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_7133139
_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 H50 Cr N4, C20 H40 K O8'
_chemical_formula_sum            'C61 H90 Cr K N4 O8'
_chemical_formula_weight         1098.46
_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             2023-07-10
_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                85.0960(10)
_cell_angle_beta                 78.0350(10)
_cell_angle_gamma                75.8430(10)
_cell_formula_units_Z            2
_cell_length_a                   11.78630(10)
_cell_length_b                   14.0237(2)
_cell_length_c                   19.3145(3)
_cell_measurement_reflns_used    39871
_cell_measurement_temperature    100
_cell_measurement_theta_max      79.3300
_cell_measurement_theta_min      2.3170
_cell_volume                     3026.20(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_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 0.993
_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    -79.00 -18.00   0.50    1.32    --  -48.20 112.00 -39.00  122
  2  \w     46.00  82.00   0.50    1.32    --   48.20-112.00-132.00   72
  3  \w   -144.00-119.00   0.50    5.29    --  -90.00-112.00-132.00   50
  4  \w    -77.00 -52.00   0.50    5.29    --  -90.00 112.00 -39.00   50
  5  \w    103.00 143.00   0.50    5.29    --  111.50 112.00 -39.00   80
  6  \w     75.00 108.00   0.50    5.29    --  111.50-112.00-132.00   66
  7  \w    -25.00  26.00   0.50    1.32    --  -48.20  19.00  30.00  102
  8  \w   -120.00 -35.00   0.50    1.32    --  -48.20 -57.00-120.00  170
  9  \w    -26.00   9.00   0.50    1.32    --  -48.20  19.00-180.00   70
 10  \w    -25.00  26.00   0.50    1.32    --  -48.20  19.00 120.00  102
 11  \w    -25.00  17.00   0.50    1.32    --   48.20 -19.00 150.00   84
 12  \w    -20.00   9.00   0.50    1.32    --   48.20 -57.00 -90.00   58
 13  \w     27.00  59.00   0.50    1.32    --   48.20  77.00-180.00   64
 14  \w     68.00 114.00   0.50    1.32    --   48.20  77.00-180.00   92
 15  \w     17.00  60.00   0.50    1.32    --   48.20 -57.00 -90.00   86
 16  \w    -70.00 -44.00   0.50    5.29    --  -90.00  61.00-120.00   52
 17  \w    -43.00 -18.00   0.50    5.29    --  -90.00  45.00  90.00   50
 18  \w     94.00 132.00   0.50    5.29    --  111.50  77.00  90.00   76
 19  \w     57.00 105.00   0.50    5.29    --  111.50 -94.00 -60.00   96
 20  \w    103.00 135.00   0.50    5.29    --  111.50  30.00 -90.00   64
 21  \w     60.00 104.00   0.50    5.29    --  111.50-125.00-150.00   88
 22  \w     41.00  66.00   0.50    5.29    --  111.50 -61.00-120.00   50
 23  \w     56.00  91.00   0.50    5.29    --  111.50-125.00  30.00   70
 24  \w     73.00 102.00   0.50    5.29    --  111.50 -94.00  30.00   58
 25  \w     80.00 105.00   0.50    5.29    --  111.50 -77.00 -30.00   50
 26  \w     41.00  75.00   0.50    5.29    --  111.50 -94.00  90.00   68
 27  \w     44.00  74.00   0.50    5.29    --  111.50 -77.00 -30.00   60
 28  \w    121.00 147.00   0.50    5.29    --  111.50  45.00  90.00   52
 29  \w     40.00  77.00   0.50    5.29    --  111.50 -94.00-180.00   74
 30  \w    122.00 158.00   0.50    5.29    --  111.50  45.00  30.00   72
 31  \w    103.00 160.00   0.50    5.29    --  111.50  15.00-180.00  114
 32  \w    113.00 150.00   0.50    5.29    --  111.50  61.00 -30.00   74
 33  \w    135.00 161.00   0.50    5.29    --  111.50  77.00  90.00   52
 34  \w     50.00 111.00   0.50    5.29    --  111.50-125.00   0.00  122
 35  \w     63.00 110.00   0.50    5.29    --  111.50 -79.00 122.14   94
 36  \w     42.00  68.00   0.50    5.29    --  111.50 -61.00 -90.00   52
 37  \w    119.00 145.00   0.50    5.29    --  111.50 125.00-120.00   52
 38  \w     62.00 104.00   0.50    5.29    --  111.50 -77.00 -90.00   84
 39  \w     42.00 105.00   0.50    5.29    --  111.50 -94.00  60.00  126
 40  \w     40.00  73.00   0.50    5.29    --  111.50 -63.00   2.30   66
 41  \w     52.00  78.00   0.50    5.29    --  111.50 -77.00-150.00   52
 42  \w     75.00 124.00   0.50    5.29    --  111.50 -88.00 115.82   98
 43  \w     42.00  67.00   0.50    5.29    --  111.50-125.00 120.00   50
 44  \w    137.00 174.00   0.50    5.29    --  111.50  61.00  90.00   74
 45  \w    149.00 174.00   0.50    5.29    --  111.50 125.00  60.00   50
 46  \w    124.00 169.00   0.50    5.29    --  111.50  45.00 120.00   90
 47  \w    104.00 175.00   0.50    5.29    --  111.50  15.00 -60.00  142
 48  \w     43.00  98.00   0.50    5.29    --  111.50 -77.00-180.00  110
 49  \w    106.00 156.00   0.50    5.29    --  111.50 125.00 -90.00  100
 50  \w     61.00  86.00   0.50    5.29    --  111.50 -94.00   0.00   50
 51  \w     43.00  69.00   0.50    5.29    --  111.50-132.00  23.98   52
 52  \w     82.00 117.00   0.50    5.29    --  111.50-132.00  23.98   70
 53  \w    105.00 153.00   0.50    5.29    --  111.50  45.00 -30.00   96
 54  \w    123.00 149.00   0.50    5.29    --  111.50  15.00 -90.00   52
 55  \w    106.00 141.00   0.50    5.29    --  111.50 125.00  30.00   70
 56  \w    142.00 168.00   0.50    5.29    --  111.50 125.00  30.00   52
 57  \w    103.00 130.00   0.50    5.29    --  111.50  45.00 150.00   54
 58  \w     40.00  65.00   0.50    5.29    --  111.50 -61.00 -60.00   50
 59  \w    133.00 177.00   0.50    5.29    --  111.50  77.00-180.00   88
 60  \w     96.00 170.00   0.50    5.29    --  111.50 125.00 150.00  148
 61  \w     68.00 116.00   0.50    5.29    --  111.50 -88.00  46.63   96
 62  \w    106.00 132.00   0.50    5.29    --  111.50  77.00-180.00   52
 63  \w     43.00  68.00   0.50    5.29    --  111.50 -61.00-150.00   50
 64  \w     72.00 105.00   0.50    5.29    --  111.50 -77.00-120.00   66
 65  \w     60.00 105.00   0.50    5.29    --  111.50 -94.00 120.00   90
 66  \w    111.00 153.00   0.50    5.29    --  111.50  30.00 120.00   84
 67  \w     98.00 128.00   0.50    5.29    --  111.50  61.00-150.00   60
 68  \w    135.00 166.00   0.50    5.29    --  111.50  61.00-150.00   62
 69  \w     91.00 142.00   0.50    5.29    --  111.50 144.00-145.39  102
 70  \w     94.00 156.00   0.50    5.29    --  111.50  77.00 150.00  124
 71  \w     62.00 103.00   0.50    5.29    --  111.50 -94.00-120.00   82
 72  \w    127.00 153.00   0.50    5.29    --  111.50  61.00 -90.00   52
 73  \w     96.00 125.00   0.50    5.29    --  111.50  61.00 -90.00   58
 74  \w     79.00 104.00   0.50    5.29    --  111.50 -77.00  60.00   50
 75  \w     79.00 104.00   0.50    5.29    --  111.50 -94.00-150.00   50
 76  \w     62.00 111.00   0.50    5.29    --  111.50-125.00-180.00   98
 77  \w     40.00  67.00   0.50    5.29    --  111.50 -77.00   0.00   54
 78  \w     86.00 111.00   0.50    5.29    --  111.50-125.00 120.00   50
 79  \w    102.00 128.00   0.50    5.29    --  111.50  30.00-180.00   52
 80  \w    127.00 153.00   0.50    5.29    --  111.50  15.00  30.00   52
 81  \w    109.00 150.00   0.50    5.29    --  111.50  15.00  90.00   82
 82  \w    116.00 142.00   0.50    5.29    --  111.50  61.00 -60.00   52
 83  \w     41.00  66.00   0.50    5.29    --  111.50 -61.00  30.00   50
 84  \w    114.00 139.00   0.50    5.29    --  111.50  61.00 120.00   50
 85  \w     43.00  68.00   0.50    5.29    --  111.50 -61.00 150.00   50
 86  \w     49.00  91.00   0.50    5.29    --  111.50 -94.00 -90.00   84
 87  \w    130.00 167.00   0.50    5.29    --  111.50 125.00 120.00   74
 88  \w    105.00 130.00   0.50    5.29    --  111.50  77.00   0.00   50
 89  \w    145.00 170.00   0.50    5.29    --  111.50  77.00   0.00   50
 90  \w     93.00 125.00   0.50    5.29    --  111.50  77.00  60.00   64
 91  \w    134.00 178.00   0.50    5.29    --  111.50  77.00  60.00   88
 92  \w     95.00 121.00   0.50    5.29    --  111.50 -88.00 -18.96   52
 93  \w     42.00  70.00   0.50    5.29    --  111.50 -61.00  90.00   56
;
_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      0.0243731000
_diffrn_orient_matrix_UB_12      -0.1131630000
_diffrn_orient_matrix_UB_13      0.0056863000
_diffrn_orient_matrix_UB_21      0.0023443000
_diffrn_orient_matrix_UB_22      -0.0025637000
_diffrn_orient_matrix_UB_23      -0.0798732000
_diffrn_orient_matrix_UB_31      0.1351839000
_diffrn_orient_matrix_UB_32      -0.0063696000
_diffrn_orient_matrix_UB_33      -0.0156391000
_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  0.0390
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            73988
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.865
_diffrn_reflns_theta_min         2.340
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.602
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.497
_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 red'
_exptl_crystal_density_diffrn    1.206
_exptl_crystal_description       block
_exptl_crystal_F_000             1182
_exptl_crystal_size_max          0.176
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.075
_refine_diff_density_max         0.685
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     714
_refine_ls_number_reflns         13099
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0403
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0552P)^2^+0.9879P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1085
_refine_ls_wR_factor_ref         0.1102
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12240
_reflns_number_total             13099
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01690d2.cif
_cod_data_source_block           raad14_abs
_cod_depositor_comments
'Adding full bibliography for 7133137--7133141.cif.'
_cod_database_code               7133139
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C61H90CrKN4O8
_chemical_oxdiff_usercomment     'Crystallized from THF/hexanes.'
_shelx_estimated_absorpt_t_max   0.829
_shelx_estimated_absorpt_t_min   0.657
_olex2_refinement_description
;
1. 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
2. Restrained distances
 O7-C54 \\sim O7B-C54B
 with sigma of 0.02
 C55B-C54B \\sim C55-C54 \\sim C56-C55 \\sim C56-C55B \\sim C57-C56
 with sigma of 0.02
3. Others
 Sof(H56C)=Sof(H56D)=Sof(H57C)=Sof(H57D)=Sof(O7B)=Sof(C55B)=Sof(H55C)=
 Sof(H55D)=Sof(C54B)=Sof(H54C)=Sof(H54D)=1-FVAR(1)
 Sof(O7)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H56A)=
 Sof(H56B)=Sof(H57A)=Sof(H57B)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C3(H3), C10(H10), C19(H19), C20(H20), C36(H36), C39(H39)
4.b Secondary CH2 refined with riding coordinates:
 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), C56(H56C,H56D), C57(H57A,H57B), C57(H57C,H57D), C58(H58A,
 H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C55B(H55C,H55D),
 C54B(H54C,H54D)
4.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)
4.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 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              43042
_shelx_hkl_checksum              27837
_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 1.348
_oxdiff_exptl_absorpt_empirical_full_min 0.722