C-C bond cleavage and carbonylation enabled by an NNN-pincer uranium scaffold <i>via</i> metal-arene interaction.
Pang, Yue; Rajeshkumar, Thayalan; Scopelliti, Rosario; Maron, Laurent; Mazzanti, Marinella; Chemical science 16 (2025) 16101–16109; doi:10.1039/d5sc04248h

data_1575209
_publ_section_title
;
 C-C bond cleavage and carbonylation enabled by an NNN-pincer uranium
 scaffold <i>via</i> metal-arene interaction.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              16101
_journal_page_last               16109
_journal_paper_doi               10.1039/d5sc04248h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C59 H86 N3 O3 U, 2[C4H8O]'
_chemical_formula_sum            'C67 H102 N3 O5 U'
_chemical_formula_weight         1267.603
_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_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-06-06 deposited with the CCDC.	2025-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.1738(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.4069(4)
_cell_length_b                   15.1709(2)
_cell_length_c                   30.0450(4)
_cell_measurement_reflns_used    16330
_cell_measurement_temperature    140.00(12)
_cell_measurement_theta_max      72.4510
_cell_measurement_theta_min      3.2190
_cell_volume                     12895.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.44.93a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.92a 64-bit (release 31-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.93a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.9963
_diffrn_measured_fraction_theta_max 0.9687
_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   -112.00 -14.00   1.00   10.00    --  -40.66 -48.00  17.00   98
  2  \w    -48.00   5.00   1.00   10.00    --  -40.66  48.00 164.00   53
  3  \w     -7.00  18.00   1.00   10.00    --   40.66 -48.00  17.00   25
  4  \w     29.00 104.00   1.00   10.00    --   40.66  48.00 164.00   75
  5  \w     79.00 169.00   1.00   40.00    --  105.15  48.00 164.00   90
  6  \w     34.00 113.00   1.00   40.00    --  105.15 -48.00  17.00   79
  7  \w    -86.00 -17.00   1.00   10.00    --  -40.66 125.00-180.00   69
  8  \w     35.00  95.00   1.00   10.00    --   40.66-125.00 -30.00   60
  9  \w     48.00  75.00   1.00   10.00    --   40.66  38.00 -30.00   27
 10  \w    113.00 167.00   1.00   40.00    --  105.15 111.00  60.00   54
 11  \w     76.00 120.00   1.00   40.00    --  105.15 -45.00 150.00   44
 12  \w    115.00 167.00   1.00   40.00    --  105.15 111.00 120.00   52
 13  \w     36.00  64.00   1.00   40.00    --  105.15 -45.00 150.00   28
 14  \w    107.00 140.00   1.00   40.00    --  105.15 178.00-120.00   33
 15  \w    103.00 178.00   1.00   40.00    --  105.15  77.00  90.00   75
 16  \w     32.00 109.00   1.00   40.00    --  105.15-111.00  60.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0541994000
_diffrn_orient_matrix_UB_12      -0.0008721000
_diffrn_orient_matrix_UB_13      0.0095733000
_diffrn_orient_matrix_UB_21      -0.0039714000
_diffrn_orient_matrix_UB_22      0.0601205000
_diffrn_orient_matrix_UB_23      0.0408369000
_diffrn_orient_matrix_UB_31      -0.0034835000
_diffrn_orient_matrix_UB_32      -0.0818137000
_diffrn_orient_matrix_UB_33      0.0298688000
_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  0.0782
_diffrn_reflns_av_unetI/netI     0.0899
_diffrn_reflns_Laue_measured_fraction_full 0.9963
_diffrn_reflns_Laue_measured_fraction_max 0.9687
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            67959
_diffrn_reflns_point_group_measured_fraction_full 0.9963
_diffrn_reflns_point_group_measured_fraction_max 0.9687
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         72.92
_diffrn_reflns_theta_min         3.12
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.454
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.468
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.93a (Rigaku Oxford Diffraction, 2025)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       prism
_exptl_crystal_F_000             5236.441
_exptl_crystal_size_max          0.193
_exptl_crystal_size_mid          0.044
_exptl_crystal_size_min          0.038
_refine_diff_density_max         3.2595
_refine_diff_density_min         -1.9480
_refine_diff_density_rms         0.2165
_refine_ls_d_res_high            0.8065
_refine_ls_d_res_low             14.1456
_refine_ls_goodness_of_fit_ref   1.0224
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    317
_refine_ls_number_parameters     1412
_refine_ls_number_reflns         24945
_refine_ls_number_restraints     1812
_refine_ls_restrained_S_all      0.9852
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0549
_refine_ls_shift/su_max          -0.0009
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0609P)^2^+2.6153P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1253
_refine_ls_wR_factor_ref         0.1399
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              24
_reflns_limit_h_min              -35
_reflns_limit_k_max              18
_reflns_limit_k_min              0
_reflns_limit_l_max              37
_reflns_limit_l_min              -23
_reflns_number_gt                18276
_reflns_number_total             24945
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc04248h3.cif
_cod_data_source_block           YP254
_cod_depositor_comments
'Adding full bibliography for 1575203--1575209.cif.'
_cod_original_formula_sum        'C67 H102 N3 O5 U1'
_cod_database_code               1575209
_chemical_oxdiff_formula         'C67 H102 N3 O5 U1'
_chemical_oxdiff_usercomment     'CSD: SORCEJ'
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C58-C57
 1.54 with sigma of 0.02
 C21-C20 \\sim C23-C20 \\sim C22-C20 \\sim C20-C119 \\sim C20-C121 \\sim
C20-C120
 with sigma of 0.02
 C21-C22 \\sim C22-C23 \\sim C21-C23
 with sigma of 0.02
 C119-C121 \\sim C121-C120 \\sim C119-C120
 with sigma of 0.02
 C96-C101 \\sim C96-C122
 with sigma of 0.02
 C103-C101 \\sim C102-C101 \\sim C123-C122 \\sim C124-C122
 with sigma of 0.02
 C123-C124 \\sim C103-C102
 with sigma of 0.02
 C51-C48 \\sim C51-C49 \\sim C48-C125 \\sim C50-C49 \\sim C126-C125 \\sim
C50-C127
 with sigma of 0.02
 O1-C126 \\sim O1-C127 \\sim O1-C51
 with sigma of 0.02
 C82-C79 \\sim C79-C128 \\sim C81-C79 \\sim C79-C130 \\sim C80-C79 \\sim
C79-C129
 with sigma of 0.02
 C82-C81 \\sim C81-C80 \\sim C80-C82
 with sigma of 0.02
 C129-C128 \\sim C128-C130 \\sim C129-C130
 with sigma of 0.02
 C46-C45 \\sim C45-C131 \\sim C47-C45 \\sim C45-C132
 with sigma of 0.02
 C46-C47 \\sim C131-C132
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C20 \\sim C21 \\sim C120 \\sim C119 \\sim C23 \\sim C121 \\sim C22: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C51 \\sim O1 \\sim C49 \\sim C48 \\sim C125 \\sim C50 \\sim C126 \\sim C127:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C79 \\sim C82 \\sim C128 \\sim C81 \\sim C130 \\sim C129 \\sim C80: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C96 \\sim C101 \\sim C103 \\sim C123 \\sim C102 \\sim C124 \\sim C122: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C45 \\sim C46 \\sim C131 \\sim C47 \\sim C132: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
Uanis(C31) \\sim Ueq, Uanis(C58) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C119)=Sof(H11a)=Sof(H11b)=Sof(H11c)=Sof(C120)=Sof(H12a)=Sof(H12b)=
 Sof(H12c)=Sof(C121)=Sof(H12d)=Sof(H12e)=Sof(H12f)=1-FVAR(1)
 Sof(C21)=Sof(H21a)=Sof(H21b)=Sof(H21c)=Sof(C22)=Sof(H22a)=Sof(H22b)=Sof(H22c)=
 Sof(C23)=Sof(H23a)=Sof(H23b)=Sof(H23c)=FVAR(1)
 Sof(C124)=Sof(H12m)=Sof(H12n)=Sof(H12o)=Sof(C123)=Sof(H12p)=Sof(H12q)=
 Sof(H12r)=Sof(C122)=Sof(H122)=1-FVAR(2)
 Sof(C101)=Sof(H101)=Sof(C102)=Sof(H10a)=Sof(H10b)=Sof(H10c)=Sof(C103)=
 Sof(H10d)=Sof(H10e)=Sof(H10f)=FVAR(2)
 Sof(H51c)=Sof(H51d)=Sof(C125)=Sof(H12i)=Sof(H12j)=Sof(C48)=Sof(H48a)=
 Sof(H48b)=Sof(C126)=Sof(H12k)=Sof(H12l)=1-FVAR(3)
 Sof(H51a)=Sof(H51b)=Sof(C127)=Sof(H12g)=Sof(H12h)=Sof(C49)=Sof(H49a)=
 Sof(H49b)=Sof(C50)=Sof(H50a)=Sof(H50b)=FVAR(3)
 Sof(C130)=Sof(H13g)=Sof(H13h)=Sof(H13i)=Sof(C128)=Sof(H12s)=Sof(H12t)=
 Sof(H12u)=Sof(C129)=Sof(H12v)=Sof(H12w)=Sof(H12x)=1-FVAR(4)
 Sof(C80)=Sof(H80a)=Sof(H80b)=Sof(H80c)=Sof(C81)=Sof(H81a)=Sof(H81b)=Sof(H81c)=
 Sof(C82)=Sof(H82a)=Sof(H82b)=Sof(H82c)=FVAR(4)
 Sof(H45a)=Sof(C131)=Sof(H13a)=Sof(H13b)=Sof(H13c)=Sof(C132)=Sof(H13d)=
 Sof(H13e)=Sof(H13f)=1-FVAR(5)
 Sof(H45)=Sof(C46)=Sof(H46a)=Sof(H46b)=Sof(H46c)=Sof(C47)=Sof(H47a)=Sof(H47b)=
 Sof(H47c)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33), C42(H42), C45(H45), C45(H45a), C89(H89), C92(H92),
 C101(H101), C104(H104), C122(H122)
6.b Secondary CH2 refined with riding coordinates:
 C51(H51c,H51d), C51(H51a,H51b), C52(H52a,H52b), C53(H53a,H53b), C54(H54a,
 H54b), C55(H55a,H55b), C56(H56a,H56b), C57(H57a,H57b), C58(H58a,H58b),
 C59(H59a,H59b), C107(H10m,H10n), C108(H10o,H10p), C109(H10q,H10r), C110(H11d,
 H11e), C111(H11f,H11g), C112(H11h,H11i), C113(H11j,H11k), C114(H11l,H11m),
 C115(H11n,H11o), C116(H11p,H11q), C117(H11r,H11s), C118(H11t,H11u), C127(H12g,
 H12h), C125(H12i,H12j), C48(H48a,H48b), C49(H49a,H49b), C126(H12k,H12l),
 C50(H50a,H50b)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C11(H11), C13(H13), C26(H26), C27(H27), C28(H28), C38(H38),
 C39(H39), C40(H40), C61(H61), C63(H63), C70(H70), C72(H72), C85(H85), C86(H86),
  C87(H87), C97(H97), C98(H98), C99(H99)
6.d Idealised Me refined as rotating group:
 C15(H15a,H15b,H15c), C16(H16a,H16b,H16c), C17(H17a,H17b,H17c), C18(H18a,H18b,
 H18c), C19(H19a,H19b,H19c), C21(H21a,H21b,H21c), C22(H22a,H22b,H22c), C23(H23a,
 H23b,H23c), C31(H31a,H31b,H31c), C32(H32a,H32b,H32c), C34(H34a,H34b,H34c),
 C35(H35a,H35b,H35c), C43(H43a,H43b,H43c), C44(H44a,H44b,H44c), C46(H46a,H46b,
 H46c), C47(H47a,H47b,H47c), C74(H74a,H74b,H74c), C75(H75a,H75b,H75c), C76(H76a,
 H76b,H76c), C77(H77a,H77b,H77c), C78(H78a,H78b,H78c), C80(H80a,H80b,H80c),
 C81(H81a,H81b,H81c), C82(H82a,H82b,H82c), C90(H90a,H90b,H90c), C91(H91a,H91b,
 H91c), C93(H93a,H93b,H93c), C94(H94a,H94b,H94c), C102(H10a,H10b,H10c),
 C103(H10d,H10e,H10f), C105(H10g,H10h,H10i), C106(H10j,H10k,H10l), C119(H11a,
 H11b,H11c), C120(H12a,H12b,H12c), C121(H12d,H12e,H12f), C124(H12m,H12n,H12o),
 C123(H12p,H12q,H12r), C130(H13g,H13h,H13i), C128(H12s,H12t,H12u), C129(H12v,
 H12w,H12x), C131(H13a,H13b,H13c), C132(H13d,H13e,H13f)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 597 electrons were 
found in a volume of 3183\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C4H8O] per formula unit 
which account for 640 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_date_sample_data_collection 2025-02-11
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.037
_oxdiff_exptl_absorpt_empirical_full_min 0.616