Flavanthrone ‒ a new ligand with accessible radical anion and dianion states: preparation of zwitterionic {(Cp2V)2(flavanthrone)} and {(Cp2V)2(chloranil)} complexes
Konarev, Dmitri V.; Andronov, Mikhail G.; Batov, Mikhail S.; Kuzmin, Alexey V.; Khasanov, Salavat S.; Shestakov, Alexander F.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N.; New Journal of Chemistry 44 (2020) 10849–10858; doi:10.1039/D0NJ01208D

data_7059655
_publ_section_title
;
 Flavanthrone -- a new ligand with accessible radical anion and dianion
 states: preparation of zwitterionic {(Cp2V)2(flavanthrone)} and
 {(Cp2V)2(chloranil)} complexes
;
_journal_issue                   26
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              10849
_journal_page_last               10858
_journal_paper_doi               10.1039/D0NJ01208D
_journal_volume                  44
_journal_year                    2020
_chemical_formula_moiety
'2(C16 H36 P), (C28 H12 N2 O2), 0.5(C6 H4 Cl2)'
_chemical_formula_sum            'C63 H86 Cl N2 O2 P2'
_chemical_formula_weight         1000.72
_chemical_melting_point          ?
_chemical_name_common            no
_chemical_name_systematic
'dianion salt of flavanthrone with tetrabutylphosphonium cations, o-dichlobenzene solvate'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-01-15
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2020-02-22 deposited with the CCDC.	2020-05-18 downloaded from the CCDC.
;
_cell_angle_alpha                89.892(7)
_cell_angle_beta                 84.445(6)
_cell_angle_gamma                72.298(7)
_cell_formula_units_Z            2
_cell_length_a                   10.4142(6)
_cell_length_b                   15.4474(15)
_cell_length_c                   18.1276(16)
_cell_measurement_reflns_used    3535
_cell_measurement_temperature    109(2)
_cell_measurement_theta_max      23.4160
_cell_measurement_theta_min      3.7540
_cell_volume                     2763.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      109(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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     50.00  85.00   1.00  110.00    --   11.89 178.00  30.00   35
  2  \w    -61.00  -8.00   1.00  110.00    --  -12.20 -37.00  90.00   53
  3  \w    -14.00  12.00   1.00  110.00    --  -12.20 -99.00   0.00   26
  4  \w    -41.00  65.00   1.00  110.00    --  -12.20  77.00 -90.00  106
  5  \w    -33.00  22.00   1.00  110.00    --  -12.20  37.00-120.00   55
  6  \w    -85.00   6.00   1.00  110.00    --  -12.20 -77.00  30.00   91
;
_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      -0.0045139000
_diffrn_orient_matrix_UB_12      0.0431620000
_diffrn_orient_matrix_UB_13      0.0153291000
_diffrn_orient_matrix_UB_21      -0.0126643000
_diffrn_orient_matrix_UB_22      0.0196506000
_diffrn_orient_matrix_UB_23      -0.0349950000
_diffrn_orient_matrix_UB_31      -0.0705684000
_diffrn_orient_matrix_UB_32      0.0087025000
_diffrn_orient_matrix_UB_33      0.0093473000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0603
_diffrn_reflns_av_unetI/netI     0.1040
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            22488
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         3.450
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.172
_exptl_absorpt_correction_T_max  0.998
_exptl_absorpt_correction_T_min  0.994
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.202
_exptl_crystal_description       block
_exptl_crystal_F_000             1082
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: o-dichlorobenzene/n-hexane'
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.126
_exptl_crystal_size_min          0.077
_refine_diff_density_max         0.343
_refine_diff_density_min         -0.503
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     815
_refine_ls_number_reflns         9658
_refine_ls_number_restraints     634
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.1390
_refine_ls_R_factor_gt           0.0738
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0783P)^2^+0.6399P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1621
_refine_ls_wR_factor_ref         0.2036
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5462
_reflns_number_total             9658
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj01208d2.cif
_cod_data_source_block           Flavanthrone2Bu4P05DCB
_cod_depositor_comments
;
The following automatic conversions were performed:

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

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 7059654--7059658.cif.

 Adding full bibliography for 7059654--7059658.cif.
;
_cod_database_code               7059655
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C126  H172  Cl2  N4  O4  P4  '
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.933
_reflns_odcompleteness_completeness 99.15
_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. Restrained distances
 C706-Cl72 \\sim C701-Cl71
 with sigma of 0.02
 C706-C701 \\sim C701-C702 \\sim C702-C703 \\sim C703-C704 \\sim C704-C705
\\sim C705-C706
 with sigma of 0.02
 C706-C702 \\sim C706-C704 \\sim C703-C701 \\sim C703-C705 \\sim C701-C705
\\sim C702-C704
 with sigma of 0.04
 Cl72-C705 \\sim Cl72-C701 \\sim Cl71-C706 \\sim Cl71-C702
 with sigma of 0.04
 P401-C405 \\sim P501-C509
 with sigma of 0.02
 P401-C409 \\sim P501-C505
 with sigma of 0.02
 P401-C401 \\sim P501-C501
 with sigma of 0.02
 P401-C413 \\sim P501-C513
 with sigma of 0.02
 C416-C415 \\sim C516-C515
 with sigma of 0.02
 C407-C408 \\sim C511-C512
 with sigma of 0.02
 C407-C406 \\sim C511-C510
 with sigma of 0.02
 C405-C406 \\sim C509-C510
 with sigma of 0.02
 C404-C403 \\sim C504-C503
 with sigma of 0.02
 C410-C409 \\sim C506-C505
 with sigma of 0.02
 C410-C411 \\sim C506-C507
 with sigma of 0.02
 C415-C414 \\sim C515-C514
 with sigma of 0.02
 C402-C401 \\sim C502-C501
 with sigma of 0.02
 C402-C403 \\sim C502-C503
 with sigma of 0.02
 C412-C411 \\sim C508-C507
 with sigma of 0.02
 C414-C413 \\sim C514-C513
 with sigma of 0.02
 P401-C406 \\sim P501-C510
 with sigma of 0.04
 P401-C410 \\sim P501-C506
 with sigma of 0.04
 P401-C402 \\sim P501-C502
 with sigma of 0.04
 P401-C414 \\sim P501-C514
 with sigma of 0.04
 C416-C414 \\sim C516-C514
 with sigma of 0.04
 C407-C405 \\sim C511-C509
 with sigma of 0.04
 C408-C406 \\sim C512-C510
 with sigma of 0.04
 C405-C409 \\sim C509-C505
 with sigma of 0.04
 C405-C401 \\sim C509-C501
 with sigma of 0.04
 C405-C413 \\sim C509-C513
 with sigma of 0.04
 C404-C402 \\sim C504-C502
 with sigma of 0.04
 C410-C412 \\sim C506-C508
 with sigma of 0.04
 C409-C401 \\sim C505-C501
 with sigma of 0.04
 C409-C411 \\sim C505-C507
 with sigma of 0.04
 C409-C413 \\sim C505-C513
 with sigma of 0.04
 C415-C413 \\sim C515-C513
 with sigma of 0.04
 C401-C403 \\sim C501-C503
 with sigma of 0.04
 C401-C413 \\sim C501-C513
 with sigma of 0.04
3. Restrained planarity
 Cl71, Cl72, C701, C702, C703, C704, C705, C706
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Cl71 \\sim Cl72 \\sim C701 \\sim C702 \\sim C703 \\sim C704 \\sim C705 \\sim
C706: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
2A
C405 \\sim C406 \\sim C407 \\sim C408 \\sim C509 \\sim C510 \\sim C511 \\sim
C512: within 5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
5A
C410 \\sim C412 \\sim C506 \\sim C508: within 5A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 5A
C401 \\sim C402 \\sim C403 \\sim C404 \\sim C501 \\sim C502 \\sim C503 \\sim
C504: within 5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
5A
C414 \\sim C415 \\sim C416 \\sim C514 \\sim C515 \\sim C516: within 5A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 5A
5. Rigid body (RIGU) restrains
 Cl71, Cl72, C701, C702, C703, C704, C705, C706
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(P501)=Sof(C501)=Sof(H50A)=Sof(H50B)=Sof(C502)=Sof(H50C)=Sof(H50D)=
 Sof(C503)=Sof(H50E)=Sof(H50F)=Sof(C504)=Sof(H50G)=Sof(H50H)=Sof(H50I)=
 Sof(C505)=Sof(H50J)=Sof(H50K)=Sof(C506)=Sof(H50L)=Sof(H50M)=Sof(C507)=
 Sof(H50N)=Sof(H50O)=Sof(C508)=Sof(H50P)=Sof(H50Q)=Sof(H50R)=Sof(C509)=
 Sof(H50S)=Sof(H50T)=Sof(C510)=Sof(H51A)=Sof(H51B)=Sof(C511)=Sof(H51C)=
 Sof(H51D)=Sof(C512)=Sof(H51E)=Sof(H51F)=Sof(H51G)=Sof(C513)=Sof(H51H)=
 Sof(H51I)=Sof(C514)=Sof(H51J)=Sof(H51K)=Sof(C515)=Sof(H51L)=Sof(H51M)=
 Sof(C516)=Sof(H51N)=Sof(H51O)=Sof(H51P)=1-FVAR(1)
 Sof(P401)=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(H40I)=
 Sof(C405)=Sof(H40J)=Sof(H40K)=Sof(C406)=Sof(H40L)=Sof(H40M)=Sof(C407)=
 Sof(H40N)=Sof(H40O)=Sof(C408)=Sof(H40P)=Sof(H40Q)=Sof(H40R)=Sof(C409)=
 Sof(H40S)=Sof(H40T)=Sof(C410)=Sof(H41A)=Sof(H41B)=Sof(C411)=Sof(H41C)=
 Sof(H41D)=Sof(C412)=Sof(H41E)=Sof(H41F)=Sof(H41G)=Sof(C413)=Sof(H41H)=
 Sof(H41I)=Sof(C414)=Sof(H41J)=Sof(H41K)=Sof(C415)=Sof(H41L)=Sof(H41M)=
 Sof(C416)=Sof(H41N)=Sof(H41O)=Sof(H41P)=FVAR(1)
 Fixed Sof: Cl72(0.5) Cl71(0.5) C701(0.5) C702(0.5) H702(0.5) C703(0.5)
 H703(0.5) C704(0.5) H704(0.5) C705(0.5) H705(0.5) C706(0.5)
7.a Free rotating group:
 Cl72(Cl71,C701,C702,C703,C704,C705,C706)
7.b Secondary CH2 refined with riding coordinates:
 C301(H30A,H30B), C302(H30C,H30D), C303(H30E,H30F), C305(H30J,H30K), C306(H30L,
 H30M), C307(H30N,H30O), C309(H30S,H30T), C310(H31A,H31B), C311(H31C,H31D),
 C313(H31H,H31I), C314(H31J,H31K), C315(H31L,H31M), C401(H40A,H40B), C402(H40C,
 H40D), C403(H40E,H40F), C405(H40J,H40K), C406(H40L,H40M), C407(H40N,H40O),
 C409(H40S,H40T), C410(H41A,H41B), C411(H41C,H41D), C413(H41H,H41I), C414(H41J,
 H41K), C415(H41L,H41M), C501(H50A,H50B), C502(H50C,H50D), C503(H50E,H50F),
 C505(H50J,H50K), C506(H50L,H50M), C507(H50N,H50O), C509(H50S,H50T), C510(H51A,
 H51B), C511(H51C,H51D), C513(H51H,H51I), C514(H51J,H51K), C515(H51L,H51M)
7.c Aromatic/amide H refined with riding coordinates:
 C101(H101), C102(H102), C106(H106), C107(H107), C108(H108), C109(H109),
 C1T(H1T), C204(H204), C208(H208), C209(H209), C212(H212), C213(H213),
 C702(H702), C703(H703), C704(H704), C705(H705)
7.d Idealised Me refined as rotating group:
 C304(H30G,H30H,H30I), C308(H30P,H30Q,H30R), C312(H31E,H31F,H31G), C316(H31N,
 H31O,H31P), C404(H40G,H40H,H40I), C408(H40P,H40Q,H40R), C412(H41E,H41F,H41G),
 C416(H41N,H41O,H41P), C504(H50G,H50H,H50I), C508(H50P,H50Q,H50R), C512(H51E,
 H51F,H51G), C516(H51N,H51O,H51P)
;
_shelx_res_checksum              73185
_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 1.090
_oxdiff_exptl_absorpt_empirical_full_min 0.948