Switching of Charge Transport Pathways via Delocalization Changes in Single-molecule Metallacycles Junctions.
Li, Ruihao; Lu, Zhengyu; Cai, Yuanting; Jiang, Feng; Tang, Chun; Chen, Zhixin; Zheng, Jueting; Pi, Jiuchan; Zhang, Rui; Liu, Junyang; Chen, Zhao-Bin; Yang, Yang; Shi, Jia; Hong, Wenjing; Xia, Haiping; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b06400

data_4126382
_publ_section_title
;
 Switching of Charge Transport Pathways via Delocalization Changes in
 Single-molecule Metallacycles Junctions.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b06400
_journal_year                    2017
_chemical_formula_moiety         'C82 H69 N O3 Os P3 S2, C H2 Cl2, B F4'
_chemical_formula_sum            'C83 H71 B Cl2 F4 N O3 Os P3 S2'
_chemical_formula_weight         1635.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-05-23
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.741(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.5713(18)
_cell_length_b                   12.6213(5)
_cell_length_c                   23.1715(17)
_cell_measurement_reflns_used    2970
_cell_measurement_temperature    180.00(14)
_cell_measurement_theta_max      61.2560
_cell_measurement_theta_min      3.9150
_cell_volume                     7314.2(9)
_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      180.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1903
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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   -111.00 -76.00   1.00    8.00    --  -32.31-178.00-180.00   35
  2  \w    -37.00  18.00   1.00    8.00    --   32.31 -57.00 -30.00   55
  3  \w    -37.00  56.00   1.00    8.00    --   32.31 -57.00  90.00   93
  4  \w      9.00 102.00   1.00    8.00    --   32.31  57.00-120.00   93
  5  \w   -145.00-101.00   1.00   24.00    --  -86.00 -92.00  30.00   44
  6  \w     50.00  86.00   1.00   24.00    --   93.97  25.00-150.00   36
  7  \w     23.00 123.00   1.00   24.00    --   93.97 -77.00-180.00  100
  8  \w     37.00  74.00   1.00   24.00    --   93.97 -38.00-180.00   37
  9  \w     23.00  71.00   1.00   24.00    --   93.97 -38.00-120.00   48
 10  \w     60.00 163.00   1.00   24.00    --   93.97  25.00 120.00  103
 11  \w     99.00 124.00   1.00   24.00    --   93.97 -38.00-120.00   25
 12  \w    102.00 134.00   1.00   24.00    --   93.97 -25.00 120.00   32
 13  \w     26.00  87.00   1.00   24.00    --   93.97 -25.00 120.00   61
 14  \w    134.00 161.00   1.00   24.00    --   93.97  25.00-150.00   27
 15  \w    114.00 142.00   1.00   24.00    --   93.97  64.00-180.00   28
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0201633000
_diffrn_orient_matrix_UB_12      0.0590330000
_diffrn_orient_matrix_UB_13      0.0462075000
_diffrn_orient_matrix_UB_21      0.0374824000
_diffrn_orient_matrix_UB_22      0.0934662000
_diffrn_orient_matrix_UB_23      0.0006419000
_diffrn_orient_matrix_UB_31      -0.0444137000
_diffrn_orient_matrix_UB_32      0.0520709000
_diffrn_orient_matrix_UB_33      -0.0534457000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0555
_diffrn_reflns_av_unetI/netI     0.0818
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            11170
_diffrn_reflns_point_group_measured_fraction_full 0.629
_diffrn_reflns_point_group_measured_fraction_max 0.629
_diffrn_reflns_theta_full        61.819
_diffrn_reflns_theta_max         61.819
_diffrn_reflns_theta_min         3.535
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.616
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63101
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.485
_exptl_crystal_description       needle
_exptl_crystal_F_000             3312
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.282
_refine_diff_density_min         -1.334
_refine_diff_density_rms         0.111
_refine_ls_abs_structure_details
;
 Flack x determined using 1315 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.023(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     898
_refine_ls_number_reflns         7215
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0487
_refine_ls_R_factor_gt           0.0414
_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^)+(0.0352P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0929
_refine_ls_wR_factor_ref         0.1026
_reflns_Friedel_coverage         0.274
_reflns_Friedel_fraction_full    0.270
_reflns_Friedel_fraction_max     0.270
_reflns_number_gt                6496
_reflns_number_total             7215
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b06400_si_003.cif
_cod_data_source_block           4
_cod_database_code               4126382
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     59.94
_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. Shared sites
{S2, C21}
{C20, S3}
3. Rigid bond restraints
 Os1, C1N, N1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.0001
4. Uiso/Uaniso restraints and constraints
Uanis(S2) = Uanis(C21)
Uanis(C20) = Uanis(S3)
5. Others
 Sof(C21)=Sof(H21)=Sof(S3)=1-FVAR(1)
 Sof(C20)=Sof(H20)=Sof(S2)=FVAR(1)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C35)=Sof(H35A)=
 Sof(H35B)=1-FVAR(2)
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C41)=Sof(H41A)=
 Sof(H41B)=Sof(C40)=Sof(H40)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=
 Sof(H45B)=FVAR(2)
 Fixed Sof: H19(0.4) H19A(0.6) H22(0.4) H22A(0.6)
6.a Ternary CH refined with riding coordinates:
 C30(H30), C40(H40)
6.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C42(H42A,H42B), C1S(H1SA,H1SB), C43(H43A,H43B), C41(H41A,
 H41B), C31(H31A,H31B), C33(H33A,H33B), C44(H44A,H44B), C32(H32A,H32B),
 C35(H35A,H35B), C45(H45A,H45B)
6.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C125(H125), C314(H314), C315(H315), C5(H5), C13(H13), C235(H235),
 C115(H115), C325(H325), C3(H3), C19(H19), C19(H19A), C9(H9), C16(H16),
 C111(H111), C225(H225), C231(H231), C134(H134), C321(H321), C123(H123),
 C124(H124), C17(H17), C121(H121), C135(H135), C22(H22), C22(H22A), C221(H221),
 C15(H15), C122(H122), C311(H311), C334(H334), C234(H234), C114(H114),
 C132(H132), C323(H323), C335(H335), C224(H224), C332(H332), C333(H333),
 C313(H313), C131(H131), C324(H324), C215(H215), C223(H223), C113(H113),
 C212(H212), C112(H112), C133(H133), C232(H232), C322(H322), C222(H222),
 C213(H213), C211(H211), C312(H312), C331(H331), C233(H233), C214(H214),
 C21(H21)
6.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C)
;
_shelx_shelxl_version_number     2014/7
_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 2.338
_oxdiff_exptl_absorpt_empirical_full_min 0.618