Chloro- and Trifluoromethyl-Substituted Flanking-Ring m-Terphenyl Isocyanides: η6-Arene Binding to Zero-Valent Molybdenum Centers and Comparison to Alkyl-Substituted Derivatives
Treffly B. Ditri; Alex E. Carpenter; Donald S. Ripatti; Curtis E. Moore; Arnold L. Rheingold; Joshua S. Figueroa; Inorganic Chemistry 52 (2013) 13216–13229; doi:10.1021/ic402130p

data_4336745
_publ_section_title
;
 Chloro- and Trifluoromethyl-Substituted Flanking-Ring m-Terphenyl
 Isocyanides: \h6-Arene Binding to Zero-Valent Molybdenum Centers and
 Comparison to Alkyl-Substituted Derivatives
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              13216
_journal_page_last               13229
_journal_paper_doi               10.1021/ic402130p
_journal_volume                  52
_journal_year                    2013
_chemical_formula_moiety         'C93 H111 Mo N3, 2.5(C2 H3 N), C4 H10 O'
_chemical_formula_sum            'C102 H128.5 Mo N5.5 O'
_chemical_formula_weight         1543.54
_chemical_name_common            Mo(kappa1-C-CNArDipp(eta6-Dipp))(CNArDipp2)2
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-08-19
_audit_creation_method
;
  Olex2 1.2-beta
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.526(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.281(3)
_cell_length_b                   12.0656(12)
_cell_length_c                   41.585(5)
_cell_measurement_reflns_used    1540
_cell_measurement_temperature    100
_cell_measurement_theta_max      21.873
_cell_measurement_theta_min      2.252
_cell_volume                     9046(2)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_collection       'Bruker APEX2 v2013-2.0 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
M. C. Burla, R. Caliandro, M. Camalli, B. Carrozzini, G. L. Cascarano, 
L. De Caro, C. Giacovazzo, G. Polidori and R. Spagna, 
SIR2004: an improved tool for crystal structure determination and refinement. 
J. Appl. Cryst. (2005). 38, 381-388.
;
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.772
_diffrn_measured_fraction_theta_max 0.765
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0668
_diffrn_reflns_av_unetI/netI     0.1590
_diffrn_reflns_Laue_measured_fraction_full 0.772
_diffrn_reflns_Laue_measured_fraction_max 0.765
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            17343
_diffrn_reflns_point_group_measured_fraction_full 0.772
_diffrn_reflns_point_group_measured_fraction_max 0.765
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.382
_diffrn_reflns_theta_min         2.031
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker TXS'
_exptl_absorpt_coefficient_mu    0.194
_exptl_absorpt_correction_T_max  0.0916
_exptl_absorpt_correction_T_min  0.0627
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0501 before and 0.0391 after correction.
The Ratio of minimum to maximum transmission is 0.6845.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.133
_exptl_crystal_description       Block
_exptl_crystal_F_000             3316
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.600
_refine_diff_density_min         -0.770
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1010
_refine_ls_number_reflns         12714
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.1563
_refine_ls_R_factor_gt           0.0712
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0665P)^2^+4.8055P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1435
_refine_ls_wR_factor_ref         0.1780
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6858
_reflns_number_total             12714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic402130p_si_001_01.cif
_cod_data_source_block           JFig894
_cod_original_cell_volume        9045.9(19)
_cod_original_formula_sum        'C102 H128.50 Mo N5.50 O'
_cod_database_code               4336745
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C1H-C1A
 1.6 with sigma of 0.02
 C63-C62 = C63A-C62
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C55A) = Uanis(C55)
Uanis(C57) = Uanis(C57A)
Uanis(C1I) = Uanis(C97) = Uanis(C96) = Uanis(N6) = Uanis(C1B) = Uanis(O1) 
= Uanis(C1H) = Uanis(C1A) = Uanis(C1C) = Uanis(N1B)
Uanis(C1G) = Uanis(C1F) = Uanis(O1B) = Uanis(C1E) = Uanis(C1D)
Uanis(C22A) = Uanis(C22)
Uanis(C61A) = Uanis(C61)
Uanis(C63) = Uanis(C63A)
4. others
 Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(H56A)=Sof(C57A)=Sof(H57D)=
 Sof(H57E)=Sof(H57F)=1-FVAR(1)
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(H56)=Sof(C57)=Sof(H57A)=Sof(H57B)=
 Sof(H57C)=FVAR(1)
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(H23A)=1-FVAR(2)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(H23)=FVAR(2)
 Sof(C61A)=Sof(H61D)=Sof(H61E)=Sof(H61F)=Sof(H62A)=Sof(C63A)=Sof(H63D)=
 Sof(H63E)=Sof(H63F)=1-FVAR(3)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(H62)=Sof(C63)=Sof(H63A)=Sof(H63B)=
 Sof(H63C)=FVAR(3)
 Fixed Sof: O1(0.25) N1B(0.75) N6(0.75) H1AA(0.75) H1AB(0.75) H1AC(0.75)
 H1AD(0.25) H1AE(0.25) H1AF(0.25) C1B(0.25) H1BA(0.25) H1BB(0.25) C1C(0.75)
 C1H(0.25) H1HA(0.25) H1HB(0.25) C1I(0.25) H1IA(0.25) H1IB(0.25) H1IC(0.25)
 C96(0.75) C97(0.75) H97A(0.75) H97B(0.75) H97C(0.75) O1B(0.75) C1D(0.75)
 H1DA(0.75) H1DB(0.75) H1DC(0.75) C1E(0.75) H1EA(0.75) H1EB(0.75) C1F(0.75)
 H1FA(0.75) H1FB(0.75) C1G(0.75) H1GA(0.75) H1GB(0.75) H1GC(0.75)
5.a Ternary CH refined with riding coordinates:
 C23(H23), C23(H23A), C26(H26), C29(H29), C32(H32), C53(H53), C56(H56),
 C56(H56A), C59(H59), C62(H62), C62(H62A), C83(H83), C86(H86), C89(H89),
 C92(H92)
5.b Secondary CH2 refined with riding coordinates:
 C1B(H1BA,H1BB), C1H(H1HA,H1HB), C1E(H1EA,H1EB), C1F(H1FA,H1FB)
5.c Me refined with riding coordinates:
 C1A(H1AA,H1AB,H1AC), C1A(H1AD,H1AE,H1AF)
5.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14), C18(H18), C19(H19),
 C20(H20), C36(H36), C37(H37), C38(H38), C42(H42), C43(H43), C44(H44), C48(H48),
  C49(H49), C50(H50), C66(H66), C67(H67), C68(H68), C72(H72), C73(H73),
 C74(H74), C78(H78), C79(H79), C80(H80)
5.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C22A(H22D,H22E,H22F), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C33(H33A,H33B,H33C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C),
 C55(H55A,H55B,H55C), C55A(H55D,H55E,H55F), C57(H57A,H57B,H57C), C57A(H57D,H57E,
 H57F), C58(H58A,H58B,H58C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C),
 C61A(H61D,H61E,H61F), C63(H63A,H63B,H63C), C63A(H63D,H63E,H63F), C82(H82A,H82B,
 H82C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C87(H87A,H87B,H87C), C88(H88A,
 H88B,H88C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C93(H93A,H93B,H93C),
 C1I(H1IA,H1IB,H1IC), C97(H97A,H97B,H97C), C1D(H1DA,H1DB,H1DC), C1G(H1GA,H1GB,
 H1GC), C98(H98A,H98B,H98C)
;
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.966
_shelx_res_checksum              30515
_shelxl_version_number           2013-2