Modulation of Proton-Coupled Electron Transfer through Molybdenum-Quinonoid Interactions.
Henthorn, Justin T.; Agapie, Theodor; Inorganic chemistry 55 (2016) 5337–5342; doi:10.1021/acs.inorgchem.6b00331

data_4347547
_publ_section_title
;
 Modulation of Proton-Coupled Electron Transfer through
 Molybdenum-Quinonoid Interactions.
;
_journal_issue                   11
_journal_name_full               'Inorganic chemistry'
_journal_page_first              5337
_journal_page_last               5342
_journal_paper_doi               10.1021/acs.inorgchem.6b00331
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety
'4(C32 H39 Mo O4 P2), 4(C F3 O3 S), 2(C3 H7 N O)'
_chemical_formula_sum            'C138 H170 F12 Mo4 N2 O30 P8 S4'
_chemical_formula_weight         3324.51
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-04
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.729(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.285(3)
_cell_length_b                   26.445(2)
_cell_length_c                   17.9449(13)
_cell_measurement_reflns_used    9029
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      31.10
_cell_measurement_theta_min      2.30
_cell_volume                     14341(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1071
_diffrn_reflns_av_unetI/netI     0.0771
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            421078
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         32.580
_diffrn_reflns_theta_min         0.674
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.578
_exptl_absorpt_correction_T_max  0.7467
_exptl_absorpt_correction_T_min  0.6390
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/4 (Bruker,2014/4) was used for absorption correction. wR2(int) was 0.0777 before and 0.0705 after correction. The Ratio of minimum to maximum transmission is 0.8558. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.540
_exptl_crystal_description       block
_exptl_crystal_F_000             6848
_refine_diff_density_max         2.493
_refine_diff_density_min         -2.309
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1902
_refine_ls_number_reflns         51632
_refine_ls_number_restraints     81
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1027
_refine_ls_R_factor_gt           0.0609
_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^)+(0.0289P)^2^+54.4319P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1226
_refine_ls_wR_factor_ref         0.1369
_reflns_Friedel_coverage         0.000
_reflns_number_gt                35841
_reflns_number_total             51632
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00331_si_001.cif
_cod_data_source_block           3
_cod_database_code               4347547
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C6) = Uanis(O3)
Uanis(N1A) = Uanis(C5) = Uanis(O2)
Uanis(S1) = Uanis(C16)
Uanis(N1) = Uanis(C6) = Uanis(C9) = Uanis(C7)
3. Same fragment restrains
{S007, F00I, F00K, F00V, O00S, O00X, O00Y, C04K} sigma for 1-2: 0.02, 1-3: 0.02
as
{S00G, F02A, F04Q, F057, O04R, O05D, O055, C05C}
{S007, F00I, F00K, F00V, O00S, O00X, O00Y, C04K} sigma for 1-2: 0.02, 1-3: 0.02
as
{S1, F7, F11, F17, O4, O04S, O13, C16}
{O02M, N02E, C05A, C05F, C05G} sigma for 1-2: 0.01, 1-3: 0.01
as
{O2, N1A, C5, C8, C18}
{O02M, N02E, C05A, C05F, C05G} sigma for 1-2: 0.01, 1-3: 0.01
as
{O3, N1, C6, C7, C9}
4. Others
 Sof(S1)=Sof(F7)=Sof(F11)=Sof(F17)=Sof(O4)=Sof(O04S)=Sof(O13)=Sof(C16)=1-FVAR(1)
 Sof(S00G)=Sof(F02A)=Sof(F04Q)=Sof(F057)=Sof(O04R)=Sof(O05D)=Sof(O055)=
 Sof(C05C)=FVAR(1)
 Sof(O2)=Sof(N1A)=Sof(C5)=Sof(H5)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C18)=
 Sof(H18A)=Sof(H18B)=Sof(H18C)=1-FVAR(2)
 Sof(O3)=Sof(N1)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C01T(H01T), C02Q(H02Q), C02X(H02X), C03I(H03I), C03R(H03R), C045(H045),
 C01S(H01S), C02H(H02H), C03U(H03), C035(H035), C03C(H0AA), C03Z(H3AA),
 C04C(H04Z), C04J(H5AA), C040(H040), C041(H041), C02T(H02T), C02Y(H02Y),
 C03M(H3BA), C028(H028), C053(H053), C059(H059)
5.b Aromatic/amide H refined with riding coordinates:
 C01I(H01I), C03B(H03B), C03H(H03H), C03S(H03S), C03X(H03X), C03Y(H03Y),
 C04M(H04M), C027(H027), C01K(H01K), C01L(H01L), C01O(H01O), C01P(H01P),
 C01U(H01U), C01Y(H01Y), C02R(H02R), C03A(H03P), C029(H029), C030(H030),
 C02B(H02D), C02C(H02E), C03G(H1AA), C03V(H2AA), C04D(H04), C04E(H4AA),
 C04L(H6AA), C038(H038), C02G(H02G), C02J(H02J), C04F(H5BA), C04H(H6BA),
 C04X(H8BA), C04Z(H9BA), C037(H037), C043(H043), C5(H5), C05A(H05S), C6(H6)
5.c Idealised Me refined as rotating group:
 C02W(H02A,H02B,H02C), C03F(H03A,H03C,H03D), C03J(H03E,H03F,H03G), C03T(H03J,
 H03K,H03L), C04P(H04A,H04B,H04C), C04S(H04D,H04E,H04F), C04Y(H04G,H04H,H04I),
 C031(H03M,H03N,H03O), C01Z(H01A,H01B,H01C), C03K(H03Q,H03T,H03U), C03O(H03V,
 H03W,H03Z), C04G(H04J,H04K,H04L), C04U(H04N,H04O,H04P), C044(H04Q,H04R,H04S),
 C046(H04T,H04U,H04V), C049(H04W,H04X,H04Y), C04N(H7AA,H,HA), C04T(H8AA,HB,HC),
 C04V(H9AA,HD,HE), C04W(H0BA,HF,HG), C042(H1BA,HH,HI), C048(H2BA,HJ,HK),
 C054(H05A,H05B,H05C), C056(H05D,H05E,H05F), C02U(H02F,H02I,H02K), C04B(H4BA,HL,
 HM), C04O(H7BA,HN,HO), C05B(H05G,H05H,H05I), C047(H0CA,HP,HQ), C051(H05J,H05K,
 H05L), C052(H05M,H05N,H05O), C058(H05P,H05Q,H05R), C8(H8A,H8B,H8C), C18(H18A,
 H18B,H18C), C05F(H05T,H05U,H05V), C05G(H05W,H05X,H05Y), C7(H7A,H7B,H7C),
 C9(H9A,H9B,H9C)
5.d Idealised tetrahedral OH refined as rotating group:
 O00M(H00M), O00L(H00L), O00Q(H00Q), O00N(H00N)
;
_shelx_res_checksum              68121
_shelx_hkl_checksum              18347
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'