Experimental and Computational Study of the Exchange Interaction between the V(III) Centers in the Vanadium-Cyclal Dimer
Reiß, Andreas; Reimann, Maximilian Kai; Jin, Chengyu; Wachter-Lehn, Martha; Kremer, Reinhard; Pöttgen, Rainer; Fink, Karin; Klopper, Wim; Feldmann, Claus; Dalton Transactions  (2023) –; doi:10.1039/D3DT03243D

data_7714395
_publ_section_title
;
 Experimental and Computational Study of the Exchange Interaction between
 the V(III) Centers in the Vanadium-Cyclal Dimer
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT03243D
_journal_year                    2023
_chemical_formula_moiety         'C22 H46 N8 V2'
_chemical_formula_sum            'C22 H46 N8 V2'
_chemical_formula_weight         524.55
_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     iterative
_audit_creation_date             2023-08-17
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-08-17 deposited with the CCDC.	2023-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.22(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.050(4)
_cell_length_b                   8.508(2)
_cell_length_c                   13.565(5)
_cell_measurement_reflns_used    5028
_cell_measurement_temperature    210
_cell_measurement_theta_max      54.74
_cell_measurement_theta_min      3.43
_cell_volume                     1267.8(7)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      210.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'STOE IPDS II'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0662
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            8264
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         2.261
_exptl_absorpt_coefficient_mu    0.763
_exptl_absorpt_correction_T_max  0.6800
_exptl_absorpt_correction_T_min  0.1462
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'X-Area X-Red 1.63.4.0 (STOE, 2017)'
_exptl_crystal_colour            'dark green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_description       block
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.214
_refine_diff_density_min         -0.432
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         2493
_refine_ls_number_restraints     1099
_refine_ls_restrained_S_all      2.015
_refine_ls_R_factor_all          0.0660
_refine_ls_R_factor_gt           0.0611
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1102P)^2^+0.6185P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1659
_refine_ls_wR_factor_ref         0.1721
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2170
_reflns_number_total             2493
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03243d2.cif
_cod_data_source_block           v2(hcyclal)2
_cod_database_code               7714395
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.862
_shelx_estimated_absorpt_t_min   0.750
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
2. Restrained distances
 C2A-C1A \\sim C7A-C6A \\sim C8A-C7A \\sim C10A-C11A \\sim C9A-C10A \\sim
C4A-C5A \\sim C3A-C4A \\sim C8B-
 C7B \\sim C9B-C8B \\sim C10B-C11B \\sim C5B-C6B \\sim C4B-C5B \\sim C2B-C1B
\\sim C3B-C2B
 with sigma of 0.02
 N4A-C7A \\sim C8A-C6A \\sim N2A-C1A \\sim C2A-N1A \\sim C8A-C11A \\sim C3A-C1A
\\sim N1A-C2A \\sim N2A-
 C7A \\sim C6A-C8A \\sim N1A-C2A \\sim C1A-N2A \\sim C6A-C8A \\sim C7A-N4A
\\sim C1B-C4B \\sim N1B-C5B ~
 C6B-N3B \\sim C10B-N4B \\sim C11B-C9B \\sim N1B-C2B \\sim C1B-C3B \\sim
N2B-C8B \\sim C7B-C9B \\sim C9B-
 C7B \\sim C8B-N2B \\sim C3B-C1B
 with sigma of 0.04
 N3B-C6B \\sim N3A-C5A \\sim N3A-C9A \\sim N3B-C10B \\sim N4B-C11B \\sim
N4A-C11A \\sim N4B-C9B \\sim N4A-
 C8A \\sim N2B-C7B \\sim N2B-C3B \\sim N2A-C6A \\sim N2A-C2A \\sim N1B-C1B
\\sim N1A-C1A \\sim N1B-C4B ~
 N1A-C3A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N4A \\sim N3A \\sim N1A \\sim N2A \\sim C11A \\sim C10A \\sim C9A \\sim C5A
\\sim C4A \\sim C3A \\sim C1A \\sim C2A \\sim C6A \\sim C7A \\sim C8A \\sim N1B
\\sim N2B \\sim N4B \\sim N3B \\sim C1B \\sim C2B \\sim C3B \\sim C7B \\sim C8B
\\sim C9B \\sim C11B \\sim C10B \\sim C6B \\sim C5B \\sim C4B: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 1.7A
Uanis(C6A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(N2A) \\sim Ueq, Uanis(C8A)
\\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(N3B) \\sim Ueq, Uanis(C10A) \\sim Ueq,
Uanis(C9A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(N3A)
\\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(N2B) \\sim Ueq, Uanis(C1A) \\sim Ueq,
Uanis(C10B) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C5B)
\\sim Ueq, Uanis(C4B) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C2B) \\sim Ueq,
Uanis(N4A) \\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(C7B)
\\sim Ueq, Uanis(N1B) \\sim Ueq, Uanis(C8B) \\sim Ueq, Uanis(N4B) \\sim Ueq,
Uanis(C9B) \\sim Ueq, Uanis(C11B) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.1
4. Rigid body (RIGU) restrains
 N4A, N3A, N1A, N2A, C11A, C10A, C9A, C5A, C4A, C3A, C1A, C2A, C6A, C7A, C8A,
 N1B, N2B, N4B, N3B, C1B, C2B, C3B, C7B, C8B, C9B, C11B, C10B, C6B, C5B, C4B
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
5. Others
 Fixed Sof: N4A(0.5) H4A(0.5) N3A(0.5) N1A(0.5) N2A(0.5) C11A(0.5) H11A(0.5)
 H11B(0.5) C10A(0.5) H10A(0.5) H10B(0.5) C9A(0.5) H9AA(0.5) H9AB(0.5) C5A(0.5)
 H5AA(0.5) H5AB(0.5) C4A(0.5) H4AA(0.5) H4AB(0.5) C3A(0.5) H3AA(0.5) H3AB(0.5)
 C1A(0.5) H1AA(0.5) H1AB(0.5) C2A(0.5) H2AA(0.5) H2AB(0.5) C6A(0.5) H6AA(0.5)
 H6AB(0.5) C7A(0.5) H7AA(0.5) H7AB(0.5) C8A(0.5) H8AA(0.5) H8AB(0.5) N1B(0.5)
 N2B(0.5) N4B(0.5) H4B(0.5) N3B(0.5) C1B(0.5) H1BA(0.5) H1BB(0.5) C2B(0.5)
 H2BA(0.5) H2BB(0.5) C3B(0.5) H3BA(0.5) H3BB(0.5) C7B(0.5) H7BA(0.5) H7BB(0.5)
 C8B(0.5) H8BA(0.5) H8BB(0.5) C9B(0.5) H9BA(0.5) H9BB(0.5) C11B(0.5) H11C(0.5)
 H11D(0.5) C10B(0.5) H10C(0.5) H10D(0.5) C6B(0.5) H6BA(0.5) H6BB(0.5) C5B(0.5)
 H5BA(0.5) H5BB(0.5) C4B(0.5) H4BA(0.5) H4BB(0.5)
6.a Ternary CH refined with riding coordinates:
 N4A(H4A), N4B(H4B)
6.b Secondary CH2 refined with riding coordinates:
 C11A(H11A,H11B), C10A(H10A,H10B), C9A(H9AA,H9AB), C5A(H5AA,H5AB), C4A(H4AA,
 H4AB), C3A(H3AA,H3AB), C1A(H1AA,H1AB), C2A(H2AA,H2AB), C6A(H6AA,H6AB),
 C7A(H7AA,H7AB), C8A(H8AA,H8AB), C1B(H1BA,H1BB), C2B(H2BA,H2BB), C3B(H3BA,H3BB),
  C7B(H7BA,H7BB), C8B(H8BA,H8BB), C9B(H9BA,H9BB), C11B(H11C,H11D), C10B(H10C,
 H10D), C6B(H6BA,H6BB), C5B(H5BA,H5BB), C4B(H4BA,H4BB)
;
_shelx_res_checksum              35605
_olex2_submission_special_instructions 'No special instructions were received'