Multi-electron reduction of sulfur and carbon disulfide using binuclear uranium(iii) borohydride complexes
Arnold, Polly L.; Stevens, Charlotte J.; Bell, Nicola L.; Lord, Rianne M.; Goldberg, Jonathan M.; Nichol, Gary S.; Love, Jason B.; Chem. Sci. 8 (2017) 3609–; doi:10.1039/C7SC00382J

data_1545549
_publ_section_title
;
 Multi-electron reduction of sulfur and carbon disulfide using binuclear
 uranium(iii) borohydride complexes
;
_journal_issue                   5
_journal_name_full               'Chem. Sci.'
_journal_page_first              3609
_journal_paper_doi               10.1039/C7SC00382J
_journal_volume                  8
_journal_year                    2017
_chemical_formula_moiety         'C61 H48 N8 S9 U2'
_chemical_formula_sum            'C61 H48 N8 S9 U2'
_chemical_formula_weight         1657.67
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             15-05-21
_audit_creation_method
;
Rigaku CrystalClear-SM Expert 2.1 b32
;
_audit_update_record
;
2016-05-16 deposited with the CCDC.
2017-03-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   28.579(8)
_cell_length_b                   28.912(8)
_cell_length_c                   33.323(8)
_cell_measurement_reflns_used    18436
_cell_measurement_temperature    125(2)
_cell_measurement_theta_max      75.0
_cell_measurement_theta_min      23.8
_cell_volume                     27534(13)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.1 b32 (Rigaku, 2014)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.1 b32 (Rigaku, 2014)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.1 b32 (Rigaku, 2014)
;
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_diffrn_ambient_temperature      125(2)
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type
;
Rigaku Pilatus 200K
;
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.2206
_diffrn_reflns_av_unetI/netI     0.1391
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            231223
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.687
_diffrn_reflns_theta_max         67.872
_diffrn_reflns_theta_min         2.023
_diffrn_source                   'Sealed Tube'
_exptl_absorpt_coefficient_mu    12.013
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.268
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_description       'red needle'
_exptl_crystal_F_000             9576
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         3.285
_refine_diff_density_min         -5.047
_refine_diff_density_rms         0.379
_refine_ls_abs_structure_details
;
 Flack x determined using 7901 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.445(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.456
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1150
_refine_ls_number_reflns         49276
_refine_ls_number_restraints     275
_refine_ls_restrained_S_all      1.454
_refine_ls_R_factor_all          0.1886
_refine_ls_R_factor_gt           0.1684
_refine_ls_shift/su_max          1.410
_refine_ls_shift/su_mean         0.027
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4167
_refine_ls_wR_factor_ref         0.4471
_reflns_Friedel_coverage         0.870
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                34052
_reflns_number_total             49276
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc00382j2.cif
_cod_data_source_block           shelxl_3
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Multi-scan' changed to
'multi-scan' according to
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

 Adding full bibliography for 1545549--1545553.cif.

2019-02-07
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C183 H144 N24 S27 U6'
_cod_original_formula_weight         4973.01
_cod_original_formula_moiety         '3(C61 H48 N8 S9 U2)'
_cod_original_formula_units_Z            4
_cod_database_code               1545549
_shelx_estimated_absorpt_t_max   0.197
_shelx_estimated_absorpt_t_min   0.197
_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. Restrained distances
 C46-N47
 1.4 with sigma of 0.001
 N47-C43
 1.4 with sigma of 0.001
 C46-C45
 1.39 with sigma of 0.001
 C45-C44
 1.39 with sigma of 0.001
 C43-C44
 1.39 with sigma of 0.001
 C46-C48
 1.51 with sigma of 0.001
 C48-C51
 1.57 with sigma of 0.001
 C48-C49
 1.57 with sigma of 0.001
 C43-C42
 1.4 with sigma of 0.001
 C42-N41
 1.32 with sigma of 0.001
 C53-C48
 1.51 with sigma of 0.01
 C55C-C56C
 1.4 with sigma of 0.01
 C54C-C53C
 1.4 with sigma of 0.01
 C55C-C54C
 1.4 with sigma of 0.01
 C77C-C118
 1.39 with sigma of 0.02
 C45B-C44B
 1.39 with sigma of 0.01
 C45B-C46B
 1.39 with sigma of 0.01
 C44B-C43B
 1.39 with sigma of 0.01
 C43B-N47B
 1.4 with sigma of 0.01
 N47B-C46B
 1.4 with sigma of 0.01
 C78B-C77B
 1.4 with sigma of 0.02
 C79B-C78B
 1.4 with sigma of 0.02
 C76B-C77B
 1.4 with sigma of 0.02
 C61C-C60C
 1.37 with sigma of 0.02
 C72C-C73C
 1.37 with sigma of 0.02
 C49-C248
 1.52 with sigma of 0.02
 C51-C52
 1.52 with sigma of 0.02
 C79B-N80B
 1.4 with sigma of 0.02
 C53-N57
 1.4 with sigma of 0.02
 C53-C54
 1.4 with sigma of 0.02
 N57-C53
 1.4 with sigma of 0.01
 N57-C56
 1.4 with sigma of 0.01
 C53-C54
 1.4 with sigma of 0.01
 C54-C55
 1.4 with sigma of 0.01
 C56-C55
 1.4 with sigma of 0.01
 N79-C78
 1.4 with sigma of 0.01
 C78-C77
 1.4 with sigma of 0.01
 C75-N79
 1.4 with sigma of 0.01
 C254-C17
 1.56 with sigma of 0.01
 N79-C78
 1.4 with sigma of 0.01
 N79-C75
 1.4 with sigma of 0.01
 C78-C77
 1.4 with sigma of 0.01
 C77-C193
 1.4 with sigma of 0.02
 C75-C193
 1.4 with sigma of 0.02
 C78-C17
 1.51 with sigma of 0.02
 C17C-C105
 1.51 with sigma of 0.02
 C1AA-C105
 1.52 with sigma of 0.02
 C74-C75
 1.4 with sigma of 0.01
 C74-N73
 1.32 with sigma of 0.01
 C49C-C50C
 1.51 with sigma of 0.01
 C56B-C55B
 1.39 with sigma of 0.01
 C79C-C77C
 2.25 with sigma of 0.02
 C118-C76C
 2.25 with sigma of 0.02
 C43B-C46B
 2.25 with sigma of 0.02
 C43B-C45B
 2.25 with sigma of 0.02
 C44B-C46B
 2.25 with sigma of 0.02
 C77B-C79B
 2.25 with sigma of 0.04
 C78B-C76B
 2.25 with sigma of 0.04
 C79B-C76B
 2.25 with sigma of 0.04
 C56B-C53B
 2.25 with sigma of 0.04
 C54-C56
 2.25 with sigma of 0.04
 C56-C53
 2.25 with sigma of 0.02
 C53-C55
 2.25 with sigma of 0.02
 C56-C54
 2.25 with sigma of 0.02
 C75-C78
 2.25 with sigma of 0.02
 C17-C222
 2.6 with sigma of 0.04
 C78-C193
 2.25 with sigma of 0.02
 C77-C75
 2.25 with sigma of 0.02
 C78-C75
 2.25 with sigma of 0.02
 C78-C254
 2.6 with sigma of 0.04
 C55C-C53C
 2.25 with sigma of 0.04
 N73-C75
 2.4 with sigma of 0.02
 N79-C74
 2.4 with sigma of 0.02
 C21C-C23C
 2.24 with sigma of 0.02
 C46B-C51B
 2.4 with sigma of 0.02
3. Restrained planarity
 N80C, C79C, C77C, C76C
 with sigma of 0.1
 C66, C67, C72, C71, C70, C69, C65, C64, C9H, C68, C60, C61, C62, C63
 with sigma of 0.1
 C79C, C118, C77C, C76C, N80C
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
S14C \\sim C13C \\sim S11C \\sim S12C: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
S9B \\sim C8B \\sim S7B \\sim S10B: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
S7 \\sim C9 \\sim S8 \\sim S10: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
S3 \\sim C4 \\sim S5 \\sim S6: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
S7C \\sim C9C \\sim S8C \\sim S10C: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
S7C \\sim C9C \\sim S8C \\sim S10C: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uiso(N80C) = Uiso(N47C)
Uiso(C77C) = Uiso(C54C)
Uiso(N80C) = Uiso(C76C) = Uiso(C77C) = Uiso(C118) = Uiso(C79C)
Uiso(C49) = Uiso(C248)
Uiso(N79) = Uiso(C78) = Uiso(C77) = Uiso(C193) = Uiso(C75)
Uiso(N57) = Uiso(C53) = Uiso(C54) = Uiso(C55) = Uiso(C56)
Uiso(C1AA) = Uiso(C105)
Uiso(N73) = Uiso(C74) = Uiso(C75)
Uiso(C1AA) = Uiso(C105) = Uiso(C17C) = Uiso(C16C) = Uiso(C148)
5. Rigid body (RIGU) restrains
 S14C, C13C, S11C, S12C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S7B, C8B, S9B, S10B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S7, C9, S10, S8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S3, C4, S5, S6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{S8C, C9C, S10C, S7C} sigma for 1-2: 0.02, 1-3: 0.02
as
{S9B, C8B, S10B, S7B}
{S3B, C4B, S6B, S5B} sigma for 1-2: 0.02, 1-3: 0.02
as
{S14B, C13B, S11B, S12B}
{S6, C4, S5, S3} sigma for 1-2: 0.02, 1-3: 0.02
as
{S6B, C4B, S5B, S3B}
{N73, C74, C75} sigma for 1-2: 0.02, 1-3: 0.02
as
{N59, C58, C56}
{N47C, C43C, C44C, C45C, C46C} sigma for 1-2: 0.02, 1-3: 0.02
as
{N47, C43, C44, C45, C46}
{C15, C16, C17, C254, C222} sigma for 1-2: 0.02, 1-3: 0.02
as
{C52, C51, C48, C49, C248}
{C76C, C255, N74C, C73C} sigma for 1-2: 0.02, 1-3: 0.02
as
{C23C, C25C, N26C, C27C}
{C40B, C39B, C38B, C37B, C35B, C34B} sigma for 1-2: 0.02, 1-3: 0.02
as
{C27B, C28B, C29B, C30B, C31B, C32B}
{C27C, C28C, C29C, C30C, C31C, C32C} sigma for 1-2: 0.02, 1-3: 0.02
as
{C40C, C39C, C38C, C37C, C35C, C34C}
{N24B, C23B, C22B, C21B, C20B} sigma for 1-2: 0.02, 1-3: 0.02
as
{C38, C72C, C65, C61, C60}
{C17C, C16C, C148} sigma for 1-2: 0.02, 1-3: 0.02
as
{C48C, C51C, C52C}
{C49B, C180} sigma for 1-2: 0.02, 1-3: 0.02
as
{C51B, C52B}
7.a Secondary CH2 refined with riding coordinates:
 C51(HM,HN), C49(HO,HP), C16(H0BA,H1BA), C254(H2BA,H3BA), C16C(H4CA,H5CA),
 C16B(H16A,H16B), C18B(H18A,H18B), C51C(H2FA,H3FA), C49B(H49A,H49B), C50C(H7FA,
 H8FA), C51B(H51A,H51B), C105(H4GA,H5GA)
7.b Aromatic/amide H refined with riding coordinates:
 C74(H), C54C(HA), C55C(HB), C58(HC), C55(HD), C54(HE), C44C(HF), C45C(HG),
 C44(HH), C45(HI), C75B(H75B), C118(HT), C77C(HU), C255(HV), C25C(HW), C22C(HX),
  C21C(HY), C22(HZ), C22B(H22B), C21B(H21B), C39B(H39B), C38B(H38B), C37B(H37B),
  C66C(H0AA), C28B(H28B), C29B(H29B), C30B(H30B), C72B(H72B), C33C(H1AA),
 C39C(H2AA), C38C(H3AA), C37C(H4AA), C39(H5AA), C63B(H63B), C58C(H6AA),
 C63C(H7BA), C62B(H62B), C28C(H8BA), C29C(H9BA), C30C(H0CA), C36(H1CA),
 C69B(H69B), C44B(H44B), C45B(H45B), C33(H2CA), C77(H3CA), C36C(H9CA),
 C69(H0DA), C61B(H61B), C29(H1DA), C42(H2DA), C70B(H70B), C66B(H66B),
 C71B(H71B), C25(H3DA), C36B(H36B), C33B(H33B), C25B(H25B), C71C(H4DA),
 C71(H5DA), C61C(H6DA), C42B(H42B), C69C(H7DA), C30(H8DA), C70C(H9DA),
 C28(H0EA), C62C(H1EA), C68(H2EA), C37(H3EA), C78B(H78B), C77B(H77B),
 C42C(H4EA), C55B(H55B), C54B(H54B), C38(H5EA), C72C(H6EA), C65(H7EA),
 C61(H8EA), C63(H9EA), C62(H0FA), C70(H1FA), C58B(H58B), C0AA(H2GA), C193(H3GA)
7.c Fitted hexagon refined as free rotating group:
 C61(C60,C9H,C64,C63,C62)
7.d Idealised Me refined as rotating group:
 C52(HJ,HK,HL), C248(HQ,HR,HS), C15(H7AA,H8AA,H9AA), C222(H4BA,H5BA,H6BA),
 C148(H6CA,H7CA,H8CA), C52C(H4FA,H5FA,H6FA), C180(H18C,H18D,H18E), C19B(H19A,
 H19B,H19C), C49C(H9FA,H0GA,H1GA), C15B(H15A,H15B,H15C), C52B(H52A,H52B,H52C),
 C1AA(H6GA,H7GA,H8GA)
;
_shelx_res_checksum              59819
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'