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_7229726
_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
'0.5(C19.52 H43.19 N), 0.5(C16.77 H38.32 N), C32 H16 N8 O V, 0.23(C5 H9), 0.24(C3 H5)'
_chemical_formula_sum            'C52 H60 N9 O V'
_chemical_formula_weight         878.03
_chemical_melting_point          ?
_chemical_name_common            no
_chemical_name_systematic
'salt of vanadyl phthalocyanine with tetrapentylammonium cation'
_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
_audit_creation_date             2017-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-10-23 deposited with the CCDC.
2017-12-13 downloaded from the CCDC.
;
_cell_angle_alpha                67.700(3)
_cell_angle_beta                 71.527(3)
_cell_angle_gamma                78.147(2)
_cell_formula_units_Z            2
_cell_length_a                   11.8287(4)
_cell_length_b                   13.0419(4)
_cell_length_c                   16.6492(5)
_cell_measurement_reflns_used    17872
_cell_measurement_temperature    116.7(6)
_cell_measurement_theta_max      32.5610
_cell_measurement_theta_min      1.7570
_cell_volume                     2243.27(14)
_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_temperature      116.7(6)
_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    -22.00  62.00   1.00   60.00    --   20.14 -99.00 -30.00   84
  2  \w     -9.00  94.00   1.00   60.00    --   20.14  57.00 -30.00  103
  3  \w    -14.00  97.00   1.00   60.00    --   20.14  77.00  90.00  111
  4  \w    -56.00  45.00   1.00   60.00    --   20.14 -37.00-180.00  101
  5  \w    -56.00  39.00   1.00   60.00    --   20.14 -37.00  30.00   95
  6  \w      7.00  93.00   1.00   60.00    --   20.14  57.00-150.00   86
  7  \w     35.00  81.00   1.00   60.00    --   20.14 178.00-150.00   46
  8  \w    -94.00 -57.00   1.00   60.00    --  -20.45 150.00  19.99   37
  9  \w    -80.00 -49.00   1.00   60.00    --  -20.45 128.00 177.85   31
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0553
_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            44912
_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         1.783
_exptl_absorpt_coefficient_mu    0.271
_exptl_absorpt_correction_T_max  0.992
_exptl_absorpt_correction_T_min  0.967
_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    1.300
_exptl_crystal_description       block
_exptl_crystal_F_000             932
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane/0-dichlorobenzene'
_exptl_crystal_size_max          0.391
_exptl_crystal_size_mid          0.222
_exptl_crystal_size_min          0.097
_refine_diff_density_max         0.448
_refine_diff_density_min         -0.315
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.074(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1183
_refine_ls_number_reflns         26754
_refine_ls_number_restraints     699
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0586
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0492P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0927
_refine_ls_wR_factor_ref         0.1019
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                22238
_reflns_number_total             26754
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ce01918a2.cif
_cod_data_source_block           VoPcPentyl4N
_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        2243.27(13)
_cod_database_code               7229726
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.926(15)
 0.074(15)
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
{C316, C325}
{C313, C328}
{C203, C223}
4. Uiso/Uaniso restraints and constraints
C313 \\sim C314 \\sim C315 \\sim C325 \\sim C327: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(C301) \\sim Ueq, Uanis(C302) \\sim Ueq, Uanis(C303) \\sim Ueq,
Uanis(C304) \\sim Ueq, Uanis(C305) \\sim Ueq, Uanis(C306) \\sim Ueq,
Uanis(C307) \\sim Ueq, Uanis(C308) \\sim Ueq, Uanis(C309) \\sim Ueq,
Uanis(C310) \\sim Ueq, Uanis(C311) \\sim Ueq, Uanis(C312) \\sim Ueq,
Uanis(C313) \\sim Ueq, Uanis(C314) \\sim Ueq, Uanis(C315) \\sim Ueq,
Uanis(C316) \\sim Ueq, Uanis(C317) \\sim Ueq, Uanis(C318) \\sim Ueq,
Uanis(C319) \\sim Ueq, Uanis(C320) \\sim Ueq, Uanis(C322) \\sim Ueq,
Uanis(C323) \\sim Ueq, Uanis(C324) \\sim Ueq, Uanis(C325) \\sim Ueq,
Uanis(C327) \\sim Ueq, Uanis(C201) \\sim Ueq, Uanis(C202) \\sim Ueq,
Uanis(C203) \\sim Ueq, Uanis(C204) \\sim Ueq, Uanis(C205) \\sim Ueq,
Uanis(C206) \\sim Ueq, Uanis(C207) \\sim Ueq, Uanis(C208) \\sim Ueq,
Uanis(C209) \\sim Ueq, Uanis(C210) \\sim Ueq, Uanis(C211) \\sim Ueq,
Uanis(C212) \\sim Ueq, Uanis(C213) \\sim Ueq, Uanis(C214) \\sim Ueq,
Uanis(C215) \\sim Ueq, Uanis(C216) \\sim Ueq, Uanis(C217) \\sim Ueq,
Uanis(C218) \\sim Ueq, Uanis(C219) \\sim Ueq, Uanis(C220) \\sim Ueq,
Uanis(C501) \\sim Ueq, Uanis(C502) \\sim Ueq, Uanis(C503) \\sim Ueq,
Uanis(C504) \\sim Ueq, Uanis(C505) \\sim Ueq, Uanis(C506) \\sim Ueq,
Uanis(C507) \\sim Ueq, Uanis(C508) \\sim Ueq, Uanis(C509) \\sim Ueq,
Uanis(C510) \\sim Ueq, Uanis(C511) \\sim Ueq, Uanis(C512) \\sim Ueq,
Uanis(C513) \\sim Ueq, Uanis(C514) \\sim Ueq, Uanis(C515) \\sim Ueq,
Uanis(C516) \\sim Ueq, Uanis(C517) \\sim Ueq, Uanis(C518) \\sim Ueq,
Uanis(C519) \\sim Ueq, Uanis(C520) \\sim Ueq, Uanis(C521) \\sim Ueq,
Uanis(C522) \\sim Ueq, Uanis(C523) \\sim Ueq, Uanis(C524) \\sim Ueq,
Uanis(C525) \\sim Ueq, Uanis(C526) \\sim Ueq, Uanis(C527) \\sim Ueq,
Uanis(C528) \\sim Ueq, Uanis(C529) \\sim Ueq, Uanis(C530) \\sim Ueq,
Uanis(C531) \\sim Ueq, Uanis(C532) \\sim Ueq, Uanis(C101) \\sim Ueq,
Uanis(C102) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C104) \\sim Ueq,
Uanis(C105) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C107) \\sim Ueq,
Uanis(C108) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C110) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C113) \\sim Ueq,
Uanis(C114) \\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(C116) \\sim Ueq,
Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C119) \\sim Ueq,
Uanis(C120) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C123) \\sim Ueq, Uanis(C124) \\sim Ueq, Uanis(C125) \\sim Ueq,
Uanis(C126) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(C128) \\sim Ueq,
Uanis(C129) \\sim Ueq, Uanis(C130) \\sim Ueq, Uanis(C131) \\sim Ueq,
Uanis(C132) \\sim Ueq, Uanis(C222) \\sim Ueq, Uanis(C321) \\sim Ueq,
Uanis(C221) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C204) = Uanis(C221)
Uanis(C222) = Uanis(C205)
Uanis(C317) = Uanis(C321)
Uanis(C314) = Uanis(C325)
Uanis(C316) = Uanis(C325)
Uanis(C313) = Uanis(C328)
Uanis(C326) = Uanis(C315)
Uanis(C314) = Uanis(C327)
Uanis(C203) = Uanis(C223)
5. Others
 Fixed Sof: C203(0.83876) C204(0.83876) H20G(0.83876) H20H(0.83876)
 C205(0.83876) H20I(0.83876) H20J(0.83876) H20K(0.83876) C313(0.68078)
 C314(0.68078) H31J(0.68078) H31K(0.68078) C315(0.68078) H31L(0.68078)
 H31M(0.68078) H31N(0.68078) C316(0.54568) C317(0.54568) H31Q(0.54568)
 H31R(0.54568) C318(0.54568) H31S(0.54568) H31T(0.54568) C319(0.54568)
 H31U(0.54568) H31V(0.54568) C320(0.54568) H32A(0.54568) H32B(0.54568)
 H32C(0.54568) C321(0.45432) H32D(0.45432) H32E(0.45432) C322(0.45432)
 H32F(0.45432) H32G(0.45432) C323(0.45432) H32H(0.45432) H32I(0.45432)
 C324(0.45432) H32J(0.45432) H32K(0.45432) H32L(0.45432) C325(0.45432)
 C326(0.31922) H32M(0.31922) H32N(0.31922) H32O(0.31922) C327(0.31922)
 H32P(0.31922) H32Q(0.31922) C328(0.31922) C221(0.16124) H22D(0.16124)
 H22E(0.16124) C222(0.16124) H22F(0.16124) H22G(0.16124) H22H(0.16124)
 C223(0.16124)
6.a Secondary CH2 refined with riding coordinates:
 C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H), C206(H20L,
 H20M), C207(H20N,H20O), C208(H20P,H20Q), C209(H20R,H20S), C211(H21D,H21E),
 C212(H21F,H21G), C213(H21H,H21I), C214(H21J,H21K), C216(H21O,H21P), C217(H21Q,
 H21R), C218(H21S,H21T), C219(H21U,H21V), 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), C321(H32D,H32E), C322(H32F,H32G), C323(H32H,H32I), C327(H32P,H32Q),
 C221(H22D,H22E)
6.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), C517(H517), C518(H518),
 C519(H519), C520(H520), C521(H521), C522(H522), C523(H523), C524(H524),
 C525(H525), C526(H526), C527(H527), C528(H528), C529(H529), C530(H530),
 C531(H531), C532(H532)
6.c Idealised Me refined as rotating group:
 C205(H20I,H20J,H20K), C210(H21A,H21B,H21C), C215(H21L,H21M,H21N), C220(H22A,
 H22B,H22C), C305(H30I,H30J,H30K), C310(H31A,H31B,H31C), C315(H31L,H31M,H31N),
 C320(H32A,H32B,H32C), C324(H32J,H32K,H32L), C326(H32M,H32N,H32O), C222(H22F,
 H22G,H22H)
;
_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
;