00-122.00   0.50    4.27    --  -90.00 -97.00 151.00   50
  4  \w    -74.00 -49.00   0.50    4.27    --  -90.00  97.00-100.00   50
  5  \w     41.00 104.00   0.50    4.27    --  111.50 -97.00 151.00  126
  6  \w    123.00 149.00   0.50    4.27    --  111.50  97.00-100.00   52
  7  \w    -17.00  25.00   0.50    1.07    --  -48.20  19.00 -30.00   84
  8  \w    -61.00  21.00   0.50    1.07    --  -48.20  57.00  90.00  164
  9  \w    -61.00  22.00   0.50    1.07    --  -48.20  57.00-150.00  166
 10  \w    -62.00  23.00   0.50    1.07    --  -48.20  57.00   0.00  170
 11  \w    -84.00 -34.00   0.50    1.07    --  -48.20 -57.00-180.00  100
 12  \w    -46.00 -21.00   0.50    4.27    --  -90.00  45.00 -90.00   50
 13  \w    -51.00 -26.00   0.50    4.27    --  -90.00  45.00  60.00   50
 14  \w    -50.00 -19.00   0.50    4.27    --  -90.00  45.00 120.00   62
 15  \w    130.00 156.00   0.50    4.27    --  111.50  45.00  60.00   52
 16  \w     58.00 102.00   0.50    4.27    --  111.50 -94.00  60.00   88
 17  \w    101.00 135.00   0.50    4.27    --  111.50  31.00  34.65   68
 18  \w     46.00 105.00   0.50    4.27    --  111.50 -94.00-120.00  118
 19  \w     91.00 128.00   0.50    4.27    --  111.50  77.00 -60.00   74
 20  \w    134.00 178.00   0.50    4.27    --  111.50  77.00 -60.00   88
 21  \w     41.00  68.00   0.50    4.27    --  111.50 -61.00-150.00   54
 22  \w     40.00 102.00   0.50    4.27    --  111.50 -94.00 120.00  124
 23  \w     41.00  70.00   0.50    4.27    --  111.50 -61.00  60.00   58
 24  \w     80.00 105.00   0.50    4.27    --  111.50 -94.00 -90.00   50
 25  \w     78.00 104.00   0.50    4.27    --  111.50 -94.00  30.00   52
 26  \w    103.00 171.00   0.50    4.27    --  111.50  30.00 -60.00  136
 27  \w     41.00  66.00   0.50    4.27    --  111.50 -61.00 150.00   50
 28  \w    102.00 132.00   0.50    4.27    --  111.50  30.00-150.00   60
 29  \w    103.00 140.00   0.50    4.27    --  111.50  15.00-180.00   74
 30  \w    116.00 142.00   0.50    4.27    --  111.50  45.00 150.00   52
 31  \w     82.00 107.00   0.50    4.27    --  111.50-125.00 -30.00   50
 32  \w    103.00 133.00   0.50    4.27    --  111.50  30.00-120.00   60
 33  \w     97.00 177.00   0.50    4.27    --  111.50  77.00  60.00  160
 34  \w     78.00 104.00   0.50    4.27    --  111.50 -94.00 -30.00   52
 35  \w     46.00  71.00   0.50    4.27    --  111.50 -62.00-120.72   50
 36  \w     40.00  82.00   0.50    4.27    --  111.50 -77.00-180.00   84
 37  \w     49.00  99.00   0.50    4.27    --  111.50 -94.00   0.00  100
 38  \w    142.00 173.00   0.50    4.27    --  111.50 112.00  63.98   62
 39  \w     74.00 106.00   0.50    4.27    --  111.50-100.00-125.94   64
 40  \w     46.00  72.00   0.50    4.27    --  111.50 -94.00 -90.00   52
 41  \w    103.00 136.00   0.50    4.27    --  111.50 112.00  63.98   66
 42  \w     40.00  69.00   0.50    4.27    --  111.50 -61.00 -60.00   58
 43  \w     78.00 107.00   0.50    4.27    --  111.50-105.00 -37.61   58
 44  \w     99.00 163.00   0.50    4.27    --  111.50  61.00 -30.00  128
 45  \w     96.00 122.00   0.50    4.27    --  111.50-138.00 171.16   52
 46  \w    141.00 167.00   0.50    4.27    --  111.50 125.00 120.00   52
 47  \w     75.00 101.00   0.50    4.27    --  111.50 -77.00   0.00   52
 48  \w     40.00  71.00   0.50    4.27    --  111.50 -61.00  30.00   62
 49  \w     41.00  67.00   0.50    4.27    --  111.50-100.00-125.94   52
 50  \w     41.00  77.00   0.50    4.27    --  111.50 -81.00  34.75   72
 51  \w     96.00 121.00   0.50    4.27    --  111.50 -81.00  34.75   50
 52  \w     48.00  97.00   0.50    4.27    --  111.50 -77.00-150.00   98
 53  \w     40.00  68.00   0.50    4.27    --  111.50 -77.00   0.00   56
 54  \w     54.00  79.00   0.50    4.27    --  111.50 -84.00-138.71   50
 55  \w    149.00 175.00   0.50    4.27    --  111.50  15.00-180.00   52
 56  \w     45.00  70.00   0.50    4.27    --  111.50 -77.00  90.00   50
 57  \w     92.00 118.00   0.50    4.27    --  111.50 -88.00 152.60   52
 58  \w     41.00  87.00   0.50    4.27    --  111.50-131.00 -71.23   92
 59  \w     41.00  67.00   0.50    4.27    --  111.50 -61.00   0.00   52
 60  \w    119.00 145.00   0.50    4.27    --  111.50  73.00  70.38   52
 61  \w     44.00  70.00   0.50    4.27    --  111.50 -77.00 120.00   52
 62  \w     62.00 101.00   0.50    4.27    --  111.50 -94.00  90.00   78
 63  \w     42.00  68.00   0.50    4.27    --  111.50-109.00-153.60   52
 64  \w     74.00 106.00   0.50    4.27    --  111.50-109.00-153.60   64
 65  \w    101.00 150.00   0.50    4.27    --  111.50  15.00-120.00   98
 66  \w    106.00 146.00   0.50    4.27    --  111.50  61.00-120.00   80
 67  \w    105.00 170.00   0.50    4.27    --  111.50  77.00  30.00  130
 68  \w     71.00  97.00   0.50    4.27    --  111.50 -81.00  59.18   52
 69  \w     42.00  68.00   0.50    4.27    --  111.50 -61.00-180.00   52
 70  \w     85.00 111.00   0.50    4.27    --  111.50 -84.00-138.71   52
 71  \w     69.00  95.00   0.50    4.27    --  111.50 -77.00-120.00   52
 72  \w     51.00  78.00   0.50    4.27    --  111.50 -77.00 -30.00   54
 73  \w     62.00 102.00   0.50    4.27    --  111.50 -77.00 150.00   80
 74  \w     42.00  68.00   0.50    4.27    --  111.50 -94.00 150.00   52
 75  \w     64.00 111.00   0.50    4.27    --  111.50-125.00  60.00   94
 76  \w     43.00  78.00   0.50    4.27    --  111.50-125.00 150.00   70
 77  \w    127.00 153.00   0.50    4.27    --  111.50  45.00-180.00   52
 78  \w    114.00 140.00   0.50    4.27    --  111.50  45.00 -30.00   52
 79  \w    149.00 177.00   0.50    4.27    --  111.50  15.00-150.00   56
 80  \w    124.00 150.00   0.50    4.27    --  111.50  15.00 -30.00   52
 81  \w    107.00 134.00   0.50    4.27    --  111.50  15.00  60.00   54
 82  \w    117.00 143.00   0.50    4.27    --  111.50  61.00 -90.00   52
 83  \w     80.00 105.00   0.50    4.27    --  111.50 -77.00 -60.00   50
 84  \w    117.00 143.00   0.50    4.27    --  111.50 125.00-180.00   52
 85  \w    114.00 167.00   0.50    4.27    --  111.50 125.00-120.00  106
 86  \w    107.00 163.00   0.50    4.27    --  111.50 125.00 -90.00  112
 87  \w    133.00 159.00   0.50    4.27    --  111.50 125.00   0.00   52
 88  \w     48.00 109.00   0.50    4.27    --  111.50 -82.00 -72.07  122
 89  \w    117.00 165.00   0.50    4.27    --  111.50  30.00   0.00   96
;
_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      -0.0352344000
_diffrn_orient_matrix_UB_12      0.0044200000
_diffrn_orient_matrix_UB_13      -0.0730567000
_diffrn_orient_matrix_UB_21      -0.0006990000
_diffrn_orient_matrix_UB_22      0.1161984000
_diffrn_orient_matrix_UB_23      -0.0348485000
_diffrn_orient_matrix_UB_31      0.1331375000
_diffrn_orient_matrix_UB_32      -0.0452077000
_diffrn_orient_matrix_UB_33      -0.0292250000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            66068
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.809
_diffrn_reflns_theta_min         2.468
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.039
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.437
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
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            'clear brown'
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_description       block
_exptl_crystal_F_000             1106
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.187
_exptl_crystal_size_min          0.112
_refine_diff_density_max         0.768
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     659
_refine_ls_number_reflns         12309
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0563
_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^)+(0.1005P)^2^+0.8231P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1483
_refine_ls_wR_factor_ref         0.1510
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11586
_reflns_number_total             12309
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01690d2.cif
_cod_data_source_block           raad13_abs
_cod_depositor_comments
'Adding full bibliography for 7133137--7133141.cif.'
_cod_database_code               7133137
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C61H92CrLiN4O5
_chemical_oxdiff_usercomment     'Crystallized from THF/pentane.'
_shelx_estimated_absorpt_t_max   0.804
_shelx_estimated_absorpt_t_min   0.636
_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.a Ternary CH refined with riding coordinates:
 C3(H3), C9(H9), C36(H36), C39(H39)
2.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C21(H21A,H21B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,
 H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B),
 C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B),
  C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C1S(H1SA,
 H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C14(H14), C15(H15), C16(H16), C17(H17), C25(H25),
 C26(H26), C27(H27), C28(H28), C32(H32), C33(H33), C34(H34)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              1362
_shelx_hkl_checksum              77671
_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 1.706
_oxdiff_exptl_absorpt_empirical_full_min 0.572