Na[Tc(CO)(CN<i>p</i>-F-Ar<sup>DArF2</sup>)<sub>4</sub>]: an isocyanide analogue of the elusive Na[Tc(CO)<sub>5</sub>].
Salsi, Federico; Hagenbach, Adelheid; Figueroa, Joshua S.; Abram, Ulrich; Chemical communications (Cambridge, England) 59 (2023) 4028–4031; doi:10.1039/d3cc00946g

data_7131398
_publ_section_title
;
 Na[Tc(CO)(CN<i>p</i>-F-Ar<sup>DArF2</sup>)<sub>4</sub>]: an isocyanide
 analogue of the elusive Na[Tc(CO)<sub>5</sub>].
;
_journal_issue                   27
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              4028
_journal_page_last               4031
_journal_paper_doi               10.1039/d3cc00946g
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety
'C93 H32 F52 N4 O Tc, C18 H36 N2 Na O6, 0.5(C4 H8 O), 0.25(C7 H8)'
_chemical_formula_sum            'C114.75 H74 F52 N6 Na O7.5 Tc'
_chemical_formula_weight         2765.79
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-12-08
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2023-01-30 deposited with the CCDC.	2023-03-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.0673(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.0710(4)
_cell_length_b                   23.6777(4)
_cell_length_c                   24.0500(5)
_cell_measurement_reflns_used    9739
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      73.74
_cell_measurement_theta_min      2.82
_cell_volume                     11880.1(4)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL n/a (Sheldrick, 2015)'
_computing_structure_solution    'XT n/a (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CMOS area detector'
_diffrn_detector_type            'PHOTON 100'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       'Bruker D8 Venture Duo'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'W/C multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~2,3~
_diffrn_reflns_av_R_equivalents  0.0918
_diffrn_reflns_av_unetI/netI     0.0528
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            154012
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.430
_diffrn_reflns_theta_min         2.613
_diffrn_source                   'micro-focus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Incoatec I\mS 1.0'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.280
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5775
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1370 before and 0.0727 after correction.
The Ratio of minimum to maximum transmission is 0.7666.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_description       plate
_exptl_crystal_F_000             5546
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.949
_refine_diff_density_min         -2.016
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1574
_refine_ls_number_reflns         22513
_refine_ls_number_restraints     244
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1133
_refine_ls_R_factor_gt           0.0883
_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^)+(0.1568P)^2^+39.8351P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2425
_refine_ls_wR_factor_ref         0.2647
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16821
_reflns_number_total             22513
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00946g2.cif
_cod_data_source_block           Tcminus1
_cod_depositor_comments
'Adding full bibliography for 7131398--7131400.cif.'
_cod_original_formula_sum        'C114.75 H74 F52 N6 Na O7.50 Tc'
_cod_database_code               7131398
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.611
_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
 C1A-C1B \\sim C1B-C1E
 with sigma of 0.02
 C3-C1A \\sim C3-C1B
 with sigma of 0.04
 C11-C12 \\sim C12-C13 \\sim C13-C14 \\sim C14-C15 \\sim C15-C16 \\sim C16-C11
 with sigma of 0.02
 C11-C15 \\sim C11-C13 \\sim C16-C14 \\sim C12-C16 \\sim C13-C15 \\sim C12-C14
 with sigma of 0.04
 C10-C16 \\sim C10-C12
 with sigma of 0.04
 C6-C7 \\sim C7-C8 \\sim C8-C9
 with sigma of 0.02
 O2-C6 \\sim O2-C9
 with sigma of 0.02
 O2-C7 \\sim O2-C8
 with sigma of 0.04
 C7-C9 \\sim C6-C8
 with sigma of 0.04
 F01Y-C04A \\sim F2-C04A
 with sigma of 0.02
 F03N-C04A \\sim F03O-C04A
 with sigma of 0.02
 F046-C04A \\sim F0-C04A
 with sigma of 0.02
 F01B-C040 \\sim F01C-C040
 with sigma of 0.02
 F01U-C040 \\sim F01V-C040
 with sigma of 0.02
 F03C-C040 \\sim F03D-C040
 with sigma of 0.02
3. Restrained planarity
 C10, C11, C12, C13, C14, C15, C16
 with sigma of 0.1
4. Rigid bond restraints
 O3C, C10C, C11C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C10C, C9C, O3C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C3 \\sim O19 \\sim C1A \\sim C1B \\sim C1E: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
O2 \\sim C6 \\sim C7 \\sim C8 \\sim C9: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(NaC) = Uanis(C1C) = Uanis(C2C) = Uanis(O1C) = Uanis(C3C) = Uanis(C4C) =
Uanis(O2C) = Uanis(C5C) = Uanis(C6C) = Uanis(C7C) = Uanis(C8C) = Uanis(O4C) =
Uanis(C9C) = Uanis(C10C) = Uanis(O3C) = Uanis(C11C) = Uanis(C12C) = Uanis(C13C)
= Uanis(C14C) = Uanis(O5C) = Uanis(C15C) = Uanis(C17C) = Uanis(C18C) =
Uanis(N2C) = Uanis(NaD) = Uanis(N1D) = Uanis(C1D) = Uanis(C2D) = Uanis(O1D) =
Uanis(C3D) = Uanis(C4D) = Uanis(O2D) = Uanis(C5D) = Uanis(C6D) = Uanis(C7D) =
Uanis(C8D) = Uanis(O4D) = Uanis(C9D) = Uanis(C10D) = Uanis(O3D) = Uanis(C11D) =
Uanis(C12D) = Uanis(C13D) = Uanis(C14D) = Uanis(O5D) = Uanis(O6D) = Uanis(C17D)
= Uanis(C18D) = Uanis(N2D) = Uanis(C16C) = Uanis(O6C) = Uanis(C15D) =
Uanis(C16D)
Uanis(NaC) = Uanis(C3C) = Uanis(C5C) = Uanis(C9C) = Uanis(C11C) = Uanis(C15C) =
Uanis(C17C) = Uanis(C1C) = Uanis(NaD) = Uanis(C4C) = Uanis(O2C) = Uanis(C6C) =
Uanis(C7C) = Uanis(C13C) = Uanis(C12C) = Uanis(O3C) = Uanis(O4C) = Uanis(C8C) =
Uanis(C2C) = Uanis(O1C) = Uanis(C16C) = Uanis(O6C) = Uanis(C14C) = Uanis(O5C) =
Uanis(C18C) = Uanis(N2C)
Uanis(C11C) = Uanis(C10C) = Uanis(O3C)
Uanis(NaC) = Uanis(C1C) = Uanis(C2C) = Uanis(O1C) = Uanis(C3C) = Uanis(C4C) =
Uanis(O2C) = Uanis(C5C) = Uanis(C6C) = Uanis(C7C) = Uanis(C8C) = Uanis(O4C) =
Uanis(C9C) = Uanis(C10C) = Uanis(O3C) = Uanis(C11C) = Uanis(C12C) = Uanis(C13C)
= Uanis(C14C) = Uanis(O5C) = Uanis(C15C) = Uanis(C17C) = Uanis(C18C) =
Uanis(N2C) = Uanis(NaD) = Uanis(C1D) = Uanis(C2D) = Uanis(O1D) = Uanis(C3D) =
Uanis(C4D) = Uanis(O2D) = Uanis(C5D) = Uanis(C6D) = Uanis(C7D) = Uanis(C8D) =
Uanis(O4D) = Uanis(C9D) = Uanis(C10D) = Uanis(O3D) = Uanis(C11D) = Uanis(C12D)
= Uanis(C13D) = Uanis(C14D) = Uanis(O5D) = Uanis(C15D) = Uanis(C17D) =
Uanis(C18D) = Uanis(N2D) = Uanis(C16C) = Uanis(O6C) = Uanis(C16D) = Uanis(O6D)
Uanis(O2D) = Uanis(NaC) = Uanis(N1C) = Uanis(C5C) = Uanis(C17C) = Uanis(C3C) =
Uanis(C15C) = Uanis(C11C) = Uanis(NaD) = Uanis(C9C) = Uanis(C1C) = Uanis(C10C)
= Uanis(O3C) = Uanis(C12C) = Uanis(O5C) = Uanis(N1D) = Uanis(C8D) = Uanis(O4D)
= Uanis(C10D) = Uanis(C11D) = Uanis(O2C) = Uanis(C6C) = Uanis(O6C) =
Uanis(C18C) = Uanis(C1D) = Uanis(O1D) = Uanis(C14D) = Uanis(C16D) = Uanis(C5D)
= Uanis(C4C) = Uanis(C6D) = Uanis(O1C) = Uanis(C16C) = Uanis(N2C) = Uanis(C12D)
= Uanis(C9D) = Uanis(C13C) = Uanis(O4C) = Uanis(C7C) = Uanis(C2D) = Uanis(C2C)
= Uanis(C3D) = Uanis(C4D) = Uanis(C8C) = Uanis(C14C) = Uanis(O5D) = Uanis(O3D)
= Uanis(C15D) = Uanis(C17D) = Uanis(C7D) = Uanis(C18D) = Uanis(O6D) =
Uanis(C13D) = Uanis(N2D)
Uanis(O3C) = Uanis(C9C) = Uanis(C10C)
Uiso(O2) = Uiso(C6) = Uiso(C7) = Uiso(C8) = Uiso(C9)
Uiso(O2) = Uiso(C6) = Uiso(C7) = Uiso(C8) = Uiso(C9) = Uiso(C10) = Uiso(C11) =
Uiso(C12) = Uiso(C13) = Uiso(C14) = Uiso(C15) = Uiso(C16)
Uanis(F046) = Uanis(F2) = Uanis(F03O) = Uanis(F01Y) = Uanis(F03N) = Uanis(F0)
Uanis(F01C) = Uanis(F01B) = Uanis(F03D) = Uanis(F03C) = Uanis(F01V) =
Uanis(F01U)
6. Rigid body (RIGU) restrains
 O3C, C10C, C11C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10C, C9C, O3C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3, O19, C1A, C1B, C1E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C11, C12, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C6, C7, C8, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{NaD, N1D, C1D, C2D, O1D, C3D, C4D, O2D, C5D, C6D, C7D, C8D, O4D, C9D, C10D,
O3D, C11D, C12D, C13D, C14D, O5D, C15D, C16D, O6D, C17D, C18D, N2D} sigma for
1-2: 0.02, 1-3: 0.04
as in
{NaC, N1C, C1C, C2C, O1C, C3C, C4C, O2C, C5C, C6C, C7C, C8C, O4C, C9C, C10C,
O3C, C11C, C12C, C13C, C14C, O5C, C15C, C16C, O6C, C17C, C18C, N2C}
8. Others
 Sof(NaD)=Sof(N1D)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(C2D)=Sof(H2DA)=Sof(H2DB)=
 Sof(O1D)=Sof(C3D)=Sof(H3DA)=Sof(H3DB)=Sof(C4D)=Sof(H4DA)=Sof(H4DB)=Sof(O2D)=
 Sof(C5D)=Sof(H5DA)=Sof(H5DB)=Sof(C6D)=Sof(H6DA)=Sof(H6DB)=Sof(C7D)=Sof(H7DA)=
 Sof(H7DB)=Sof(C8D)=Sof(H8DA)=Sof(H8DB)=Sof(O4D)=Sof(C9D)=Sof(H9DA)=Sof(H9DB)=
 Sof(C10D)=Sof(H10C)=Sof(H10D)=Sof(O3D)=Sof(C11D)=Sof(H11C)=Sof(H11D)=Sof(C12D)=
 Sof(H12C)=Sof(H12D)=Sof(C13D)=Sof(H13C)=Sof(H13D)=Sof(C14D)=Sof(H14C)=
 Sof(H14D)=Sof(O5D)=Sof(C15D)=Sof(H15C)=Sof(H15D)=Sof(C16D)=Sof(H16C)=Sof(H16D)=
 Sof(O6D)=Sof(C17D)=Sof(H17C)=Sof(H17D)=Sof(C18D)=Sof(H18C)=Sof(H18D)=Sof(N2D)=
 1-FVAR(1)
 Sof(NaC)=Sof(N1C)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(C2C)=Sof(H2CA)=Sof(H2CB)=
 Sof(O1C)=Sof(C3C)=Sof(H3CA)=Sof(H3CB)=Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(O2C)=
 Sof(C5C)=Sof(H5CA)=Sof(H5CB)=Sof(C6C)=Sof(H6CA)=Sof(H6CB)=Sof(C7C)=Sof(H7CA)=
 Sof(H7CB)=Sof(C8C)=Sof(H8CA)=Sof(H8CB)=Sof(O4C)=Sof(C9C)=Sof(H9CA)=Sof(H9CB)=
 Sof(C10C)=Sof(H10A)=Sof(H10B)=Sof(O3C)=Sof(C11C)=Sof(H11A)=Sof(H11B)=Sof(C12C)=
 Sof(H12A)=Sof(H12B)=Sof(C13C)=Sof(H13A)=Sof(H13B)=Sof(C14C)=Sof(H14A)=
 Sof(H14B)=Sof(O5C)=Sof(C15C)=Sof(H15A)=Sof(H15B)=Sof(C16C)=Sof(H16A)=Sof(H16B)=
 Sof(O6C)=Sof(C17C)=Sof(H17A)=Sof(H17B)=Sof(C18C)=Sof(H18A)=Sof(H18B)=Sof(N2C)=
 FVAR(1)
 Sof(F03O)=Sof(F2)=Sof(F0)=1-FVAR(2)
 Sof(F01Y)=Sof(F03N)=Sof(F046)=FVAR(2)
 Sof(F03D)=Sof(F01C)=Sof(F01V)=1-FVAR(3)
 Sof(F01B)=Sof(F01U)=Sof(F03C)=FVAR(3)
 Fixed Sof: O2(0.25) C6(0.25) H6A(0.25) H6B(0.25) C7(0.25) H7A(0.25) H7B(0.25)
 C8(0.25) H8A(0.25) H8B(0.25) C9(0.25) H9A(0.25) H9B(0.25) C10(0.25) H10E(0.25)
 H10F(0.25) H10G(0.25) C11(0.25) C12(0.25) H12(0.25) C13(0.25) H13(0.25)
 C14(0.25) H14(0.25) C15(0.25) H15(0.25) C16(0.25) H16(0.25) C3(0.25) H3A(0.25)
 H3B(0.25) O19(0.25) C1A(0.25) H1AA(0.25) H1AB(0.25) C1B(0.25) H1BA(0.25)
 H1BB(0.25) C1E(0.25) H1EA(0.25) H1EB(0.25)
9.a Free rotating group:
 O2(C6,C7,C8,C9), C10(C11,C12,C13,C14,C15,C16), C3(O19,C1A,C1B,C1E)
9.b Secondary CH2 refined with riding coordinates:
 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(H10A,H10B), C11C(H11A,H11B), C12C(H12A,H12B), C13C(H13A,H13B), C14C(H14A,
 H14B), C15C(H15A,H15B), C16C(H16A,H16B), C17C(H17A,H17B), C18C(H18A,H18B),
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C1D(H1DA,H1DB), C2D(H2DA,
 H2DB), C3D(H3DA,H3DB), C4D(H4DA,H4DB), C5D(H5DA,H5DB), C6D(H6DA,H6DB),
 C7D(H7DA,H7DB), C8D(H8DA,H8DB), C9D(H9DA,H9DB), C10D(H10C,H10D), C11D(H11C,
 H11D), C12D(H12C,H12D), C13D(H13C,H13D), C14D(H14C,H14D), C15D(H15C,H15D),
 C16D(H16C,H16D), C17D(H17C,H17D), C18D(H18C,H18D), C3(H3A,H3B), C1A(H1AA,H1AB),
  C1B(H1BA,H1BB), C1E(H1EA,H1EB)
9.c Me refined with riding coordinates:
 C10(H10E,H10F,H10G)
9.d Aromatic/amide H refined with riding coordinates:
 C1K(H1K), C1M(H1M), C01P(H01P), C020(H020), C022(H022), C024(H024),
 C026(H026), C027(H027), C02C(H02C), C02F(H02F), C02G(H02G), C02H(H02H),
 C02I(H02I), C02K(H02K), C02M(H02M), C02N(H02N), C02Q(H02Q), C02S(H02S),
 C02V(H02V), C02Y(H02Y), C035(H035), C036(H036), C037(H037), C03A(H03A),
 C03I(H03I), C03K(H03K), C03L(H03L), C03R(H03R), C03S(H03S), C03T(H03T),
 C041(H041), C047(H047), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
;
_shelx_res_checksum              41270
_shelx_hkl_checksum              57577
_olex2_submission_special_instructions 'No special instructions were received'