Crystalline salts of metal phthalocyanine radical anions [M{Pc(•3-)}](•-) (M = Cu(II), Pb(II), V(IV)O, Sn(IV)Cl2) with cryptand(Na+) cations: structure, optical and magnetic properties
Konarev, Dmitri V.; Faraonov, Maxim A.; Kuz`min, Alexey V.; Khasanov, Salavat S.; Nakano, Yoshiaki; Norko, Semen I.; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N.; Batov, Mikhail S.; New J. Chem. 41 (2017) 6866–6874; doi:10.1039/C7NJ00530J

data_7056293
_publ_section_title
;
 Crystalline salts of metal phthalocyanine radical anions
 [M{Pc(&#x2022;3-)}](&#x2022;-) (M = Cu(II), Pb(II), V(IV)O, Sn(IV)Cl2)
 with cryptand(Na+) cations: structure, optical and magnetic properties
;
_journal_issue                   14
_journal_name_full               'New J. Chem.'
_journal_page_first              6866
_journal_page_last               6874
_journal_paper_doi               10.1039/C7NJ00530J
_journal_volume                  41
_journal_year                    2017
_chemical_compound_source        no
_chemical_formula_moiety
'C32 H16 N8 Pb, 1(C18 H36 N2 Na O6), C6 H4 Cl2'
_chemical_formula_sum            'C56 H56 Cl2 N10 Na O6 Pb'
_chemical_formula_weight         1266.18
_chemical_melting_point          ?
_chemical_name_common            no
_chemical_name_systematic
'lead phthalocyanine salt with cryptand[2,2,2] sodium cations, dichlorobenzene solvate'
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-01-20
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-01-21 deposited with the CCDC.
2017-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.2322(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.73638(18)
_cell_length_b                   30.5287(4)
_cell_length_c                   14.2894(2)
_cell_measurement_reflns_used    24383
_cell_measurement_temperature    150.00(14)
_cell_measurement_theta_max      28.9810
_cell_measurement_theta_min      1.6660
_cell_volume                     5246.00(13)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 20.9131
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     46.00  79.00   1.00   95.00    --  -14.46-178.00 -30.00   33
  2  \w     47.00  73.00   1.00   95.00    --  -14.46 178.00-120.00   26
  3  \w    -64.00  45.00   1.00   95.00    --   16.81 -57.00 -30.00  109
  4  \w    -10.00  64.00   1.00   95.00    --   16.81  57.00-120.00   74
  5  \w    -24.00   2.00   1.00   95.00    --   16.81 -99.00  30.00   26
  6  \w    -72.00  42.00   1.00   95.00    --   16.81 -77.00  90.00  114
  7  \w     11.00  45.00   1.00   95.00    --   16.81 -57.00-120.00   34
;
_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      0.0456812000
_diffrn_orient_matrix_UB_12      -0.0146562000
_diffrn_orient_matrix_UB_13      0.0157955000
_diffrn_orient_matrix_UB_21      -0.0362423000
_diffrn_orient_matrix_UB_22      -0.0178415000
_diffrn_orient_matrix_UB_23      -0.0196572000
_diffrn_orient_matrix_UB_31      0.0089487000
_diffrn_orient_matrix_UB_32      0.0025930000
_diffrn_orient_matrix_UB_33      -0.0461150000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0208
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            47083
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.650
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.389
_exptl_absorpt_correction_T_max  0.700
_exptl_absorpt_correction_T_min  0.572
_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    1.603
_exptl_crystal_description       block
_exptl_crystal_F_000             2548
_exptl_crystal_preparation       ', Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: o-dichlorobenzene'
_exptl_crystal_size_max          0.273
_exptl_crystal_size_mid          0.214
_exptl_crystal_size_min          0.145
_refine_diff_density_max         0.660
_refine_diff_density_min         -0.531
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1084
_refine_ls_number_reflns         10687
_refine_ls_number_restraints     1707
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0253
_refine_ls_R_factor_gt           0.0217
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0225P)^2^+7.4728P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0504
_refine_ls_wR_factor_ref         0.0522
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9774
_reflns_number_total             10687
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7nj00530j2.cif
_cod_data_source_block           PbPccrypt222Na
_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 
;
_cod_database_code               7056293
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C56 H56 N10 Pb1 O6 Na1 Cl2'
_reflns_odcompleteness_completeness 99.96
_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
2. Uiso/Uaniso restraints and constraints
C201 \\sim C202 \\sim C203 \\sim C204 \\sim C205 \\sim C206 \\sim C207 \\sim
C208 \\sim C209 \\sim C210 \\sim C211 \\sim C212 \\sim C213 \\sim C214 \\sim
C215 \\sim C216 \\sim C217 \\sim C218 \\sim C301 \\sim C302 \\sim C303 \\sim
C304 \\sim C305 \\sim C306 \\sim C307 \\sim C308 \\sim C309 \\sim C310 \\sim
C311 \\sim C312 \\sim C313 \\sim C314 \\sim C315 \\sim C316 \\sim C317 \\sim
C318 \\sim C401 \\sim C402 \\sim C403 \\sim C404 \\sim C405 \\sim C406 \\sim
C407 \\sim C408 \\sim C409 \\sim C410 \\sim C411 \\sim C412 \\sim C413 \\sim
C414 \\sim C415 \\sim C416 \\sim C417 \\sim C418: within 1.7A with sigma of
0.001 and sigma for terminal atoms of 0.002
O201 \\sim O202 \\sim O203 \\sim O204 \\sim O205 \\sim O206 \\sim O301 \\sim
O302 \\sim O303 \\sim O304 \\sim O305 \\sim O306 \\sim O401 \\sim O402 \\sim
O403 \\sim O404 \\sim O405 \\sim O406: within 1.7A with sigma of 0.001 and
sigma for terminal atoms of 0.002
N201 \\sim N202 \\sim N301 \\sim N302 \\sim N401 \\sim N402: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
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(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(C401) \\sim Ueq, Uanis(C402) \\sim Ueq, Uanis(C403) \\sim Ueq,
Uanis(C404) \\sim Ueq, Uanis(C405) \\sim Ueq, Uanis(C406) \\sim Ueq,
Uanis(C407) \\sim Ueq, Uanis(C408) \\sim Ueq, Uanis(C409) \\sim Ueq,
Uanis(C410) \\sim Ueq, Uanis(C411) \\sim Ueq, Uanis(C412) \\sim Ueq,
Uanis(C413) \\sim Ueq, Uanis(C414) \\sim Ueq, Uanis(C415) \\sim Ueq,
Uanis(C416) \\sim Ueq, Uanis(C417) \\sim Ueq, Uanis(C418) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.02
Uanis(O201) \\sim Ueq, Uanis(O202) \\sim Ueq, Uanis(O203) \\sim Ueq,
Uanis(O204) \\sim Ueq, Uanis(O205) \\sim Ueq, Uanis(O206) \\sim Ueq,
Uanis(O301) \\sim Ueq, Uanis(O302) \\sim Ueq, Uanis(O303) \\sim Ueq,
Uanis(O304) \\sim Ueq, Uanis(O305) \\sim Ueq, Uanis(O306) \\sim Ueq,
Uanis(O401) \\sim Ueq, Uanis(O402) \\sim Ueq, Uanis(O403) \\sim Ueq,
Uanis(O404) \\sim Ueq, Uanis(O405) \\sim Ueq, Uanis(O406) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.001
Uanis(N201) \\sim Ueq, Uanis(N202) \\sim Ueq, Uanis(N301) \\sim Ueq,
Uanis(N302) \\sim Ueq, Uanis(N401) \\sim Ueq, Uanis(N402) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.02
Uanis(Na2) = Uanis(Na3) = Uanis(Na4)
3. Same fragment restrains
{Na2, N201, N202, C201, C202, O201, C203, C204, O202, C205, C206, C207, C208,
O203, C209, C210, O204, C211, C212, C213, C214, O205, C215, C216, O206, C217,
C218} sigma for 1-2: 0.02, 1-3: 0.02
as
{Na3, N301, N302, C301, C302, O301, C303, C304, O302, C305, C306, C307, C308,
O303, C309, C310, O304, C311, C312, C313, C314, O305, C315, C316, O306, C317,
C318}
{Na2, N201, N202, C201, C202, O201, C203, C204, O202, C205, C206, C207, C208,
O203, C209, C210, O204, C211, C212, C213, C214, O205, C215, C216, O206, C217,
C218} sigma for 1-2: 0.02, 1-3: 0.02
as
{Na4, N401, N402, C401, C402, O401, C403, C404, O402, C405, C406, C407, C408,
O403, C409, C410, O404, C411, C412, C413, C414, O405, C415, C416, O406, C417,
C418}
4. Others
 Fixed Sof: Na2(0.54109) N201(0.54109) N202(0.54109) C201(0.54109)
 H20A(0.54109) H20B(0.54109) C202(0.54109) H20C(0.54109) H20D(0.54109)
 O201(0.54109) C203(0.54109) H20E(0.54109) H20F(0.54109) C204(0.54109)
 H20G(0.54109) H20H(0.54109) O202(0.54109) C205(0.54109) H20I(0.54109)
 H20J(0.54109) C206(0.54109) H20K(0.54109) H20L(0.54109) C207(0.54109)
 H20M(0.54109) H20N(0.54109) C208(0.54109) H20O(0.54109) H20P(0.54109)
 O203(0.54109) C209(0.54109) H20Q(0.54109) H20R(0.54109) C210(0.54109)
 H21A(0.54109) H21B(0.54109) O204(0.54109) C211(0.54109) H21C(0.54109)
 H21D(0.54109) C212(0.54109) H21E(0.54109) H21F(0.54109) C213(0.54109)
 H21G(0.54109) H21H(0.54109) C214(0.54109) H21I(0.54109) H21J(0.54109)
 O205(0.54109) C215(0.54109) H21K(0.54109) H21L(0.54109) C216(0.54109)
 H21M(0.54109) H21N(0.54109) O206(0.54109) C217(0.54109) H21O(0.54109)
 H21P(0.54109) C218(0.54109) H21Q(0.54109) H21R(0.54109) Na3(0.19621)
 N301(0.19621) N302(0.19621) C301(0.19621) H30A(0.19621) H30B(0.19621)
 C302(0.19621) H30C(0.19621) H30D(0.19621) O301(0.19621) C303(0.19621)
 H30E(0.19621) H30F(0.19621) C304(0.19621) H30G(0.19621) H30H(0.19621)
 O302(0.19621) C305(0.19621) H30I(0.19621) H30J(0.19621) C306(0.19621)
 H30K(0.19621) H30L(0.19621) C307(0.19621) H30M(0.19621) H30N(0.19621)
 C308(0.19621) H30O(0.19621) H30P(0.19621) O303(0.19621) C309(0.19621)
 H30Q(0.19621) H30R(0.19621) C310(0.19621) H31A(0.19621) H31B(0.19621)
 O304(0.19621) C311(0.19621) H31C(0.19621) H31D(0.19621) C312(0.19621)
 H31E(0.19621) H31F(0.19621) C313(0.19621) H31G(0.19621) H31H(0.19621)
 C314(0.19621) H31I(0.19621) H31J(0.19621) O305(0.19621) C315(0.19621)
 H31K(0.19621) H31L(0.19621) C316(0.19621) H31M(0.19621) H31N(0.19621)
 O306(0.19621) C317(0.19621) H31O(0.19621) H31P(0.19621) C318(0.19621)
 H31Q(0.19621) H31R(0.19621) Na4(0.26278) N401(0.26278) N402(0.26278)
 C401(0.26278) H40A(0.26278) H40B(0.26278) C402(0.26278) H40C(0.26278)
 H40D(0.26278) O401(0.26278) C403(0.26278) H40E(0.26278) H40F(0.26278)
 C404(0.26278) H40G(0.26278) H40H(0.26278) O402(0.26278) C405(0.26278)
 H40I(0.26278) H40J(0.26278) C406(0.26278) H40K(0.26278) H40L(0.26278)
 C407(0.26278) H40M(0.26278) H40N(0.26278) C408(0.26278) H40O(0.26278)
 H40P(0.26278) O403(0.26278) C409(0.26278) H40Q(0.26278) H40R(0.26278)
 C410(0.26278) H41A(0.26278) H41B(0.26278) O404(0.26278) C411(0.26278)
 H41C(0.26278) H41D(0.26278) C412(0.26278) H41E(0.26278) H41F(0.26278)
 C413(0.26278) H41G(0.26278) H41H(0.26278) C414(0.26278) H41I(0.26278)
 H41J(0.26278) O405(0.26278) C415(0.26278) H41K(0.26278) H41L(0.26278)
 C416(0.26278) H41M(0.26278) H41N(0.26278) O406(0.26278) C417(0.26278)
 H41O(0.26278) H41P(0.26278) C418(0.26278) H41Q(0.26278) H41R(0.26278)
5.a Free rotating group:
 Na2(N201,N202,C201,C202,O201,C203,C204,O202,C205,C206,C207,C208,O203,C209,
 C210,O204,C211,C212,C213,C214,O205,C215,C216,O206,C217,C218)
5.b Secondary CH2 refined with riding coordinates:
 C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H), C205(H20I,
 H20J), C206(H20K,H20L), C207(H20M,H20N), C208(H20O,H20P), C209(H20Q,H20R),
 C210(H21A,H21B), C211(H21C,H21D), C212(H21E,H21F), C213(H21G,H21H), C214(H21I,
 H21J), C215(H21K,H21L), C216(H21M,H21N), C217(H21O,H21P), C218(H21Q,H21R),
 C301(H30A,H30B), C302(H30C,H30D), C303(H30E,H30F), C304(H30G,H30H), C305(H30I,
 H30J), C306(H30K,H30L), C307(H30M,H30N), C308(H30O,H30P), C309(H30Q,H30R),
 C310(H31A,H31B), C311(H31C,H31D), C312(H31E,H31F), C313(H31G,H31H), C314(H31I,
 H31J), C315(H31K,H31L), C316(H31M,H31N), C317(H31O,H31P), C318(H31Q,H31R),
 C401(H40A,H40B), C402(H40C,H40D), C403(H40E,H40F), C404(H40G,H40H), C405(H40I,
 H40J), C406(H40K,H40L), C407(H40M,H40N), C408(H40O,H40P), C409(H40Q,H40R),
 C410(H41A,H41B), C411(H41C,H41D), C412(H41E,H41F), C413(H41G,H41H), C414(H41I,
 H41J), C415(H41K,H41L), C416(H41M,H41N), C417(H41O,H41P), C418(H41Q,H41R)
5.c 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), C3(H3), C4(H4), C5(H5), C6(H6)
;
_olex2_submission_original_sample_id PbPc-crypt222
_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 1.052
_oxdiff_exptl_absorpt_empirical_full_min 0.957