Pnictogen-based vanadacyclobutadiene complexes.
Jafari, Mehrafshan G.; Russell, John B.; Myung, Hwan; Kwon, Seongyeon; Carroll, Patrick J.; Gau, Michael R.; Baik, Mu-Hyun; Mindiola, Daniel J.; Chemical science 15 (2024) 19752–19763; doi:10.1039/d4sc05884d

data_1572995
_publ_section_title
;
 Pnictogen-based vanadacyclobutadiene complexes.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              19752
_journal_page_last               19763
_journal_paper_doi               10.1039/d4sc05884d
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C41 H54 N3 V, C5 H12'
_chemical_formula_sum            'C46 H66 N3 V'
_chemical_formula_weight         711.95
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-20
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2024-08-21 deposited with the CCDC.	2024-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 145.799(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.2051(15)
_cell_length_b                   12.7630(2)
_cell_length_c                   27.536(2)
_cell_measurement_reflns_used    34697
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.9700
_cell_measurement_theta_min      2.2190
_cell_volume                     4189.0(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'HPC area detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix 3000HE'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.969
_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     26.00  52.00   0.50   45.00    --  -14.00  37.00 -30.00   52
  2  \w    -30.00  20.00   0.50   45.00    --  -14.00  37.00 -30.00  100
  3  \w    -48.00  -3.00   0.50   45.00    --   14.62 -37.00 -30.00   90
  4  \w    -25.00  13.00   0.50   45.00    --  -14.00 -77.00   0.00   76
  5  \w     -7.00  22.00   0.50   45.00    --  -14.00 -99.00   0.00   58
  6  \w     23.00  49.00   0.50   45.00    --   14.62 -99.00 -30.00   52
  7  \w    -24.00   6.00   0.50   45.00    --  -14.00 -77.00  60.00   60
  8  \w    -44.00   5.00   0.50   45.00    --   14.62 -19.00  90.00   98
  9  \w     -1.00  58.00   0.50   45.00    --   14.62  57.00  60.00  118
 10  \w     10.00  57.00   0.50   45.00    --   14.62  57.00 120.00   94
 11  \w     25.00  59.00   0.50   45.00    --   14.62  57.00 150.00   68
 12  \w    -53.00 -13.00   0.50   45.00    --   14.62 -19.00 150.00   80
 13  \w    -46.00 -12.00   0.50   45.00    --   14.62 -19.00 120.00   68
 14  \w    -82.00 -21.00   0.50   45.00    --  -14.00 -37.00   0.00  122
 15  \w    -56.00 -22.00   0.50   45.00    --   14.62 -19.00 -90.00   68
 16  \w     -7.00  21.00   0.50   45.00    --  -14.00 -99.00-120.00   56
 17  \w     21.00  50.00   0.50   45.00    --   14.62-112.00-127.00   58
 18  \w     -5.00  20.00   0.50   45.00    --  -14.00 -99.00-150.00   50
 19  \w     -4.00  21.00   0.50   45.00    --  -14.00 -99.00-180.00   50
 20  \w    -53.00 -28.00   0.50   45.00    --   14.62 -19.00-120.00   50
 21  \w    -27.00   1.00   0.50   45.00    --  -14.00  37.00-150.00   56
 22  \w      5.00  49.00   0.50   45.00    --  -14.00  37.00-150.00   88
 23  \w     -6.00  55.00   0.50   45.00    --   14.62  57.00-150.00  122
 24  \w     -7.00  18.00   0.50   45.00    --   14.62  77.00-150.00   50
 25  \w    -51.00 -24.00   0.50   45.00    --  -14.00 125.00-180.00   54
 26  \w    -57.00 -32.00   0.50   45.00    --   14.62 -19.00-180.00   50
 27  \w    -57.00 -31.00   0.50   45.00    --  -14.00 112.00 -34.00   52
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-i'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0400780000
_diffrn_orient_matrix_UB_12      0.0085335000
_diffrn_orient_matrix_UB_13      0.0069149000
_diffrn_orient_matrix_UB_21      0.0146044000
_diffrn_orient_matrix_UB_22      -0.0538481000
_diffrn_orient_matrix_UB_23      0.0098869000
_diffrn_orient_matrix_UB_31      -0.0414789000
_diffrn_orient_matrix_UB_32      -0.0106805000
_diffrn_orient_matrix_UB_33      -0.0442368000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            64993
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.121
_diffrn_reflns_theta_min         1.865
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.270
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44010
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SCALE3 ABSPACK'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.129
_exptl_crystal_description       block
_exptl_crystal_F_000             1544
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.274
_exptl_crystal_size_min          0.065
_refine_diff_density_max         0.416
_refine_diff_density_min         -0.406
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         9922
_refine_ls_number_restraints     141
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0591
_refine_ls_R_factor_gt           0.0422
_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^)+(0.0419P)^2^+1.5186P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1009
_refine_ls_wR_factor_ref         0.1076
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7759
_reflns_number_total             9922
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05884d2.cif
_cod_data_source_block           9605_complex2
_cod_depositor_comments
'Adding full bibliography for 1572995--1572996.cif.'
_cod_original_cell_volume        4188.9(11)
_cod_database_code               1572995
_shelx_shelxl_version_number     2019/3
_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,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H,H,H,H) groups
2. Restrained distances
 C44'-C43 = C44*-C43 = C44-C43 = C45'-C44' = C44*-C45* = C45-C44 = C45-C46 =
 C46-C45* = C45'-C46
 1.54 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C44' \\sim C42 \\sim C43 \\sim C44 \\sim C44* \\sim C45 \\sim C45' \\sim C45*
\\sim C46: within 2A with sigma of 0.003 and sigma for terminal atoms of 0.006
within 2A
4. Others
 Fixed Sof: H43A(0.4) H43B(0.4) H43C(0.38) H43D(0.38) H43E(0.22) H43F(0.22)
 C44(0.4) H44A(0.4) H44B(0.4) C44'(0.22) H44C(0.22) H44D(0.22) C44*(0.38)
 H44E(0.38) H44F(0.38) C45(0.4) H45A(0.4) H45B(0.4) C45'(0.22) H45C(0.22)
 H45D(0.22) C45*(0.38) H45E(0.38) H45F(0.38) H46D(0.38) H46E(0.38) H46F(0.38)
 H46A(0.4) H46B(0.4) H46C(0.4) H46G(0.22) H46H(0.22) H46I(0.22)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27)
5.b Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C43(H43C,H43D), C43(H43E,H43F), C44(H44A,H44B), C44'(H44C,
 H44D), C44*(H44E,H44F), C45(H45A,H45B), C45'(H45C,H45D), C45*(H45E,H45F)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C37(H37),
 C38(H38), C39(H39), C40(H40), C41(H41)
5.d X=CH2 refined with riding coordinates:
 C4(H4A,H4B)
5.e Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,
 H28B,H28C), C29(H29A,H29B,H29C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C42(H42A,H42B,H42C), C46(H46D,H46E,H46F), C46(H46A,H46B,
 H46C), C46(H46G,H46H,H46I)
;
_shelx_res_checksum              74112
_shelx_hkl_checksum              85052
_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 1.540
_oxdiff_exptl_absorpt_empirical_full_min 0.591