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_7229722
_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         '2(C32 H16 N8 O Ti), 2(C20 H44 N)'
_chemical_formula_sum            'C104 H120 N18 O2 Ti2'
_chemical_formula_weight         1749.97
_chemical_melting_point          ?
_chemical_name_common            no
_chemical_name_systematic
'salt of titanyl phthalocyanine with tetrapentylammonium cations'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-02-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-10-23 deposited with the CCDC.
2017-12-13 downloaded from the CCDC.
;
_cell_angle_alpha                67.7290(19)
_cell_angle_beta                 71.634(2)
_cell_angle_gamma                78.1997(19)
_cell_formula_units_Z            1
_cell_length_a                   11.8378(3)
_cell_length_b                   13.0103(3)
_cell_length_c                   16.5916(3)
_cell_measurement_reflns_used    25883
_cell_measurement_temperature    116.95(10)
_cell_measurement_theta_max      32.6910
_cell_measurement_theta_min      1.8130
_cell_volume                     2233.70(9)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      116.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4566
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -14.00  97.00   1.00   40.00    --   20.14  77.00-150.00  111
  2  \w     -9.00  94.00   1.00   40.00    --   20.14  57.00  90.00  103
  3  \w     -1.00  95.00   1.00   40.00    --   20.14  37.00   0.00   96
  4  \w    -56.00  45.00   1.00   40.00    --   20.14 -37.00 -60.00  101
  5  \w    -25.00  62.00   1.00   40.00    --   20.14 -99.00  90.00   87
  6  \w     48.00 110.00   1.00   40.00    --   20.14 178.00-120.00   62
  7  \w    -52.00  50.00   1.00   40.00    --   20.14 -57.00-150.00  102
  8  \w    -80.00 -44.00   1.00   40.00    --  -20.45 128.00-131.95   36
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0140689000
_diffrn_orient_matrix_UB_12      0.0410148000
_diffrn_orient_matrix_UB_13      -0.0391256000
_diffrn_orient_matrix_UB_21      -0.0530665000
_diffrn_orient_matrix_UB_22      -0.0248115000
_diffrn_orient_matrix_UB_23      0.0099832000
_diffrn_orient_matrix_UB_31      -0.0317750000
_diffrn_orient_matrix_UB_32      0.0347251000
_diffrn_orient_matrix_UB_33      0.0257157000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0187
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            46042
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         1.821
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.242
_exptl_absorpt_correction_T_max  0.985
_exptl_absorpt_correction_T_min  0.974
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.301
_exptl_crystal_description       prism
_exptl_crystal_F_000             930
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Hexane/o-dichlorobenzene'
_exptl_crystal_size_max          0.368
_exptl_crystal_size_mid          0.248
_exptl_crystal_size_min          0.198
_refine_diff_density_max         0.433
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.391(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1163
_refine_ls_number_reflns         26916
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0450
_refine_ls_R_factor_gt           0.0379
_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^)+(0.0518P)^2^+0.2776P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0920
_refine_ls_wR_factor_ref         0.0963
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                24196
_reflns_number_total             26916
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ce01918a2.cif
_cod_data_source_block           TiOPcPentyl4N
_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_original_cell_volume        2233.71(9)
_cod_database_code               7229722
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C52 H60 N9 Ti1 O1'
_chemical_oxdiff_usercomment     TiOPc_TPA
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.609(14) 0.391(14)
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. Shared sites
{C425, C411}
4. Others
 Sof(C422)=Sof(H42D)=Sof(H42E)=Sof(C423)=Sof(H42F)=Sof(H42G)=Sof(C421)=
 Sof(H42H)=Sof(H42I)=Sof(C424)=Sof(H42J)=Sof(H42K)=Sof(H42L)=Sof(C425)=1-FVAR(1)
 Sof(C411)=Sof(C412)=Sof(H41F)=Sof(H41G)=Sof(C413)=Sof(H41H)=Sof(H41I)=
 Sof(C414)=Sof(H41J)=Sof(H41K)=Sof(C415)=Sof(H41L)=Sof(H41M)=Sof(H41N)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C401(H40A,H40B), C402(H40C,H40D), C403(H40E,H40F), C404(H40G,H40H), C406(H40L,
 H40M), C407(H40N,H40O), C408(H40P,H40Q), C409(H40R,H40S), C411(H41D,H41E),
 C412(H41F,H41G), C413(H41H,H41I), C414(H41J,H41K), C416(H41O,H41P), C417(H41Q,
 H41R), C418(H41S,H41T), C419(H41U,H41V), C301(H30A,H30B), C302(H30C,H30D),
 C303(H30E,H30F), C304(H30G,H30H), C306(H30L,H30M), C307(H30N,H30O), C308(H30P,
 H30Q), C309(H30R,H30S), C311(H31D,H31E), C312(H31F,H31G), C313(H31H,H31I),
 C314(H31J,H31K), C316(H31O,H31P), C317(H31Q,H31R), C318(H31S,H31T), C319(H31U,
 H31V), C422(H42D,H42E), C423(H42F,H42G), C421(H42H,H42I)
5.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)
5.c Idealised Me refined as rotating group:
 C405(H40I,H40J,H40K), C410(H41A,H41B,H41C), C415(H41L,H41M,H41N), C420(H42A,
 H42B,H42C), C305(H30I,H30J,H30K), C310(H31A,H31B,H31C), C315(H31L,H31M,H31N),
 C320(H32A,H32B,H32C), C424(H42J,H42K,H42L)
;
_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 1.083
_oxdiff_exptl_absorpt_empirical_full_min 0.920