A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration.
Geri, Jacob B.; Szymczak, Nathaniel K.; Journal of the American Chemical Society 137 (2015) 12808–12814; doi:10.1021/jacs.5b08406

data_4124545
_publ_section_title
;
 A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile
 Hydroboration.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12808
_journal_page_last               12814
_journal_paper_doi               10.1021/jacs.5b08406
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety
'4(C54 H43 N5 O2 P2 Ru), 7(C H2 Cl2), 8(C2 F3 O2)'
_chemical_formula_sum            'C239 H186 Cl14 F24 N20 O24 P8 Ru4'
_chemical_formula_weight         5326.41
_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
_audit_creation_date             2015-01-08
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.06 svn.r3119 for OlexSys, GUI svn.r4979)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.361(7)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   11.5513(2)
_cell_length_b                   26.1563(5)
_cell_length_c                   19.7946(14)
_cell_measurement_temperature    85
_cell_volume                     5818.8(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      85
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Rigaku Saturn70 CCD'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0966
_diffrn_reflns_av_unetI/netI     0.0520
_diffrn_reflns_laue_measured_fraction_full 1.000
_diffrn_reflns_laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            97813
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         68.249
_diffrn_reflns_theta_min         2.849
_exptl_absorpt_coefficient_mu    4.824
_exptl_absorpt_correction_T_max  0.514
_exptl_absorpt_correction_T_min  0.260
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private communication'
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       plate
_exptl_crystal_F_000             2702
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.513
_refine_diff_density_min         -1.356
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     850
_refine_ls_number_reflns         10648
_refine_ls_number_restraints     438
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0714
_refine_ls_R_factor_gt           0.0679
_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^)+(0.1061P)^2^+23.5108P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1871
_refine_ls_wR_factor_ref         0.1903
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9695
_reflns_number_total             10648
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b08406_si_002.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 4124543--4124548.cif.'
_cod_database_code               4124545
_shelxl_version_number           2014-3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained planarity
 C8, C1, O5, O6
 with sigma of 0.1
 C8A, C1A, O5A, O6A
 with sigma of 0.1
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C84 \\sim C103 \\sim C25: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O5A \\sim C1A \\sim O6A \\sim C8A \\sim F6A \\sim F3A \\sim F1A: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
F6 \\sim F1 \\sim F3A \\sim C8 \\sim C1 \\sim O6 \\sim O5: within 1.7A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C8 \\sim C8A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.04
F6A \\sim F6: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.04
F1 \\sim F1A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.04
F3 \\sim F3A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.04
C1 \\sim C1A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.04
O5 \\sim O5A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.04
O6A \\sim O6: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.04
Uanis(Cl1A) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(Cl5A) \\sim Ueq: with sigma
of 0.03 and sigma for terminal atoms of 0.06
5. Same fragment restrains
{Cl1A, Cl5A, C4} sigma for 1-2: 0.02, 1-3: 0.04
as
{Cl1, Cl5, C182}
{F6, F1, F3, C8, C1, O5, O6} sigma for 1-2: 0.02, 1-3: 0.04
as
{F31, F37, F51, C153, C176, O1, O2}
{F6A, F1A, F3A, C8A, C1A, O5A, O6A} sigma for 1-2: 0.02, 1-3: 0.04
as
{F6, F1, F3, C8, C1, O5, O6}
6. Others
 Sof(F6A)=Sof(F1A)=Sof(F3A)=Sof(C8A)=Sof(C1A)=Sof(O5A)=Sof(O6A)=1-FVAR(1)
 Sof(F6)=Sof(F1)=Sof(F3)=Sof(C8)=Sof(C1)=Sof(O5)=Sof(O6)=FVAR(1)
 Fixed Sof: Cl1(0.75) Cl5(0.75) C182(0.75) H18A(0.75) H18B(0.75) Cl1A(0.25)
 Cl5A(0.25) C4(0.25) H4A(0.25) H4B(0.25) Cl2(0.75) Cl3(0.75) C2(0.75) H2A(0.75)
 H2B(0.75)
7.a Secondary CH2 refined with riding coordinates:
 C182(H18A,H18B), C4(H4A,H4B), C2(H2A,H2B)
7.b Aromatic/amide H refined with riding coordinates:
 N54(H54), C7(H7), C10(H10), C16(H16), C23(H23), C25(H25), C35(H35), C42(H42),
 C52(H52), C56(H56), C77(H77), C80(H80), C82(H82), C84(H84), C88(H88), C92(H92),
  C98(H98), C100(H100), C103(H103), C107(H107), C118(H118), C130(H130),
 C133(H133), C148(H148), C156(H156), C157(H157), C160(H160), C161(H161),
 C172(H172), C178(H178), C205(H205), C207(H207), C208(H208), C211(H211),
 C213(H213), C214(H214), C215(H215), C216(H216), C217(H217), C218(H218),
 C219(H219)
7.c Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4)
;
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'
_olex2_submission_special_instructions 'No special instructions were received'