Ligand solid-solution tuning of magnetic and mechanical properties of the van der Waals metal-organic magnet NiCl<sub>2</sub>(btd)<sub>1-<i>x</i></sub>(bod)<sub><i>x</i></sub>.
Myatt, Emily; Lata, Simrun; Pitcairn, Jem; Daisenberger, Dominik; Kronawitter, Silva M.; Hallweger, Sebastian A.; Kieslich, Gregor; Argent, Stephen P.; Tidey, Jeremiah P.; Cliffe, Matthew J.; Chemical communications (Cambridge, England) 60 (2024) 14427–14430; doi:10.1039/d4cc04214j

data_7133889
_publ_section_title
;
 Ligand solid-solution tuning of magnetic and mechanical properties of the
 van der Waals metal-organic magnet
 NiCl<sub>2</sub>(btd)<sub>1-<i>x</i></sub>(bod)<sub><i>x</i></sub>.
;
_journal_issue                   97
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              14427
_journal_page_last               14430
_journal_paper_doi               10.1039/d4cc04214j
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C12 H8 Cl2 N4 Ni O2'
_chemical_formula_sum            'C12 H8 Cl2 N4 Ni O2'
_chemical_formula_weight         369.83
_chemical_name_systematic        'nickel dichloride bis 2,1,3-benzoxadiazole'
_space_group_crystal_system      tetragonal
_space_group_IT_number           106
_space_group_name_Hall           'P 4c -2ab'
_space_group_name_H-M_alt        'P 42 b c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-08-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-16 deposited with the CCDC.	2024-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.1275(19)
_cell_length_b                   14.1275(19)
_cell_length_c                   6.8620(14)
_cell_measurement_reflns_used    1668
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      44.1260
_cell_measurement_theta_min      4.3870
_cell_volume                     1369.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 41.123a (release 20-01-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_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     11.00  36.00   1.00   60.00    --   43.12  82.00 -94.57   25
  2  \w     55.00  88.00   1.00   60.00    --   43.12  57.00 -90.00   33
  3  \w     17.00  43.00   1.00   60.00    --   43.12  71.00-140.87   26
  4  \w     55.00  81.00   1.00   60.00    --   43.12  71.00-140.87   26
  5  \w     20.00  45.00   1.00   60.00    --   43.12  55.00  23.73   25
  6  \w     53.00  79.00   1.00   60.00    --   43.12  55.00  23.73   26
  7  \w     20.00  57.00   1.00   60.00    --   43.12  44.00   1.00   37
  8  \w     62.00  95.00   1.00   60.00    --   43.12  44.00   1.00   33
  9  \w     87.00 112.00   1.00   60.00    --   43.12  42.00  92.80   25
 10  \w     16.00  42.00   1.00   60.00    --   43.12  69.00  57.36   26
 11  \w     44.00 111.00   1.00   60.00    --   43.12  69.00  57.36   67
 12  \w     25.00  89.00   1.00   60.00    --   43.12  45.00 124.86   64
 13  \w      4.00  67.00   1.00   60.00    --   43.12 -57.00-180.00   63
 14  \w     59.00 122.00   1.00   60.00    --   43.12-178.00 120.00   63
 15  \w     64.00  90.00   1.00   60.00    --   43.12 178.00-120.00   26
 16  \w    106.00 131.00   1.00   60.00    --   43.12 178.00-120.00   25
 17  \w     11.00  41.00   1.00   60.00    --   43.12  82.00  85.65   30
 18  \w     35.00 100.00   1.00   60.00    --   43.12-139.00 -58.00   65
 19  \w     16.00  41.00   1.00   60.00    --   43.12  78.00 -43.49   25
 20  \w     19.00  76.00   1.00   60.00    --   43.12 -99.00-180.00   57
 21  \w     14.00  39.00   1.00   60.00    --   43.12  77.00-137.30   25
 22  \w     12.00  37.00   1.00   60.00    --   43.12  79.00   2.78   25
 23  \w     21.00  50.00   1.00   60.00    --   43.12 -57.00 -30.00   29
 24  \w     30.00  97.00   1.00   60.00    --   43.12-131.00 116.00   67
 25  \w     13.00  47.00   1.00   60.00    --   43.12 -19.00 -30.00   34
 26  \w    -19.00  13.00   1.00   60.00    --   43.12 -38.00 -60.00   32
 27  \w     39.00  64.00   1.00   60.00    --   43.12 -38.00 -60.00   25
 28  \w    -27.00  29.00   1.00   60.00    --   43.12 -38.00  90.00   56
 29  \w    -18.00  25.00   1.00   60.00    --   43.12 -77.00-180.00   43
 30  \w    -17.00  38.00   1.00   60.00    --   43.12 -77.00 -60.00   55
 31  \w      6.00  31.00   1.00   60.00    --   43.12 -99.00 150.00   25
 32  \w     21.00  46.00   1.00   60.00    --   43.12  57.00 -90.00   25
 33  \w    -47.00 -35.00   1.00   60.00    --  -44.83 -65.00  29.90   12
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan S2'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1024063000
_diffrn_orient_matrix_UB_12      -0.0267882000
_diffrn_orient_matrix_UB_13      -0.0545555000
_diffrn_orient_matrix_UB_21      0.0369973000
_diffrn_orient_matrix_UB_22      0.0858969000
_diffrn_orient_matrix_UB_23      0.1151648000
_diffrn_orient_matrix_UB_31      0.0071161000
_diffrn_orient_matrix_UB_32      -0.0614744000
_diffrn_orient_matrix_UB_33      0.1848955000
_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  0.1107
_diffrn_reflns_av_unetI/netI     0.0799
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       5
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            2409
_diffrn_reflns_point_group_measured_fraction_full 0.859
_diffrn_reflns_point_group_measured_fraction_max 0.859
_diffrn_reflns_theta_full        39.895
_diffrn_reflns_theta_max         39.895
_diffrn_reflns_theta_min         4.426
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    5.731
_exptl_absorpt_correction_T_max  0.968
_exptl_absorpt_correction_T_min  0.837
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.63a (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            'light green'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.794
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ethanol'
_exptl_crystal_size_max          0.063
_exptl_crystal_size_mid          0.014
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.0(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     96
_refine_ls_number_reflns         352
_refine_ls_number_restraints     211
_refine_ls_restrained_S_all      0.810
_refine_ls_R_factor_all          0.0944
_refine_ls_R_factor_gt           0.0507
_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^)+(0.0552P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1000
_refine_ls_wR_factor_ref         0.1217
_reflns_Friedel_coverage         0.530
_reflns_Friedel_fraction_full    0.693
_reflns_Friedel_fraction_max     0.693
_reflns_number_gt                214
_reflns_number_total             352
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04214j2.cif
_cod_data_source_block           emmjca2
_cod_depositor_comments
'Adding full bibliography for 7133888--7133890.cif.'
_cod_original_cell_volume        1369.6(5)
_cod_database_code               7133889
_nottingham_internal_coll_name   EMMJCA
_nottingham_internal_coll_number 19395
_nottingham_internal_coll_client EM/MJC
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time 60.00
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczmjc1
_nottingham_internal_coll_date   24/03/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_process_date 26/01/2024
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 26/01/2024
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 30/07/2024
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 30/07/2024
_nottingham_internal_validation_user pczspa
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C12H10Cl2N4NiO2
_chemical_oxdiff_usercomment
'EMMJCA #19395 GVA-2045 EM/MJC fomblin oil on micromount'
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.714
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained planarity
 C10, C11, C6, C7, C8, C9
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim N3 \\sim N5 \\sim O4:
within 2.5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
Uanis(C7) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 C6, C7, C8, C9, C10, C11, N3, N5, O4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
5.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11)
;
_shelx_res_checksum              80516
_shelx_hkl_checksum              28745
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_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 1.784
_oxdiff_exptl_absorpt_empirical_full_min 0.775