Synthesis of Fused Metallaaromatics via Intramolecular C‒H Activation of Thiophenes
Zhuo, Qingde; Zhou, Xiaoxi; Kang, Huijun; Chen, Zhiyong; Yang, Yuhui; Han, Feifei; Zhang, Hong; Xia, Haiping; Organometallics 35 (2016) 1497–; doi:10.1021/acs.organomet.6b00083

data_4088438
_publ_section_title
;
 Synthesis of Fused Metallaaromatics via Intramolecular C--H Activation of
 Thiophenes
;
_journal_issue                   10
_journal_name_full               Organometallics
_journal_page_first              1497
_journal_paper_doi               10.1021/acs.organomet.6b00083
_journal_volume                  35
_journal_year                    2016
_chemical_formula_moiety         'C61 H51 Cl2 O Os P3 S, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C62.5 H54 Cl5 O Os P3 S'
_chemical_formula_weight         1313.47
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2016-01-18
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.265(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1780(3)
_cell_length_b                   21.3377(3)
_cell_length_c                   21.0918(4)
_cell_measurement_reflns_used    11252
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      29.3286
_cell_measurement_theta_min      2.9350
_cell_volume                     5795.4(2)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0420
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            12271
_diffrn_reflns_point_group_measured_fraction_full 0.733
_diffrn_reflns_point_group_measured_fraction_max 0.751
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.941
_exptl_absorpt_coefficient_mu    2.591
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73406
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_description       block
_exptl_crystal_F_000             2636
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.164
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Flack x determined using 2190 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.011(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     653
_refine_ls_number_reflns         7663
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0311
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0622P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0862
_refine_ls_wR_factor_ref         0.0880
_reflns_Friedel_coverage         0.503
_reflns_Friedel_fraction_full    0.491
_reflns_Friedel_fraction_max     0.503
_reflns_number_gt                7036
_reflns_number_total             7663
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00083_si_002.cif
_cod_data_source_block           4
_cod_original_cell_volume        5795.40(19)
_cod_original_formula_sum        'C62.50 H54 Cl5 O Os P3 S'
_cod_database_code               4088438
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H) groups
2. Shared sites
{C5, S5}
{S1, C8}
3. Restrained distances
 C2S-Cl2A
 1.77 with sigma of 0.03
 C2S-Cl2B
 1.77 with sigma of 0.03
 Cl2A-Cl2B
 2.89 with sigma of 0.03
4. Uiso/Uaniso restraints and constraints
Uanis(C2S) \\sim Ueq, Uanis(C315) \\sim Ueq: with sigma of 0.0005 and sigma for
terminal atoms of 0.001
Uanis(C5) = Uanis(S5)
Uanis(S1) = Uanis(C8)
5. Others
 Sof(H6B)=Sof(H7B)=Sof(S5)=Sof(C8)=Sof(H8)=1-FVAR(1)
 Sof(C5)=Sof(H5)=Sof(H6A)=Sof(H7A)=Sof(S1)=FVAR(1)
 Fixed Sof: C2S(0.5) H2SA(0.5) H2SB(0.5) Cl2A(0.5) Cl2B(0.5)
6.a Riding coordinates:
 O1(H1A)
6.b Ternary CH refined with riding coordinates:
 C3(H3)
6.c Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C2S(H2SA,H2SB)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C5(H5), C6(H6A), C6(H6B), C7(H7A), C7(H7B), C112(H112), C113(H113),
 C114(H114), C115(H115), C116(H116), C122(H122), C123(H123), C124(H124),
 C125(H125), C126(H126), C132(H132), C133(H133), C134(H134), C135(H135),
 C136(H136), C212(H212), C213(H213), C214(H214), C215(H215), C216(H216),
 C222(H222), C223(H223), C224(H224), C225(H225), C226(H226), C232(H232),
 C233(H233), C234(H234), C235(H235), C236(H236), C312(H312), C313(H313),
 C314(H314), C315(H315), C316(H316), C322(H322), C323(H323), C324(H324),
 C325(H325), C326(H326), C332(H332), C333(H333), C334(H334), C335(H335),
 C336(H336), C8(H8)
6.e Fitted hexagon refined as free rotating group:
 C311(C312,C313,C314,C315,C316), C321(C322,C323,C324,C325,C326)
;
_shelx_res_checksum              92941
_shelx_hkl_checksum              81480
_olex2_submission_special_instructions 'No special instructions were received'