Vanadium complexes with N-heterocyclic vinylidene ligands
Kooij, Bastiaan; Dong, Zhaowen; Varava, Paul; Fadaei-Tirani, Farzaneh; Scopelliti, Rosario; Piveteau, Laura; Severin, Kay; Chemical Communications  (2022) –; doi:10.1039/D2CC00768A

data_7129823
_publ_section_title
;
 Vanadium complexes with N-heterocyclic vinylidene ligands
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00768A
_journal_year                    2022
_chemical_formula_moiety         'C45 H66 N3 O3 V'
_chemical_formula_sum            'C45 H66 N3 O3 V'
_chemical_formula_weight         747.94
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-09-17
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6396)
;
_audit_update_record
;
2022-01-31 deposited with the CCDC.	2022-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.425(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9179(4)
_cell_length_b                   19.6672(5)
_cell_length_c                   24.8242(7)
_cell_measurement_reflns_used    4612
_cell_measurement_temperature    220.00(10)
_cell_measurement_theta_max      72.1220
_cell_measurement_theta_min      3.5600
_cell_volume                     5272.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      220.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.977
_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    -54.00  14.00   1.00   12.50    --  -40.91  99.00  -7.00   68
  2  \w     11.00  57.00   1.00   12.50    --   40.91 -99.00-112.00   46
  3  \w    105.00 137.00   1.00   50.00    --  105.15  99.00  -7.00   32
  4  \w     38.00  73.00   1.00   50.00    --  105.15 -99.00-112.00   35
  5  \w    -91.00 -14.00   1.00   12.50    --  -40.91 -57.00 -90.00   77
  6  \w    -31.00  65.00   1.00   12.50    --   40.91 -38.00 120.00   96
  7  \w    -20.00   6.00   1.00   12.50    --   40.91 -77.00-150.00   26
  8  \w    131.00 177.00   1.00   50.00    --  105.15 111.00 -60.00   46
  9  \w     79.00 178.00   1.00   50.00    --  105.15  45.00 150.00   99
 10  \w    127.00 178.00   1.00   50.00    --  105.15  77.00 -30.00   51
 11  \w    121.00 148.00   1.00   50.00    --  105.15 111.00-180.00   27
 12  \w     55.00 106.00   1.00   50.00    --  105.15-111.00 -60.00   51
 13  \w     34.00 134.00   1.00   50.00    --  105.15 -61.00 -90.00  100
 14  \w     53.00 127.00   1.00   50.00    --  105.15 -61.00  30.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1251529000
_diffrn_orient_matrix_UB_12      -0.0371008000
_diffrn_orient_matrix_UB_13      -0.0128706000
_diffrn_orient_matrix_UB_21      -0.0671747000
_diffrn_orient_matrix_UB_22      0.0643616000
_diffrn_orient_matrix_UB_23      0.0156254000
_diffrn_orient_matrix_UB_31      -0.0126794000
_diffrn_orient_matrix_UB_32      0.0249356000
_diffrn_orient_matrix_UB_33      -0.0593752000
_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  0.0403
_diffrn_reflns_av_unetI/netI     0.0481
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            25540
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.644
_diffrn_reflns_theta_min         3.600
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.822
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.452
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
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 dark orange'
_exptl_crystal_density_diffrn    0.942
_exptl_crystal_description       plate
_exptl_crystal_F_000             1616
_exptl_crystal_size_max          0.273
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.079
_refine_diff_density_max         0.312
_refine_diff_density_min         -0.306
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     640
_refine_ls_number_reflns         10235
_refine_ls_number_restraints     1102
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0909
_refine_ls_R_factor_gt           0.0611
_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^)+(0.1065P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1683
_refine_ls_wR_factor_ref         0.1880
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6724
_reflns_number_total             10235
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00768a2.cif
_cod_data_source_block           bk135
_cod_database_code               7129823
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H78 N3 O3 V1'
_shelx_estimated_absorpt_t_max   0.869
_shelx_estimated_absorpt_t_min   0.636
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C51-C2 \\sim C57-C2
 with sigma of 0.02
 C47-C46 \\sim C46-C45 \\sim C45-C47 \\sim C48-C49 \\sim C49-C50 \\sim C48-C50
 with sigma of 0.02
 C49-C44 \\sim C47-C44 \\sim C48-C44 \\sim C46-C44 \\sim C50-C44 \\sim C45-C44
 with sigma of 0.02
 C38-C36 \\sim C39-C36 \\sim C37-C36 \\sim C41-C40 \\sim C42-C40 \\sim C43-C40
 with sigma of 0.02
 C41-C42 \\sim C42-C43 \\sim C41-C43 \\sim C38-C37 \\sim C37-C39 \\sim C38-C39
 with sigma of 0.02
 O1-C32 \\sim O1-C28
 with sigma of 0.02
 C29-C30 \\sim C30-C31 \\sim C29-C31 \\sim C33-C34 \\sim C34-C35 \\sim C33-C35
 with sigma of 0.02
 C33-C32 \\sim C34-C32 \\sim C35-C32 \\sim C31-C28 \\sim C29-C28 \\sim C30-C28
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C38 \\sim C36 \\sim C39 \\sim C37 \\sim C41 \\sim C40 \\sim C43 \\sim C42 \\sim
C32 \\sim C33 \\sim C29 \\sim C28 \\sim C30 \\sim C34 \\sim C31 \\sim C35 \\sim
C49 \\sim C47 \\sim C48 \\sim C46 \\sim C50 \\sim C45 \\sim C44: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C51 \\sim C60 \\sim C62 \\sim C53 \\sim C58 \\sim C54 \\sim C61 \\sim C56 \\sim
C59 \\sim C52 \\sim C57 \\sim C55: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C29) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C30) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=1-FVAR(1)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=FVAR(1)
 Sof(C51)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54)=Sof(C55)=
 Sof(H55)=Sof(C56)=Sof(H56)=1-FVAR(2)
 Sof(C57)=Sof(C62)=Sof(H62)=Sof(C61)=Sof(H61)=Sof(C60)=Sof(H60)=Sof(C59)=
 Sof(H59)=Sof(C58)=Sof(H58)=FVAR(2)
 Sof(C40)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=
 Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=1-FVAR(3)
 Sof(C36)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=
 Sof(H38C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(3)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=1-FVAR(4)
 Sof(C28)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=
 Sof(H30C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C9(H9), C12(H12), C21(H21), C24(H24)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C17(H17), C18(H18), C19(H19), C52(H52), C53(H53),
 C54(H54), C55(H55), C56(H56), C62(H62), C61(H61), C60(H60), C59(H59), C58(H58)
6.c Fitted hexagon refined as free rotating group:
 C57(C62,C61,C60,C59,C58)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C),
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,
 H50C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 144 electrons were 
found in a volume of 1154\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.85[C5H12] per Asymmetric Unit 
which account for 143 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              69817
_shelx_hkl_checksum              3256
_shelx_fab_checksum              62889
_olex2_date_sample_data_collection 2021-09-15
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.416
_oxdiff_exptl_absorpt_empirical_full_min 0.557