Salts with titanyl and vanadyl phthalocyanine radical anions. Molecular design and effect of cations on the structure and magnetic and optical properties
Konarev, Dmitri V.; Kuzmin, Alexey V.; Khasanov, Salavat S.; Batov, Mikhail S.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N.; CrystEngComm 20 (2018) 385–; doi:10.1039/C7CE01918A

data_7229730
_publ_section_title
;
 Salts with titanyl and vanadyl phthalocyanine radical anions. Molecular
 design and effect of cations on the structure and magnetic and optical
 properties
;
_journal_issue                   4
_journal_name_full               CrystEngComm
_journal_page_first              385
_journal_paper_doi               10.1039/C7CE01918A
_journal_volume                  20
_journal_year                    2018
_chemical_compound_source        no
_chemical_formula_moiety         'C24 H52 N, C32 H16 N8 O Ti, C6 H4 Cl2'
_chemical_formula_sum            'C62 H72 Cl2 N9 O Ti'
_chemical_formula_weight         1078.08
_chemical_melting_point          ?
_chemical_name_common            no
_chemical_name_systematic
'salt of titanyl phthalocyanine with tetrahexylammonium cations, o-dichlorobenzene solate'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_symmetry_space_group_name_Hall  'P -2yc'
_symmetry_space_group_name_H-M   'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-10-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-11-04 deposited with the CCDC.
2017-12-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.059(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.2181(5)
_cell_length_b                   11.4301(2)
_cell_length_c                   21.4414(4)
_cell_measurement_reflns_used    39581
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.3180
_cell_measurement_theta_min      1.8320
_cell_volume                     5658.44(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_type            'Bruker APEX-II CCD'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.946
_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     10.89 200.89   1.00   80.00    --   28.00  73.42 -25.61  190
  2  \w     10.89 200.89   1.00   80.00    --   28.00  73.42  94.39  190
  3  \w     10.89 200.89   1.00   80.00    --   28.00  73.42 154.39  190
  4  \w     10.89 199.89   1.00   80.00    --   28.00  73.42-145.61  189
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0503
_diffrn_reflns_av_unetI/netI     0.0588
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            71322
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.276
_diffrn_reflns_theta_min         1.782
_exptl_absorpt_coefficient_mu    0.296
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97093
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             2284
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-hexane/o-dichlorobenzene'
_exptl_crystal_size_max          0.305
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.186
_refine_diff_density_max         0.549
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.065
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.43(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1360
_refine_ls_number_reflns         27307
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0835
_refine_ls_R_factor_gt           0.0544
_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^)+(0.0587P)^2^+1.9883P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1158
_refine_ls_wR_factor_ref         0.1282
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.946
_reflns_number_gt                20292
_reflns_number_total             27307
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ce01918a2.cif
_cod_data_source_block           TiOPcHexyl4NC6H4Cl2
_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_melting_point' value 'not measured' was changed to '?' -
the value is undefined or not given.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

 Adding full bibliography for 7229722--7229730.cif.
;
_cod_database_code               7229730
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.57(2)
 0.43(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Secondary CH2 refined with riding coordinates:
 C03V(H03A,H03B), C301(H30A,H30B), C302(H30C,H30D), C303(H30E,H30F), C304(H30G,
 H30H), C305(H30I,H30J), C307(H30N,H30O), C308(H30P,H30Q), C309(H30R,H30S),
 C310(H31A,H31B), C312(H31F,H31G), C313(H31H,H31I), C314(H31J,H31K), C315(H31L,
 H31M), C316(H31N,H31O), C318(H31S,H31T), C319(H31U,H31V), C320(H32A,H32B),
 C321(H32C,H32D), C322(H32E,H32F), C401(H40A,H40B), C402(H40C,H40D), C403(H40E,
 H40F), C404(H40G,H40H), C405(H40I,H40J), C407(H40N,H40O), C408(H40P,H40Q),
 C409(H40R,H40S), C410(H41A,H41B), C411(H41C,H41D), C413(H41H,H41I), C414(H41J,
 H41K), C415(H41L,H41M), C416(H41N,H41O), C417(H41P,H41Q), C419(H41U,H41V),
 C420(H42A,H42B), C421(H42C,H42D), C422(H42E,H42F), C423(H42G,H42H)
3.b Aromatic/amide H refined with riding coordinates:
 C117(H117), C118(H118), C119(H119), C120(H120), C121(H121), C122(H122),
 C123(H123), C124(H124), C125(H125), C126(H126), C127(H127), C128(H128),
 C129(H129), C130(H130), C131(H131), C132(H132), C217(H217), C218(H218),
 C219(H219), C220(H220), C221(H221), C222(H222), C223(H223), C224(H224),
 C225(H225), C226(H226), C227(H227), C228(H228), C229(H229), C230(H230),
 C231(H231), C232(H232), C63(H63), C64(H64), C65(H65), C66(H66), C53(H53),
 C54(H54), C55(H55), C56(H56)
3.c Idealised Me refined as rotating group:
 C306(H30K,H30L,H30M), C311(H31C,H31D,H31E), C317(H31P,H31Q,H31R), C323(H32G,
 H32H,H32I), C406(H40K,H40L,H40M), C412(H41E,H41F,H41G), C418(H41R,H41S,H41T),
 C424(H42I,H42J,H42K)
;
_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
;