Metallocarbonyl bromomaleimide derivatives for thiol bioconjugation and disulfide bridging: spectroscopic and biological properties.
Koprowska, Karolina; Fischer-Durand, Nathalie; Michlewska, Sylwia; Gapińska, Magdalena; Grodzicka, Marika; Makal, Anna; Krzeszczakowska, Joanna; Wrona-Piotrowicz, Anna; Lignières, Laurent; Salmain, Michèle; Rudolf, Bogna; Dalton transactions (Cambridge, England : 2003) 54 (2025) 16864–16875; doi:10.1039/d5dt02375k

data_7719802
_publ_section_title
;
 Metallocarbonyl bromomaleimide derivatives for thiol bioconjugation and
 disulfide bridging: spectroscopic and biological properties.
;
_journal_issue                   45
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16864
_journal_page_last               16875
_journal_paper_doi               10.1039/d5dt02375k
_journal_volume                  54
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C32 H38 N O20 S2, 2(C32 H39 N O20 S2), C32 H33 N O20 S2, C32 H28 N O20 S2, C32 H4 N O20 S2, C6 H14, 1[C6H14], 0.5[C6H14]'
_chemical_formula_sum            'C207 H216 N6 O120 S12'
_chemical_formula_weight         5092.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424ae for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-08 deposited with the CCDC.	2025-10-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.1682(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   26.8895(2)
_cell_length_b                   14.89266(13)
_cell_length_c                   31.0943(3)
_cell_measurement_reflns_used    43791
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.4400
_cell_measurement_theta_min      2.0880
_cell_volume                     12418.97(19)
_computing_cell_refinement       'CrysAlisPro 1.171.43.108a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.144a 64-bit (release 23-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.43.108a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXD  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -7.00  19.00   0.50    0.40    --    0.00 -86.00 -86.00   52
  2  \w    -17.00  36.00   0.50    0.40    --    0.00  86.00  31.00  106
  3  \w   -134.00 -82.00   0.50    3.20    --  -54.00 -86.00 -86.00  104
  4  \w    -55.00 -15.00   0.50    3.20    --  -54.00  86.00  31.00   80
  5  \w    -21.00  91.00   0.50    3.20    --   55.15 -86.00 -86.00  224
  6  \w    102.00 177.00   0.50    3.50    --  110.30  86.00  31.00  150
  7  \w     58.00 158.00   0.50    3.50    --  110.30 -86.00 -86.00  200
  8  \w     25.00  50.00   0.50    0.40    --    0.00 -99.00   0.00   50
  9  \w      7.00  46.00   0.50    0.40    --    0.00 -99.00-180.00   78
 10  \w     40.00  78.00   0.50    0.40    --    0.00  57.00  30.00   76
 11  \w    -13.00  38.00   0.50    0.40    --    0.00  57.00  30.00  102
 12  \w    -92.00 -44.00   0.50    0.40    --    0.00-178.00  90.00   96
 13  \w   -134.00 -77.00   0.50    3.20    --  -54.00-125.00  60.00  114
 14  \w   -141.00 -95.00   0.50    3.20    --  -54.00 -99.00-150.00   92
 15  \w   -137.00-110.00   0.50    3.20    --  -54.00 -99.00 -60.00   54
 16  \w   -128.00-102.00   0.50    3.20    --  -54.00 -99.00-180.00   52
 17  \w   -133.00 -26.00   0.50    3.20    --  -54.00 -57.00-180.00  214
 18  \w    -82.00 -14.00   0.50    3.20    --  -54.00 125.00 120.00  136
 19  \w    -86.00 -51.00   0.50    3.20    --  -54.00 125.00  90.00   70
 20  \w   -135.00 -98.00   0.50    3.20    --  -54.00-125.00 -60.00   74
 21  \w   -130.00 -35.00   0.50    3.20    --  -54.00 -57.00-150.00  190
 22  \w     79.00 176.00   0.50    3.50    --  110.30  63.00 -30.00  194
 23  \w    104.00 178.00   0.50    3.50    --  110.30 111.00 -90.00  148
 24  \w     76.00 178.00   0.50    3.50    --  110.30  63.00   0.00  204
 25  \w    126.00 151.00   0.50    3.50    --  110.30-178.00  90.00   50
 26  \w     66.00 109.00   0.50    3.50    --  110.30-178.00  90.00   86
 27  \w     80.00 144.00   0.50    3.50    --  110.30 -38.00-120.00  128
 28  \w     75.00 163.00   0.50    3.50    --  110.30  63.00 150.00  176
 29  \w    126.00 151.00   0.50    3.50    --  110.30  50.00-120.00   50
 30  \w     33.00  59.00   0.50    3.50    --  110.30 -38.00-120.00   52
 31  \w     71.00 110.00   0.50    3.50    --  110.30  50.00-120.00   78
 32  \w     65.00  91.00   0.50    3.50    --  110.30 -91.00-150.00   52
 33  \w     73.00 177.00   0.50    3.50    --  110.30  50.00  90.00  208
 34  \w     57.00 150.00   0.50    3.50    --  110.30 -50.00-150.00  186
 35  \w     30.00  57.00   0.50    3.50    --  110.30 -91.00-150.00   54
 36  \w     49.00  74.00   0.50    3.50    --  110.30 -38.00-180.00   50
 37  \w    113.00 155.00   0.50    3.50    --  110.30 -38.00-180.00   84
 38  \w     58.00 103.00   0.50    3.50    --  110.30-111.00-120.00   90
 39  \w     63.00 145.00   0.50    3.50    --  110.30 178.00-180.00  164
 40  \w     65.00  90.00   0.50    3.50    --  110.30 178.00 150.00   50
 41  \w     35.00  97.00   0.50    3.50    --  110.30-111.00-150.00  124
 42  \w     79.00 139.00   0.50    3.50    --  110.30  50.00 120.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0293904000
_diffrn_orient_matrix_UB_12      0.0816097000
_diffrn_orient_matrix_UB_13      0.0150130000
_diffrn_orient_matrix_UB_21      -0.0489442000
_diffrn_orient_matrix_UB_22      -0.0429721000
_diffrn_orient_matrix_UB_23      -0.0188474000
_diffrn_orient_matrix_UB_31      -0.0063263000
_diffrn_orient_matrix_UB_32      -0.0468049000
_diffrn_orient_matrix_UB_33      0.0434521000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            118214
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.572
_diffrn_reflns_theta_min         1.647
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.867
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.442
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.108a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.362
_exptl_crystal_description       needle
_exptl_crystal_F_000             5304
_exptl_crystal_size_max          0.508
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.073
_refine_diff_density_max         1.392
_refine_diff_density_min         -0.583
_refine_diff_density_rms         0.089
_refine_ls_abs_structure_details
;
 Flack x determined using 11712 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.015(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2847
_refine_ls_number_reflns         47390
_refine_ls_number_restraints     199
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1165
_refine_ls_R_factor_gt           0.0858
_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^)+(0.1994P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2390
_refine_ls_wR_factor_ref         0.2759
_reflns_Friedel_coverage         0.868
_reflns_Friedel_fraction_full    0.964
_reflns_Friedel_fraction_max     0.931
_reflns_number_gt                32827
_reflns_number_total             47390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02375k2.cif
_cod_data_source_block           157fc
_cod_depositor_comments
'Adding full bibliography for 7719802--7719803.cif.'
_cod_original_cell_volume        12419.0(2)
_cod_database_code               7719802
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'S2 N O12 C40 H40 '
_chemical_oxdiff_usercomment     '100(2) K'
_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 C(H,H,H) groups
2. Restrained distances
 O9C-C6C
 1.45 with sigma of 0.02
 O3E-C2E
 1.45 with sigma of 0.02
 C7E-C8E
 1.4 with sigma of 0.02
 C5C-C6C
 1.4 with sigma of 0.02
 C14J-C13J
 1.49 with sigma of 0.02
 O9L-C13L = O10L-C13L
 1.26 with sigma of 0.02
 C13L-C14L
 1.5 with sigma of 0.02
 O9L-C14L
 2.38 with sigma of 0.04
 O10L-C14L
 2.39 with sigma of 0.04
 O9L-O10L
 2.19 with sigma of 0.04
 O9L-C14L \\sim C14L-O10L
 with sigma of 0.04
 C13L-O9L \\sim C13L-O10L
 with sigma of 0.02
3. Restrained planarity
 O9L, O10L, C13L, C14L
 with sigma of 0.1
4. Rigid bond restraints
 C2E, O3E, C7E, O4E, C8E
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O3E, C2E, C7E, O4E, C8E
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S3, C1C, C2C, C7C, C8C, O4C, O3C, C3C, O5C, C9C, O6C, C10C, O2C, C5C, C4C,
 O7C, C11C, C12C, O8C, C6C, O9C, C13C, O10C, C14C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2C, O3C, C7C, C8C, O4C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C4C, O7C, C11C, O8C, C12C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C6A, O9A, C14A, C13A, O10A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C6A, O9A, C13A, C14A, O10A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C6A, O9A, C14A, C13A, C5A, O10A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C5L, C6L, O9L, C13L, O10L, C14L
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
O3E \\sim C2E: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 1.7A
O9A \\sim C13A \\sim C14A \\sim O10A \\sim C6A: within 1.7A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 1.7A
O9L \\sim O10L \\sim C13L \\sim C14L: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(O8C) \\sim Ueq, Uanis(C11C) \\sim Ueq, Uanis(C12C) \\sim Ueq, Uanis(C7C)
\\sim Ueq, Uanis(O4C) \\sim Ueq, Uanis(C8C) \\sim Ueq, Uanis(O9A) \\sim Ueq,
Uanis(C13A) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(O10A) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.1
6. Rigid body (RIGU) restrains
 O9L, O10L, C13L, C14L
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Uiso: O10C(0.5) C13C(0.5) C14C(0.5) O3E(0.10648) C7E(0.17237)
 O4E(0.21772) C8E(0.2068)
 Fixed X: O3E(0.82252)
 Fixed Y: O3E(0.80974)
 Fixed Z: O3E(0.143291)
8.a Free rotating group:
 S3(O2C,C1C,C2C,C7C,O5C,O6C,C3C,C5C,C4C,C8C,C10C,O3C,C6C,O9C,O10C,C13C,C14C,
 C9C,O4C,O7C,O8C,C11C,C12C), O9A(C13A,C14A,O10A), O3E(C7E,O4E,C8E)
8.b Ternary CH refined with riding coordinates:
 C2A(H2A), C2I(H2I), C3I(H3I), C1A(H1A), C1I(H1I), C2H(H2H), C5K(H5K),
 C3A(H3A), C3B(H3B), C3H(H3H), C4I(H4I), C4H(H4H), C3G(H3G), C1F(H1F), C5L(H5L),
  C1L(H1L), C1E(H1E), C1H(H1H), C4K(H4K), C2L(H2L), C5E(H5E), C4G(H4G),
 C3K(H3K), C2F(H2F), C3J(H3J), C4B(H4B), C4L(H4L), C2B(H2B), C1K(H1K), C3L(H3L),
  C2K(H2K), C5H(H5H), C1J(H1J), C4A(H4A), C5I(H5I), C4F(H4F), C4J(H4J),
 C1G(H1G), C5J(H5J), C4E(H4E), C1B(H1B), C2J(H2J), C2G(H2G), C3F(H3F), C5G(H5G),
  C5B(H5B)
8.c Secondary CH2 refined with riding coordinates:
 C6E(H6EA,H6EB), C6I(H6IA,H6IB), C6L(H6LA,H6LB), C6K(H6KA,H6KB), C6G(H6GA,
 H6GB), C6J(H6JA,H6JB), C6B(H6BA,H6BB), C27(H27A,H27B), C26(H26A,H26B),
 C29(H29A,H29B), C28(H28A,H28B)
8.d Me refined with riding coordinates:
 C10C(H10,H,HA), C12K(H12G,H12H,H12I), C12E(H12Y,HB,HC), C12G(H12M,H12N,H12O),
 C10H(H10M,H10N,H10O), C10B(H10S,H10T,H10U), C10I(H10A,H10B,H10C), C14H(H14M,
 H14N,H14O), C8H(H8HA,H8HB,H8HC), C10A(H10V,H10W,H10X), C12F(H12Z,HD,HE),
 C10J(H10D,H10E,H10F), C8I(H8IA,H8IB,H8IC), C10F(H10Y,HF,HG), C12B(H12S,H12T,
 H12U), C12I(H12A,H12B,H12C), C8A(H8AA,H8AB,H8AC), C10K(H10G,H10H,H10I),
 C8F(H8FA,H8FB,H8FC), C12J(H12D,H12E,H12F), C10L(H10J,H10K,H10L), C8L(H8LA,H8LB,
 H8LC), C14K(H14G,H14H,H14I), C14I(H14A,H14B,H14C), C8K(H8KA,H8KB,H8KC),
 C14E(H14V,H14W,H14X), C10G(H10P,H10Q,H10R), C8G(H8GA,H8GB,H8GC), C12H(H12P,
 H12Q,H12R), C8J(H8JA,H8JB,H8JC), C8B(H8BA,H8BB,H8BC), C12A(H12V,H12W,H12X),
 C14G(H14P,H14Q,H14R), C14B(H14S,H14T,H14U), C12L(H12J,H12K,H12L), C10E(H10Z,HH,
 HI), C14J(H14D,H14E,H14F), C30(H30A,H30B,H30C), C25(H25A,H25B,H25C), C14L(H14J,
 H14K,H14L)
8.e Aromatic/amide H refined with riding coordinates:
 N4(H4), N3(H3), N6(H6), N5(H5), N1(H1), N2(H2), C6H(H6H)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;