Distortion and electronic structure of ordered C60•− radical anions in the salt with {CoI(dppe)2CO}+ cations (dppe: 1,2-bis(diphenylphosphino)ethane)
Konarev, Dmitri V.; Kuzmin, Alexey V.; Andronov, Mikhail G.; Khasanov, Salavat S.; Batov, Mikhail S.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N.; Inorganica Chimica Acta 483 (2018) 504–509; doi:10.1016/j.ica.2018.08.046

data_1563885
_publ_section_title
;
 Distortion and electronic structure of ordered C60&#x2022;&#x2212;
 radical anions in the salt with {CoI(dppe)2CO}+ cations (dppe:
 1,2-bis(diphenylphosphino)ethane)
;
_journal_name_full               'Inorganica Chimica Acta'
_journal_page_first              504
_journal_page_last               509
_journal_paper_doi               10.1016/j.ica.2018.08.046
_journal_volume                  483
_journal_year                    2018
_chemical_formula_moiety
'C53 H48 Co O P4, 0.5(C6 H4 Cl2), C60, 0.5(C6 H14)'
_chemical_formula_sum            'C119 H57 Cl Co O P4'
_chemical_formula_weight         1720.90
_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     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                85.968(3)
_cell_angle_beta                 83.894(3)
_cell_angle_gamma                82.874(3)
_cell_formula_units_Z            2
_cell_length_a                   11.0692(3)
_cell_length_b                   18.1814(5)
_cell_length_c                   19.1296(6)
_cell_measurement_reflns_used    11051
_cell_measurement_temperature    121(6)
_cell_measurement_theta_max      28.7780
_cell_measurement_theta_min      3.7080
_cell_volume                     3792.12(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (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      121(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.834
_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      5.00  91.00   1.00   20.00    --   11.89  77.00-180.00   86
  2  \w    -57.00  41.00   1.00   20.00    --   11.89 -57.00  60.00   98
  3  \w    -58.00  41.00   1.00   20.00    --   11.89 -57.00-180.00   99
  4  \w    -90.00  16.00   1.00   20.00    --  -12.20 -77.00 -60.00  106
;
_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      -0.0108162000
_diffrn_orient_matrix_UB_12      -0.0048985000
_diffrn_orient_matrix_UB_13      0.0371558000
_diffrn_orient_matrix_UB_21      0.0429725000
_diffrn_orient_matrix_UB_22      -0.0323710000
_diffrn_orient_matrix_UB_23      -0.0004155000
_diffrn_orient_matrix_UB_31      0.0474093000
_diffrn_orient_matrix_UB_32      0.0218880000
_diffrn_orient_matrix_UB_33      0.0038099000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0377
_diffrn_reflns_av_unetI/netI     0.0652
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.834
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            39882
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.834
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.687
_diffrn_reflns_theta_min         3.393
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.410
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97542
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_density_diffrn    1.507
_exptl_crystal_description       prism
_exptl_crystal_F_000             1766
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.462
_refine_diff_density_min         -0.706
_refine_diff_density_rms         0.077
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1195
_refine_ls_number_reflns         17940
_refine_ls_number_restraints     295
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0824
_refine_ls_R_factor_gt           0.0550
_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^)+(0.0488P)^2^+4.0717P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1178
_refine_ls_wR_factor_ref         0.1331
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                13214
_reflns_number_total             17940
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ICA-2018-483-504.cif
_cod_data_source_block           c60Codppe2CO
_cod_original_cell_volume        3792.1(2)
_cod_database_code               1563885
_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
 C41-C43 \\sim C43-C42_$1 \\sim C42-C43_$1 \\sim C43_$1-C41_$1 \\sim C51-C53
\\sim C53-C52_$1 ~
 C52-C53_$1 \\sim C53_$1-C51_$1 \\sim C61-C63 \\sim C63-C62_$1 \\sim C62-C63_$1
\\sim C63_$1-C61_$1
 with sigma of 0.02
 C42-C41 \\sim C43-C42 \\sim C43-C43_$1 \\sim C43_$1-C42_$1 \\sim C42_$1-C41_$1
\\sim C52-C51 ~
 C53-C52 \\sim C53-C53_$1 \\sim C53_$1-C52_$1 \\sim C52_$1-C51_$1 \\sim C62-C61
\\sim C63-C62 \\sim C63-
 C63_$1 \\sim C63_$1-C62_$1 \\sim C62_$1-C61_$1
 with sigma of 0.02
3. Rigid bond restraints
 C41, C42, C43, C51, C52, C53, C61, C62, C63
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C41 \\sim C42 \\sim C43 \\sim C51 \\sim C52 \\sim C53 \\sim C61 \\sim C62 \\sim
C63: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C42) = Uanis(C62)
Uanis(C61) = Uanis(C41)
Uanis(C43) = Uanis(C51)
Uanis(C62) = Uanis(C52)
5. Others
 1*[Sof(C41)+Sof(H41A)+Sof(H41B)+Sof(H41C)+Sof(C42)+Sof(H42A)+Sof(H42B)+
 Sof(C43)+Sof(H43A)+Sof(H43B)]+1*[Sof(C51)+Sof(H51A)+Sof(H51B)+Sof(H51C)+
 Sof(C52)+Sof(H52A)+Sof(H52B)+Sof(C53)+Sof(H53A)+Sof(H53B)]+1*[Sof(C61)+
 Sof(H61A)+Sof(H61B)+Sof(H61C)+Sof(C62)+Sof(H62A)+Sof(H62B)+Sof(C63)+Sof(H63A)+
 Sof(H63B)]=1 with esd of 0.0001
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=
 Sof(H43A)=Sof(H43B)=FVAR(1)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=
 Sof(H53A)=Sof(H53B)=FVAR(2)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=
 Sof(H63A)=Sof(H63B)=FVAR(3)
 Fixed Sof: Cl31(0.5) Cl32(0.5) C32(0.5) C31(0.5) C36(0.5) H36(0.5) C35(0.5)
 H35(0.5) C34(0.5) H34(0.5) C33(0.5) H33(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C249(H24A,H24B), C250(H25A,H25B), C251(H25C,H25D), C252(H25E,H25F), C42(H42A,
 H42B), C43(H43A,H43B), C52(H52A,H52B), C53(H53A,H53B), C62(H62A,H62B),
 C63(H63A,H63B)
6.b Aromatic/amide H refined with riding coordinates:
 C202(H202), C203(H203), C204(H204), C205(H205), C206(H206), C208(H208),
 C209(H209), C210(H210), C211(H211), C212(H212), C214(H214), C215(H215),
 C216(H216), C217(H217), C218(H218), C220(H220), C221(H221), C222(H222),
 C223(H223), C224(H224), C226(H226), C227(H227), C228(H228), C229(H229),
 C230(H230), C232(H232), C233(H233), C234(H234), C235(H235), C236(H236),
 C238(H238), C239(H239), C240(H240), C241(H241), C242(H242), C244(H244),
 C245(H245), C246(H246), C247(H247), C248(H248), C36(H36), C35(H35), C34(H34),
 C33(H33)
6.c Fitted hexagon refined as free rotating group:
 C32(C31,C36,C35,C34,C33)
6.d Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C51(H51A,H51B,H51C), C61(H61A,H61B,H61C)
;
_shelx_res_checksum              56029
_shelx_hkl_checksum              70215