To Be or Not to Be a (4,4) Net: Reactions of 4′-{4-(N,N-Diethylaminophenyl)}- and 4′-{4-(N,N-Diphenylaminophenyl)}-3,2′:6′,3″- and 4,2′:6′,4″-Terpyridines with Cobalt(II) Thiocyanate
Rocco, Dalila; Nikoletić, Anamarija; Prescimone, Alessandro; Constable, Edwin C.; Housecroft, Catherine E.; Crystals 12 (2022) 1136–; doi:10.3390/cryst12081136

data_1567588
_publ_section_title
;
 To Be or Not to Be a (4,4) Net: Reactions of
 4&#x2032;-{4-(N,N-Diethylaminophenyl)}- and
 4&#x2032;-{4-(N,N-Diphenylaminophenyl)}-3,2&#x2032;:6&#x2032;,3&#x2033;-
 and 4,2&#x2032;:6&#x2032;,4&#x2033;-Terpyridines with Cobalt(II)
 Thiocyanate
;
_journal_issue                   8
_journal_name_full               Crystals
_journal_page_first              1136
_journal_paper_doi               10.3390/cryst12081136
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety         'C52 H50 Co N10 S2, 0.8(C H Cl3)'
_chemical_formula_sum            'C52.8 H48.8 Cl2.4 Co N10 S2'
_chemical_formula_weight         1031.55
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-12
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.533(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.3183(3)
_cell_length_b                   12.5045(2)
_cell_length_c                   15.2418(4)
_cell_measurement_reflns_used    39015
_cell_measurement_temperature    150
_cell_measurement_theta_max      72.99
_cell_measurement_theta_min      3.34
_cell_volume                     2521.87(10)
_computing_cell_refinement       'X-Area Recipe 1.37.0.0 (STOE, 2021)'
_computing_data_collection       'X-Area Pilatus3_SV 1.31.175.0 (STOE, 2021)'
_computing_data_reduction
;
X-Area Integrate 2.5.1.0 (STOE, 2021)
X-Area LANA 2.6.2.0 (STOE, 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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'EIGER2 1M'
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
 1957 frames, detector distance = 40 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  Basel-Cu-Stoe
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0183
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            22004
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         72.668
_diffrn_reflns_theta_min         4.179
_diffrn_source                   'Axo Cu'
_diffrn_source_current           1.00
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    4.982
_exptl_absorpt_correction_T_max  0.0628
_exptl_absorpt_correction_T_min  0.0325
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens in: F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard,
Copenhagen (1970), 255 - 270. Afterwards scaling of reflection intensities was
performed within STOE LANA. J. Koziskova, F. Hahn, J. Richter, J. Kozisek, Acta
Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA.
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.358
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1071
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of CHCl3 and methanol  by solvent layering'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.193
_exptl_crystal_size_min          0.16
_exptl_crystal_size_rad          0.200
_refine_diff_density_max         1.936
_refine_diff_density_min         -1.761
_refine_diff_density_rms         0.113
_refine_ls_extinction_coef       0.0029(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.941
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         4963
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      0.947
_refine_ls_R_factor_all          0.1069
_refine_ls_R_factor_gt           0.1030
_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^)+(0.1000P)^2^+15.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2365
_refine_ls_wR_factor_ref         0.2400
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4678
_reflns_number_total             4963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            NIA003_150K.cif
_cod_data_source_block           nia003_150k
_cod_original_formula_sum        'C52.80 H48.80 Cl2.40 Co N10 S2'
_cod_database_code               1567588
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.503
_shelx_estimated_absorpt_t_min   0.407
_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
 N4-C24 \\sim N5-C24 \\sim N5-C22 \\sim N4-C26 \\sim N5-C19 \\sim N4-C19
 with sigma of 0.02
 C27-C26 \\sim C22-C23 \\sim C25-C24
 with sigma of 0.02
 C29-Cl1 \\sim C29-Cl3 \\sim C29-Cl2
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl3-Cl2
 with sigma of 0.04
 N4-C19 \\sim N4-C24 \\sim N4-C26
 with sigma of 0.02
 N5-C19 \\sim N5-C24 \\sim N5-C22
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C29) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Cl2) = Uanis(Cl1) = Uanis(Cl3)
4. Rigid body (RIGU) restrains
 C23, C27, C22, C26, C25, C24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, N5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C2, C3, C4, C5, N1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C1(0.55) H1(0.55) C3(0.55) H3(0.55) N5(0.5) H24A(0.5) H24B(0.5)
 H24C(0.5) H24D(0.5) C2(0.55) H2(0.55) C26(0.5) H26A(0.5) H26B(0.5) C27(0.5)
 H27A(0.5) H27B(0.5) H27C(0.5) Cl1(0.4) N4(0.5) C23(0.5) H23A(0.5) H23B(0.5)
 H23C(0.5) C22(0.5) H22A(0.5) H22B(0.5) C29(0.4) H29(0.4) Cl3(0.4) Cl2(0.4)
 C31(0.45) H31(0.45) C30(0.45) H30(0.45) C32(0.45) H32(0.45)
6.a Riding coordinates:
 C1(H1), C3(H3), C24(H24C,H24D), C2(H2), C31(H31), C30(H30), C32(H32)
6.b Ternary CH refined with riding coordinates:
 C29(H29)
6.c Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C26(H26A,H26B), C22(H22A,H22B)
6.d Aromatic/amide H refined with riding coordinates:
 C9(H9), C5(H5), C12(H12), C7(H7), C17(H17), C15(H15), C13(H13), C21(H21),
 C14(H14), C18(H18), C20(H20)
6.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              73590
_shelx_hkl_checksum              88647
_olex2_date_sample_data_collection 2022-05-09
_olex2_date_sample_submission    2022-04-12
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in perfluoroether oil'
_olex2_submission_original_sample_id NIA003_150K
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '40.0 mm'
_stoe_detector_pixelsize_x       '0.075 mm'
_stoe_detector_pixelsize_y       '0.075 mm'
_stoe_detector_size_x            '8.0 cm'
_stoe_detector_size_y            '7.7 cm'
_stoe_evaluation_integration_a   6.5
_stoe_evaluation_integration_b   -0.4
_stoe_evaluation_integration_ems 0.017
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 98.8
_stoe_evaluation_lana_dxs_max_order 1
_stoe_evaluation_lana_dys_max_order 1
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 145.4
_stoe_evaluation_lana_max_2theta_desired 145.4
_stoe_evaluation_lana_mean_redundancy 4.4
_stoe_evaluation_lana_number_refls_after_or 22009
_stoe_evaluation_lana_number_refls_outliers 8743
_stoe_evaluation_lana_number_refls_total 30752
_stoe_evaluation_lana_number_refls_unique 4966
_stoe_evaluation_lana_number_refls_written 22009
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group 2/m
_stoe_evaluation_lana_table
;
----------------------------------------------------------------------------
2Theta          13.2   28.8   44.4   60.0   75.6   91.2  106.8  122.4  138.0
----------------------------------------------------------------------------
<Resolution>    5.33   2.96   2.01   1.50   1.26   1.08   0.96   0.88   0.83
N(total)          76    506   1529   3524   6544   6903   4872   4467   2331
<Redundancy>     1.9    2.6    3.3    4.9    6.6    6.1    3.9    3.6    2.6
Complet. [%%]    94.3   99.3  100.0   99.8  100.0  100.0   99.9   99.9   92.5
<I/sigma>      610.7  299.5  152.0   71.7   45.1   29.6   22.3   16.8   12.1
R(int)         0.022  0.021  0.027  0.027  0.029  0.030  0.040  0.069  0.145
----------------------------------------------------------------------------
;
_stoe_measurement_identifier     NIA003_150K
_stoe_measurement_max_exposure_per_frame '8.0 s'
_stoe_measurement_mean_exposure_per_frame '7.6 s'
_stoe_measurement_min_exposure_per_frame '2.0 s'
_stoe_measurement_total_exposure_time '4.2 h'
_stoe_measurement_total_frame_number 1957
_stoe_measurement_total_run_number 35
_stoe_measurement_tube_power     '50.0 W'