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_7133140
_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         'C98 H132 Cr2 K2 N8 O4, C4 H8 O'
_chemical_formula_sum            'C102 H140 Cr2 K2 N8 O5'
_chemical_formula_weight         1740.41
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-22
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2024-04-05 deposited with the CCDC.	2024-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   41.8744(3)
_cell_length_b                   41.8744(3)
_cell_length_c                   15.47760(10)
_cell_measurement_reflns_used    40056
_cell_measurement_temperature    102.6(5)
_cell_measurement_theta_max      77.7300
_cell_measurement_theta_min      2.1130
_cell_volume                     23503.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (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      102.6(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_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    -93.00 -18.00   0.50    1.00    --  -48.30 134.00 -60.00  150
  2  \w    -63.00 -14.00   0.50    3.00    --  -86.25  55.00-113.00   98
  3  \w     37.00 159.00   0.50    3.00    --  107.75  -1.00  67.00  244
  4  \w     36.00  63.00   0.50    3.00    --  107.75 -55.00 104.00   54
  5  \w    -25.00  26.00   0.50    1.00    --   48.30 -19.00-150.00  102
  6  \w    -51.00 -14.00   0.50    3.00    --  -86.25  45.00 -60.00   74
  7  \w     36.00  71.00   0.50    3.00    --  107.75 -61.00  30.00   70
  8  \w    101.00 178.00   0.50    3.00    --  107.75  89.00-149.06  154
  9  \w     36.00 106.00   0.50    3.00    --  107.75 -77.00  90.00  140
 10  \w     93.00 178.00   0.50    3.00    --  107.75  61.00 -60.00  170
 11  \w     36.00  71.00   0.50    3.00    --  107.75 -61.00-120.00   70
 12  \w    104.00 178.00   0.50    3.00    --  107.75  93.00  -0.26  148
 13  \w     97.00 168.00   0.50    3.00    --  107.75  45.00-150.00  142
 14  \w    124.00 151.00   0.50    3.00    --  107.75 125.00 -90.00   54
 15  \w     56.00  82.00   0.50    3.00    --  107.75 -77.00-180.00   52
 16  \w     74.00 100.00   0.50    3.00    --  107.75 -77.00 120.00   52
 17  \w     37.00  71.00   0.50    3.00    --  107.75 -61.00-180.00   68
 18  \w     51.00  88.00   0.50    3.00    --  107.75-135.00  53.00   74
 19  \w     50.00  79.00   0.50    3.00    --  107.75-134.00-127.00   58
 20  \w     77.00 127.00   0.50    3.00    --  107.75 -80.00  16.75  100
 21  \w    123.00 160.00   0.50    3.00    --  107.75  30.00  60.00   74
 22  \w    106.00 155.00   0.50    3.00    --  107.75 125.00  90.00   98
 23  \w     99.00 129.00   0.50    3.00    --  107.75 125.00 -60.00   60
 24  \w     42.00  68.00   0.50    3.00    --  107.75 -77.00-120.00   52
 25  \w     98.00 124.00   0.50    3.00    --  107.75 125.00  30.00   52
 26  \w    133.00 159.00   0.50    3.00    --  107.75 125.00  30.00   52
 27  \w    105.00 153.00   0.50    3.00    --  107.75  61.00-180.00   96
 28  \w     36.00  61.00   0.50    3.00    --  107.75 -61.00  60.00   50
 29  \w     79.00 106.00   0.50    3.00    --  107.75-125.00-120.00   54
 30  \w     66.00 103.00   0.50    3.00    --  107.75-125.00   0.00   74
 31  \w    122.00 148.00   0.50    3.00    --  107.75  15.00 -90.00   52
 32  \w     53.00  79.00   0.50    3.00    --  107.75 -77.00   0.00   52
 33  \w     50.00  85.00   0.50    3.00    --  107.75 -77.00  30.00   70
 34  \w     39.00  64.00   0.50    3.00    --  107.75 -77.00 120.00   50
 35  \w    114.00 145.00   0.50    3.00    --  107.75  45.00  30.00   62
 36  \w     98.00 123.00   0.50    3.00    --  107.75  30.00-150.00   50
 37  \w    153.00 178.00   0.50    3.00    --  107.75  77.00 -30.00   50
 38  \w     36.00  62.00   0.50    3.00    --  107.75 -80.00  16.75   52
 39  \w    106.00 132.00   0.50    3.00    --  107.75  45.00  30.00   52
 40  \w   -116.00 -67.00   0.50    1.00    --  -48.30-135.00  53.00   98
 41  \w    -21.00  26.00   0.50    1.00    --  -48.30  19.00 150.00   94
 42  \w     43.00  81.00   0.50    1.00    --   48.30-125.00 120.00   76
 43  \w    137.00 172.00   0.50    3.00    --  107.75  45.00   0.00   70
 44  \w     99.00 125.00   0.50    3.00    --  107.75  30.00   0.00   52
 45  \w     97.00 123.00   0.50    3.00    --  107.75  45.00-180.00   52
 46  \w     37.00  66.00   0.50    3.00    --  107.75 -61.00 120.00   58
 47  \w     85.00 111.00   0.50    3.00    --  107.75-125.00 150.00   52
 48  \w    140.00 166.00   0.50    3.00    --  107.75  61.00-150.00   52
 49  \w    102.00 128.00   0.50    3.00    --  107.75  15.00   0.00   52
 50  \w    133.00 159.00   0.50    3.00    --  107.75  15.00   0.00   52
 51  \w     86.00 131.00   0.50    3.00    --  107.75  77.00  30.00   90
 52  \w    116.00 162.00   0.50    3.00    --  107.75  77.00 120.00   92
 53  \w     36.00  61.00   0.50    3.00    --  107.75 -61.00 -60.00   50
 54  \w     66.00 109.00   0.50    3.00    --  107.75-115.00 172.80   86
 55  \w     93.00 118.00   0.50    3.00    --  107.75  61.00-180.00   50
 56  \w    106.00 132.00   0.50    3.00    --  107.75  15.00 -60.00   52
 57  \w     99.00 125.00   0.50    3.00    --  107.75  61.00-150.00   52
 58  \w    105.00 131.00   0.50    3.00    --  107.75  30.00  30.00   52
 59  \w     36.00  61.00   0.50    3.00    --  107.75 -61.00-180.00   50
 60  \w     43.00  69.00   0.50    3.00    --  107.75 -61.00  90.00   52
 61  \w     61.00 107.00   0.50    3.00    --  107.75-125.00 -90.00   92
 62  \w    122.00 148.00   0.50    3.00    --  107.75  15.00  90.00   52
 63  \w     87.00 112.00   0.50    3.00    --  107.75  77.00-180.00   50
 64  \w    130.00 169.00   0.50    3.00    --  107.75  77.00 150.00   78
 65  \w     81.00 106.00   0.50    3.00    --  107.75 -77.00 -90.00   50
 66  \w     81.00 106.00   0.50    3.00    --  107.75 -91.00  40.42   50
 67  \w     44.00  70.00   0.50    3.00    --  107.75-125.00-180.00   52
 68  \w     38.00  73.00   0.50    3.00    --  107.75-125.00 -30.00   70
 69  \w     53.00  79.00   0.50    3.00    --  107.75-125.00  90.00   52
 70  \w     39.00  65.00   0.50    3.00    --  107.75 -61.00 -30.00   52
 71  \w    146.00 172.00   0.50    3.00    --  107.75  45.00-180.00   52
 72  \w    110.00 136.00   0.50    3.00    --  107.75  61.00  60.00   52
 73  \w     89.00 115.00   0.50    3.00    --  107.75 -87.00 157.80   52
 74  \w    151.00 177.00   0.50    3.00    --  107.75  45.00  30.00   52
;
_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      0.0006706000
_diffrn_orient_matrix_UB_12      -0.0363678000
_diffrn_orient_matrix_UB_13      -0.0073705000
_diffrn_orient_matrix_UB_21      -0.0003229000
_diffrn_orient_matrix_UB_22      0.0025671000
_diffrn_orient_matrix_UB_23      -0.0992646000
_diffrn_orient_matrix_UB_31      0.0424503000
_diffrn_orient_matrix_UB_32      0.0218182000
_diffrn_orient_matrix_UB_33      -0.0006518000
_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  0.0807
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       51
_diffrn_reflns_limit_h_min       -49
_diffrn_reflns_limit_k_max       53
_diffrn_reflns_limit_k_min       -53
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            156996
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.090
_diffrn_reflns_theta_min         2.110
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.817
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.662
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
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    1.107
_exptl_crystal_description       plate
_exptl_crystal_F_000             8406
_exptl_crystal_size_max          0.201
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.853
_refine_diff_density_min         -0.944
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     582
_refine_ls_number_reflns         11157
_refine_ls_number_restraints     105
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0678
_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^)+(0.1504P)^2^+26.3877P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2045
_refine_ls_wR_factor_ref         0.2192
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9266
_reflns_number_total             11157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01690d2.cif
_cod_data_source_block           raad10_abs
_cod_depositor_comments
'Adding full bibliography for 7133137--7133141.cif.'
_cod_original_cell_volume        23503.4(4)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               7133140
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C53H74CrKN4O3
_chemical_oxdiff_usercomment     'Crystallized from THF/hexanes.'
_shelx_estimated_absorpt_t_max   0.802
_shelx_estimated_absorpt_t_min   0.601
_reflns_odcompleteness_completeness 98.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     78.89
_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
 O3-C53 = O3-C50
 1.44 with sigma of 0.02
 C53-C52 = C51-C50
 1.53 with sigma of 0.02
 C52-C51
 1.54 with sigma of 0.02
 O3-C52 = O3-C51 = C53-C51 = C52-C50
 2.38 with sigma of 0.04
 C52-C50 \\sim C53-C51
 with sigma of 0.04
 O3-C52 \\sim O3-C51
 with sigma of 0.04
 C53-C52 \\sim C52-C51 \\sim C51-C50
 with sigma of 0.02
 O3-C53 \\sim O3-C50
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O3 \\sim C50 \\sim C51 \\sim C52 \\sim C53: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(O2) = Uanis(O2B)
Uanis(C49) = Uanis(C46B)
Uanis(C48) = Uanis(C47B)
Uanis(C46) = Uanis(C49B)
4. Rigid body (RIGU) restrains
 O3, C50, C51, C52, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O2, C46, C47, C48, C49} sigma for 1-2: 0.02, 1-3: 0.02
{O2B, C49B, C48, C47B, C46B} sigma for 1-2: 0.02, 1-3: 0.02
as in
{O1, C42, C43, C44, C45}
6. Others
 Sof(H48C)=Sof(H48D)=Sof(O2B)=Sof(C49B)=Sof(H49C)=Sof(H49D)=Sof(C47B)=
 Sof(H47C)=Sof(H47D)=Sof(C46B)=Sof(H46C)=Sof(H46D)=1-FVAR(1)
 Sof(O2)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H48A)=
 Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=FVAR(1)
 Fixed Sof: O3(0.5) C50(0.5) H50A(0.5) H50B(0.5) C51(0.5) H51A(0.5) H51B(0.5)
 C52(0.5) H52A(0.5) H52B(0.5) C53(0.5) H53A(0.5) H53B(0.5)
7.a Ternary CH refined with riding coordinates:
 C3(H3), C10(H10), C19(H19), C20(H20), C36(H36), C39(H39)
7.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), C48(H48C,H48D), C49(H49A,H49B),
 C49B(H49C,H49D), C47B(H47C,H47D), C46B(H46C,H46D), C50(H50A,H50B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B)
7.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)
7.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              46801
_shelx_hkl_checksum              33522
_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 1.271
_oxdiff_exptl_absorpt_empirical_full_min 0.841