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_7229725
_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         'C32 H16 N8 O Ti, 1(C7 H15 N2)'
_chemical_formula_sum            'C39 H31 N10 O Ti'
_chemical_formula_weight         703.64
_chemical_melting_point          ?
_chemical_name_common            no
_chemical_name_systematic
'salt of titanyl phthalocyanine with N-methyldiazabicyclooctanium cation'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-05-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2017-10-23 deposited with the CCDC.
2017-12-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.444(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.5955(11)
_cell_length_b                   17.1171(10)
_cell_length_c                   19.1812(13)
_cell_measurement_reflns_used    4116
_cell_measurement_temperature    150.00(14)
_cell_measurement_theta_max      28.2600
_cell_measurement_theta_min      2.1040
_cell_volume                     6346.5(7)
_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_environment      N~2~
_diffrn_ambient_temperature      150.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.863
_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    -91.00  16.00   0.50  150.00    --  -14.62 -77.00  90.00  214
  2  \w    -66.00  41.00   0.50  150.00    --   16.65 -37.00 150.00  214
  3  \w    -71.00 -23.00   0.50  150.00    --  -14.62 -77.00  30.00   96
;
_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      -0.0088603000
_diffrn_orient_matrix_UB_12      -0.0282053000
_diffrn_orient_matrix_UB_13      0.0240793000
_diffrn_orient_matrix_UB_21      -0.0151518000
_diffrn_orient_matrix_UB_22      0.0296675000
_diffrn_orient_matrix_UB_23      0.0183007000
_diffrn_orient_matrix_UB_31      -0.0321752000
_diffrn_orient_matrix_UB_32      -0.0062824000
_diffrn_orient_matrix_UB_33      -0.0222471000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0507
_diffrn_reflns_av_unetI/netI     0.0994
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.863
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            19120
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.863
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.111
_diffrn_reflns_theta_min         1.589
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.322
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.952
_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    1.473
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2920
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane/o-dichlorobenzene'
_exptl_crystal_size_max          0.262
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.069
_refine_diff_density_max         0.417
_refine_diff_density_min         -0.344
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     585
_refine_ls_number_reflns         7370
_refine_ls_number_restraints     346
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.1149
_refine_ls_R_factor_gt           0.0613
_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^)+(0.0584P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1229
_refine_ls_wR_factor_ref         0.1467
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4546
_reflns_number_total             7370
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ce01918a2.cif
_cod_data_source_block           TiOPcMDABCO
_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               7229725
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C39 H31 N10 Ti1 O1'
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. 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
2. Uiso/Uaniso restraints and constraints
C201 \\sim C202 \\sim C203 \\sim C204 \\sim C205 \\sim C206 \\sim C207 \\sim
C301 \\sim C302 \\sim C303 \\sim C304 \\sim C305 \\sim C306 \\sim C307 \\sim
C401 \\sim C402 \\sim C403 \\sim C404 \\sim C405 \\sim C406 \\sim C407: within
1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
N201 \\sim N302 \\sim N402 \\sim N202 \\sim N301 \\sim N401: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(N301) = Uanis(N302)
Uanis(C303) = Uanis(C207)
Uanis(C203) = Uanis(C307)
Uanis(C206) = Uanis(C306)
Uanis(C407) = Uanis(C307)
Uanis(N202) = Uanis(N201)
Uanis(N401) = Uanis(N402)
3. Same fragment restrains
{N201, N202, C201, C202, C203, C204, C205, C206, C207} sigma for 1-2: 0.001,
1-3: 0.001
as
{N301, N302, C301, C302, C303, C304, C305, C306, C307}
{N201, N202, C201, C202, C203, C204, C205, C206, C207} sigma for 1-2: 0.001,
1-3: 0.001
as
{N401, N402, C401, C402, C403, C404, C405, C406, C407}
4. Others
 1*[Sof(N201)+Sof(N202)+Sof(C201)+Sof(H20A)+Sof(H20B)+Sof(C202)+Sof(H20C)+
 Sof(H20D)+Sof(C203)+Sof(H20E)+Sof(H20F)+Sof(C204)+Sof(H20G)+Sof(H20H)+
 Sof(C205)+Sof(H20I)+Sof(H20J)+Sof(C206)+Sof(H20K)+Sof(H20L)+Sof(C207)+
 Sof(H20M)+Sof(H20N)+Sof(H20O)]+1*[Sof(N301)+Sof(N302)+Sof(C301)+Sof(H30A)+
 Sof(H30B)+Sof(C302)+Sof(H30C)+Sof(H30D)+Sof(C303)+Sof(H30E)+Sof(H30F)+
 Sof(C304)+Sof(H30G)+Sof(H30H)+Sof(C305)+Sof(H30I)+Sof(H30J)+Sof(C306)+
 Sof(H30K)+Sof(H30L)+Sof(C307)+Sof(H30M)+Sof(H30N)+Sof(H30O)]+1*[Sof(N401)+
 Sof(N402)+Sof(C401)+Sof(H40A)+Sof(H40B)+Sof(C402)+Sof(H40C)+Sof(H40D)+
 Sof(C403)+Sof(H40E)+Sof(H40F)+Sof(C404)+Sof(H40G)+Sof(H40H)+Sof(C405)+
 Sof(H40I)+Sof(H40J)+Sof(C406)+Sof(H40K)+Sof(H40L)+Sof(C407)+Sof(H40M)+
 Sof(H40N)+Sof(H40O)]=1 with esd of 0.0001
 Sof(N201)=Sof(N202)=Sof(C201)=Sof(H20A)=Sof(H20B)=Sof(C202)=Sof(H20C)=
 Sof(H20D)=Sof(C203)=Sof(H20E)=Sof(H20F)=Sof(C204)=Sof(H20G)=Sof(H20H)=
 Sof(C205)=Sof(H20I)=Sof(H20J)=Sof(C206)=Sof(H20K)=Sof(H20L)=Sof(C207)=
 Sof(H20M)=Sof(H20N)=Sof(H20O)=FVAR(1)
 Sof(N301)=Sof(N302)=Sof(C301)=Sof(H30A)=Sof(H30B)=Sof(C302)=Sof(H30C)=
 Sof(H30D)=Sof(C303)=Sof(H30E)=Sof(H30F)=Sof(C304)=Sof(H30G)=Sof(H30H)=
 Sof(C305)=Sof(H30I)=Sof(H30J)=Sof(C306)=Sof(H30K)=Sof(H30L)=Sof(C307)=
 Sof(H30M)=Sof(H30N)=Sof(H30O)=FVAR(2)
 Sof(N401)=Sof(N402)=Sof(C401)=Sof(H40A)=Sof(H40B)=Sof(C402)=Sof(H40C)=
 Sof(H40D)=Sof(C403)=Sof(H40E)=Sof(H40F)=Sof(C404)=Sof(H40G)=Sof(H40H)=
 Sof(C405)=Sof(H40I)=Sof(H40J)=Sof(C406)=Sof(H40K)=Sof(H40L)=Sof(C407)=
 Sof(H40M)=Sof(H40N)=Sof(H40O)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H), C205(H20I,
 H20J), C206(H20K,H20L), C301(H30A,H30B), C302(H30C,H30D), C303(H30E,H30F),
 C304(H30G,H30H), C305(H30I,H30J), C306(H30K,H30L), C401(H40A,H40B), C402(H40C,
 H40D), C403(H40E,H40F), C404(H40G,H40H), C405(H40I,H40J), C406(H40K,H40L)
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)
5.c Idealised Me refined with everything fixed:
 C407(H40M,H40N,H40O)
5.d Idealised Me refined as rotating group:
 C207(H20M,H20N,H20O), C307(H30M,H30N,H30O)
;
_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 1.197
_oxdiff_exptl_absorpt_empirical_full_min 0.927