A di-nuclear μ-oxido rhenium(VI) complex: from deep purple to catalytic applications.
Doliner, Tobias A.; Hartmann, Peter E.; Oberwinkler, Gernot; Belaj, Ferdinand; Dupé, Antoine; Boese, A. Daniel; Schachner, Jörg A; Dalton transactions (Cambridge, England : 2003) 55 (2026) 4547–4559; doi:10.1039/d6dt00039h

data_7720391
_publ_section_title
;
 A di-nuclear &#x3bc;-oxido rhenium(VI) complex: from deep purple to
 catalytic applications.
;
_journal_issue                   11
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4547
_journal_page_last               4559
_journal_paper_doi               10.1039/d6dt00039h
_journal_volume                  55
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         '1(C37 H43 Cl2 N O3 P Re), 0.5(C6 H14)'
_chemical_formula_sum            'C37 H43 Cl2 N O3 P Re'
_chemical_formula_weight         837.79
_chemical_name_systematic
(2,4-t-butyl-6-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)phenolato)-dichlorido-oxido-triphenylphosphine-rhenium(V)
_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             2025-09-25
_audit_creation_method
;
Olex2 1.5-ac7-014
(compiled 2025.02.27 svn.r6f4c0eaf for Rigaku Oxford Diffraction, GUI svn.r7171)
;
_audit_update_record
;
2025-11-04 deposited with the CCDC.	2026-02-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.2780(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.28730(10)
_cell_length_b                   10.78790(10)
_cell_length_c                   22.2775(2)
_cell_measurement_reflns_used    49518
_cell_measurement_temperature    99.9(8)
_cell_measurement_theta_max      78.4170
_cell_measurement_theta_min      3.3330
_cell_volume                     3913.31(6)
_computing_cell_refinement       'CrysAlisPro 1.171.44.122a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 43.129a 64-bit (release 29-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.44.122a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5-ac7-014 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-014 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.9(8)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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    -43.00  -7.00   0.50    0.20    --    4.00 117.00 -70.71   72
  2  \w    -37.00  -9.00   0.50    0.20    --   12.00 120.00  -3.20   56
  3  \w    -21.00  12.00   0.50    0.20    --   12.00  92.00  95.61   66
  4  \w    100.00 174.00   0.50    0.65    --  106.75  77.00 -30.00  148
  5  \w    149.00 174.00   0.50    0.65    --  106.75  77.00 -30.00   50
  6  \w    137.00 171.00   0.50    0.65    --  106.75  77.00  30.00   68
  7  \w    134.00 172.00   0.50    0.65    --  106.75  77.00  90.00   76
  8  \w    104.00 130.00   0.50    0.65    --  106.75  77.00  30.00   52
  9  \w    103.00 151.00   0.50    0.65    --  106.75  77.00  60.00   96
 10  \w     94.00 175.00   0.50    0.65    --  106.75  45.00 150.00  162
 11  \w     91.00 178.00   0.50    0.65    --  106.75  61.00   0.00  174
 12  \w    127.00 177.00   0.50    0.65    --  106.75  45.00 -90.00  100
 13  \w    146.00 172.00   0.50    0.65    --  106.75  45.00-150.00   52
 14  \w     93.00 132.00   0.50    0.65    --  106.75  45.00-150.00   78
 15  \w     93.00 178.00   0.50    0.65    --  106.75  45.00-120.00  170
 16  \w    139.00 177.00   0.50    0.65    --  106.75  30.00  60.00   76
 17  \w     90.00 125.00   0.50    0.65    --  106.75  30.00  60.00   70
 18  \w     41.00  95.00   0.50    0.65    --  106.75   0.00  30.00  108
 19  \w      9.00  39.00   0.50    0.20    --   28.00  66.00-121.14   60
 20  \w     13.00  42.00   0.50    0.20    --   32.00  64.00 -65.27   58
 21  \w    152.00 177.00   0.50    0.65    --  106.75   0.00  30.00   50
 22  \w    130.00 168.00   0.50    0.65    --  106.75 125.00-150.00   76
 23  \w    140.00 166.00   0.50    0.65    --  106.75 125.00-180.00   52
 24  \w    123.00 157.00   0.50    0.65    --  106.75 125.00-120.00   68
 25  \w    117.00 153.00   0.50    0.65    --  106.75 125.00 -90.00   72
 26  \w    124.00 151.00   0.50    0.65    --  106.75 125.00 -30.00   54
 27  \w    124.00 163.00   0.50    0.65    --  106.75 125.00 -60.00   78
 28  \w     36.00  61.00   0.50    0.65    --  106.75 -61.00 -60.00   50
 29  \w     35.00  70.00   0.50    0.65    --  106.75 -61.00 -90.00   70
 30  \w     41.00  92.00   0.50    0.65    --  106.75 -77.00 -90.00  102
 31  \w     63.00  89.00   0.50    0.65    --  106.75 -77.00 -60.00   52
 32  \w     46.00  89.00   0.50    0.65    --  106.75 -77.00  30.00   86
 33  \w     38.00  70.00   0.50    0.65    --  106.75 -61.00  30.00   64
 34  \w     34.00  71.00   0.50    0.65    --  106.75 -61.00  60.00   74
 35  \w     41.00  67.00   0.50    0.65    --  106.75 -77.00 150.00   52
 36  \w    103.00 129.00   0.50    0.65    --  106.75-149.00 166.00   52
 37  \w     72.00 110.00   0.50    0.65    --  106.75-125.00 120.00   76
 38  \w     37.00  62.00   0.50    0.65    --  106.75-125.00 120.00   50
 39  \w     39.00  64.00   0.50    0.65    --  106.75-125.00  30.00   50
 40  \w     87.00 112.00   0.50    0.65    --  106.75-125.00  30.00   50
 41  \w     67.00  93.00   0.50    0.65    --  106.75-125.00  60.00   52
 42  \w     51.00 110.00   0.50    0.65    --  106.75-125.00 150.00  118
 43  \w     38.00  66.00   0.50    0.65    --  106.75-125.00 -30.00   56
 44  \w     82.00 111.00   0.50    0.65    --  106.75-125.00   0.00   58
 45  \w     40.00 105.00   0.50    0.65    --  106.75 -95.00 150.00  130
 46  \w     86.00 112.00   0.50    0.65    --  106.75-125.00 -30.00   52
 47  \w     86.00 112.00   0.50    0.65    --  106.75-125.00 -60.00   52
 48  \w     39.00 112.00   0.50    0.65    --  106.75-125.00-150.00  146
 49  \w     80.00 105.00   0.50    0.65    --  106.75 -95.00-180.00   50
 50  \w     78.00 104.00   0.50    0.65    --  106.75 -95.00-150.00   52
 51  \w     44.00  75.00   0.50    0.65    --  106.75 -95.00-180.00   62
 52  \w     41.00 105.00   0.50    0.65    --  106.75 -95.00-120.00  128
 53  \w     41.00  90.00   0.50    0.65    --  106.75 -95.00 -90.00   98
 54  \w     75.00 103.00   0.50    0.65    --  106.75 -95.00 120.00   56
 55  \w     79.00 105.00   0.50    0.65    --  106.75 -95.00  30.00   52
 56  \w     52.00 105.00   0.50    0.65    --  106.75 -95.00   0.00  106
 57  \w     54.00  88.00   0.50    0.65    --  110.00 -86.00-161.74   68
 58  \w    114.00 139.00   0.50    0.65    --  110.00 -86.00-161.74   50
 59  \w    -61.00 -16.00   0.50    0.20    --   -4.00 131.00-160.74   90
 60  \w   -163.00 -71.00   0.50    0.65    --  -88.00 -53.00-121.82  184
 61  \w   -139.00 -48.00   0.50    0.20    --  -64.00 -52.00 -15.04  182
 62  \w   -142.00 -51.00   0.50    0.20    --  -68.00 -56.00  72.58  182
 63  \w   -147.00-100.00   0.50    0.20    --  -80.27 -77.00 -30.00   94
 64  \w    -26.00  25.00   0.50    0.20    --  -51.45  19.00  90.00  102
 65  \w    -35.00  -3.00   0.50    0.20    --  -80.27  30.00 120.00   64
 66  \w   -105.00 -13.00   0.50    0.20    --  -80.27  77.00  60.00  184
 67  \w    -35.00  -3.00   0.50    0.20    --  -80.27  30.00  30.00   64
 68  \w    -35.00  -3.00   0.50    0.20    --  -80.27  30.00 -30.00   64
 69  \w    -51.00  -4.00   0.50    0.20    --  -80.27  45.00-120.00   94
 70  \w   -105.00 -13.00   0.50    0.20    --  -80.27  77.00-180.00  184
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0020076000
_diffrn_orient_matrix_UB_12      -0.0271482000
_diffrn_orient_matrix_UB_13      0.0678372000
_diffrn_orient_matrix_UB_21      -0.0193158000
_diffrn_orient_matrix_UB_22      0.1373877000
_diffrn_orient_matrix_UB_23      0.0121879000
_diffrn_orient_matrix_UB_31      -0.0926095000
_diffrn_orient_matrix_UB_32      -0.0280397000
_diffrn_orient_matrix_UB_33      -0.0056157000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            15976
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.481
_diffrn_reflns_theta_min         2.714
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.973
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.529
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.122a (Rigaku Oxford Diffraction, 2025)
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    1.422
_exptl_crystal_description       plate
_exptl_crystal_F_000             1680
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM / hexane'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.776
_refine_diff_density_min         -1.586
_refine_diff_density_rms         0.146
_refine_ls_abs_structure_details
;
 Flack x determined using 6503 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.038(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     890
_refine_ls_number_reflns         15976
_refine_ls_number_restraints     255
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0506
_refine_ls_R_factor_gt           0.0474
_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^)+(0.0713P)^2^+16.7244P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1232
_refine_ls_wR_factor_ref         0.1255
_reflns_Friedel_coverage         0.890
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                14988
_reflns_number_total             15976
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00039h2.cif
_cod_data_source_block           ad99-2
_cod_depositor_comments
'Adding full bibliography for 7720387--7720392.cif.'
_cod_database_code               7720391
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C37 H43 N1 O3 P1 Cl2 Re1 '
_chemical_oxdiff_usercomment     TD66
_shelx_estimated_absorpt_t_max   0.857
_shelx_estimated_absorpt_t_min   0.448
_diffrn_oxdiff_ac3_digest_hkl    416e41fd53da3f9c81756ff4391de0e30d9842
_diffrn_oxdiff_digest_creation
;
CAP 1.171.44.122a, AC 1.5-ac6-020
;
_diffrn_oxdiff_digest_hkl
;
_FRAME_DIGEST_NOT_VALID_
;
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name AD99.par
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8938(19)
 0.1062(19)
2. 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
3. Restrained distances
 C36-C35 = C33-C38 = C38-C37
 1.37 with sigma of 0.02
 C36-C37
 1.38 with sigma of 0.02
 C35-C34 = C34-C33
 1.36 with sigma of 0.02
 C36-C34 = C34-C38 = C33-C37
 2.37 with sigma of 0.04
 C36-C38
 2.38 with sigma of 0.04
 C35-C33
 2.36 with sigma of 0.04
 C56-C57 \\sim C56-C79
 with sigma of 0.02
 C56-C58 \\sim C56-C77
 with sigma of 0.02
 C56-C59 \\sim C56-C78
 with sigma of 0.02
 C16-C17 \\sim C16-C67
 with sigma of 0.02
 C16-C18 \\sim C16-C68
 with sigma of 0.02
 C16-C19 \\sim C16-C69
 with sigma of 0.02
 C36-C35 \\sim C35-C34 \\sim C34-C33 \\sim C33-C38 \\sim C38-C37 \\sim C37-C36
 with sigma of 0.02
 C36-C38 \\sim C36-C34 \\sim C38-C34 \\sim C33-C35 \\sim C33-C37 \\sim C37-C35
 with sigma of 0.04
4. Restrained planarity
 C33, C34, C35, C36, C37, C38
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19 \\sim C67 \\sim C68 \\sim C69: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C57 \\sim C58 \\sim C59 \\sim C77 \\sim C78 \\sim C79: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
6. Rigid body (RIGU) restrains
 C56, C57, C58, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C56, C77, C78, C79
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C17, C18, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C67, C68, C69
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33, C34, C35, C36, C37, C38
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C77)=Sof(H771)=Sof(H772)=Sof(H773)=Sof(C78)=Sof(H781)=Sof(H782)=Sof(H783)=
 Sof(C79)=Sof(H791)=Sof(H792)=Sof(H793)=1-FVAR(1)
 Sof(C57)=Sof(H571)=Sof(H572)=Sof(H573)=Sof(C58)=Sof(H581)=Sof(H582)=Sof(H583)=
 Sof(C59)=Sof(H591)=Sof(H592)=Sof(H593)=FVAR(1)
 Sof(C67)=Sof(H671)=Sof(H672)=Sof(H673)=Sof(C68)=Sof(H681)=Sof(H682)=Sof(H683)=
 Sof(C69)=Sof(H691)=Sof(H692)=Sof(H693)=1-FVAR(2)
 Sof(C17)=Sof(H171)=Sof(H172)=Sof(H173)=Sof(C18)=Sof(H181)=Sof(H182)=Sof(H183)=
 Sof(C19)=Sof(H191)=Sof(H192)=Sof(H193)=FVAR(2)
8.a Secondary CH2 refined with riding coordinates:
 C8(H81,H82), C48(H481,H482)
8.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C28(H28),
 C29(H29), C30(H30), C31(H31), C32(H32), C34(H34), C35(H35), C36(H36), C37(H37),
  C38(H38), C39(H39), C40(H40), C43(H43), C45(H45), C60(H60), C62(H62),
 C63(H63), C64(H64), C65(H65), C66(H66), C70(H70), C71(H71), C72(H72), C74(H74),
  C75(H75), C76(H76), C80(H80)
8.c Idealised Me refined as rotating group:
 C10(H101,H102,H103), C11(H111,H112,H113), C13(H131,H132,H133), C14(H141,H142,
 H143), C15(H151,H152,H153), C17(H171,H172,H173), C18(H181,H182,H183), C19(H191,
 H192,H193), C67(H671,H672,H673), C68(H681,H682,H683), C69(H691,H692,H693),
 C50(H501,H502,H503), C51(H511,H512,H513), C53(H531,H532,H533), C54(H541,H542,
 H543), C55(H551,H552,H553), C57(H571,H572,H573), C58(H581,H582,H583), C59(H591,
 H592,H593), C77(H771,H772,H773), C78(H781,H782,H783), C79(H791,H792,H793)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 96 electrons were 
found in a volume of 554\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
0.5 (C6 H14) per Asymmetric Unit 
which account for 100 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              34202
_shelx_fab_checksum              97094
_olex2_date_sample_data_collection 2024-08-30
_olex2_date_sample_submission    2024-08-07
_olex2_exptl_crystal_mounting_method 'The crystal was mounted on a MiTeGen loop'
_olex2_submission_original_sample_id JSA-TD66
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.590
_oxdiff_exptl_absorpt_empirical_full_min 0.758