Covalent hybrids based on Re(I) tricarbonyl complexes and polypyridine-functionalized polyoxometalate: synthesis, characterization and electronic properties
Auvray, Thomas; Santoni, Marie-Pierre; Hasenknopf, Bernold; Hanan, Garry; Dalton Trans.  (2017) –; doi:10.1039/C7DT01674C

data_7043544
_publ_section_title
;
 Covalent hybrids based on Re(I) tricarbonyl complexes and
 polypyridine-functionalized polyoxometalate: synthesis, characterization
 and electronic properties
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT01674C
_journal_year                    2017
_chemical_formula_moiety         'C16 H16 N3 O63 P2 V3 W15, 3(C16 H36 N)'
_chemical_formula_sum            'C64 H124 N6 O63 P2 V3 W15'
_chemical_formula_weight         4958.19
_chemical_name_common            D-bpy
_chemical_name_systematic        4
_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             2017-06-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-06-28 deposited with the CCDC.
2017-07-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.0308(10)
_cell_length_b                   36.9998(13)
_cell_length_c                   15.5102(5)
_cell_measurement_reflns_used    9926
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      54.050
_cell_measurement_theta_min      3.407
_cell_volume                     16086.2(10)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'APEX2 (Bruker)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1004
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            413250
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.255
_diffrn_reflns_theta_min         1.720
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    15.072
_exptl_absorpt_correction_T_max  0.1434
_exptl_absorpt_correction_T_min  0.0435
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1654 before and 0.1230 after correction.
The Ratio of minimum to maximum transmission is 0.3033.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    2.047
_exptl_crystal_description       plate
_exptl_crystal_F_000             9052
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile/diisopropyl ether'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.04
_refine_diff_density_max         3.516
_refine_diff_density_min         -1.277
_refine_diff_density_rms         0.254
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.255(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1380
_refine_ls_number_reflns         29712
_refine_ls_number_restraints     674
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0726
_refine_ls_R_factor_gt           0.0652
_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^)+(0.1109P)^2^+215.7634P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1782
_refine_ls_wR_factor_ref         0.1867
_reflns_Friedel_coverage         0.857
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                26464
_reflns_number_total             29712
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt01674c2.cif
_cod_data_source_block           auvr28
_cod_database_code               7043544
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.584
_shelx_estimated_absorpt_t_min   0.162
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.745(19)
 0.255(19)
2. 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
3. Restrained distances
 C9-C10 = C6-C10 = C7-C6 = C8-C7 = C12-C11 = C15-C14 = C13-C14 = C13-C12
 1.39 with sigma of 0.02
 N3-C11 = N3-C15 = N2-C9 = N2-C8
 1.37 with sigma of 0.02
 C16-C13
 1.5 with sigma of 0.02
 C4-C1 = C4-C3 = C4-C2
 1.54 with sigma of 0.02
 O1-C5
 1.23 with sigma of 0.01
 C16A-C12A = C8A-C12A = C8A-C4A = N1A-C4A = N1A-C2A = C6A-C2A = C6A-C10A =
 C14A-C10A = C9A-C13A = C9A-C5A = C5A-C1A = N1A-C1A = N1A-C3A = C7A-C3A = C7A-
 C11A = C15A-C11A
 1.5 with sigma of 0.02
 C15B-C11B = C7B-C11B = C7B-C3B = N1B-C3B = N1B-C1B = C5B-C1B = C9B-C5B = C9B-
 C13B = C14B-C10B = C6B-C10B = C6B-C2B = N1B-C2B = N1B-C4B = C8B-C4B = C8B-C12B
 = C16B-C12B
 1.5 with sigma of 0.02
 C9C-C13C = C9C-C5C = C5C-C1C = N1C-C1C = N1C-C2C = C6C-C2C = C6C-C10C = C14C-
 C10C = N1C-C3C = C7C-C3C = C7C-C11C = C15C-C11C = N1C-C4C = C8C-C4C = C8C-C12C
 = C16C-C12C
 1.5 with sigma of 0.02
 C13C-C5C = C14C-C6C = C15C-C7C = C16C-C8C = C9C-C1C = C10C-C2C = C11C-C3C =
 C12C-C4C = C5C-N1C = C6C-N1C = C7C-N1C = C8C-N1C
 2.5 with sigma of 0.04
4. Restrained planarity
 O1, N1, N2, N3, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
O1 \\sim N1 \\sim C5: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
C7 \\sim C8: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
N1B \\sim C1B \\sim C2B \\sim C3B \\sim C4B \\sim C5B \\sim C6B \\sim C7B \\sim
C8B \\sim C9B \\sim C10B \\sim C11B \\sim C12B \\sim C13B \\sim C14B \\sim C15B
\\sim C16B: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.002
C12C \\sim N1C \\sim C1C \\sim C2C \\sim C3C \\sim C4C \\sim C5C \\sim C6C
\\sim C7C \\sim C8C \\sim C9C \\sim C10C \\sim C11C \\sim C13C \\sim C14C \\sim
C15C \\sim C16C: within 2A with sigma of 0.003 and sigma for terminal atoms of
0.006
6. Rigid body (RIGU) restrains
 N1A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A,
 C14A, C15A, C16A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N1C, C1C, C3C, C4C, C5C, C6C, C7C, C8C, C9C, C10C, C11C, C12C, C13C, C14C,
 C15C, C16C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O1, N1, N2, N3, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 P2, O48, O49, O50, O57
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C1A(H1AA,H1AB), C2A(H2AA,H2AB),
 C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C6A(H6AA,H6AB), C7A(H7AA,H7AB),
  C8A(H8AA,H8AB), C9A(H9AA,H9AB), C10A(H10A,H10B), C11A(H11A,H11B), C12A(H12A,
 H12B), C1B(H1BA,H1BB), C2B(H2BA,H2BB), C3B(H3BA,H3BB), C4B(H4BA,H4BB),
 C5B(H5BA,H5BB), C6B(H6BA,H6BB), C7B(H7BA,H7BB), C8B(H8BA,H8BB), C9B(H9BA,H9BB),
  C10B(H10C,H10D), C11B(H11C,H11D), C12B(H12C,H12D), C1C(H1CA,H1CB), C2C(H2CA,
 H2CB), C3C(H3CA,H3CB), C4C(H4CA,H4CB), C5C(H5CA,H5CB), C6C(H6CA,H6CB),
 C7C(H7CA,H7CB), C8C(H8CA,H8CB), C9C(H9CA,H9CB), C10C(H10E,H10F), C11C(H11E,
 H11F), C12C(H12E,H12F)
7.b Me refined with riding coordinates:
 C13A(H13A,H13B,H13C), C14A(H14A,H14B,H14C), C15A(H15A,H15B,H15C), C16A(H16D,
 H16E,H16F), C13B(H13D,H13E,H13F), C14B(H14D,H14E,H14F), C15B(H15D,H15E,H15F),
 C16B(H16G,H16H,H16I), C13C(H13G,H13H,H13I), C14C(H14G,H14H,H14I), C15C(H15G,
 H15H,H15I), C16C(H16J,H16K,H16L)
7.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C7(H7), C8(H8), C10(H10), C12(H12), C14(H14), C15(H15)
7.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              4881
_shelx_fab_checksum              35503
_olex2_submission_special_instructions 'No special instructions were received'