Ionic liquid cations as methylation agent for extremely weak chalcogenido metalate nucleophiles
Dehnen, Stefanie Susanne; Peters, Bertram; Santner, Silke; Donsbach, Carsten; Smarsly, Bernd; Voepel, Pascal; Chemical Science  (2019) –; doi:10.1039/C9SC01358J

data_1550923
_publ_section_title
;
 Ionic liquid cations as methylation agent for extremely weak chalcogenido
 metalate nucleophiles
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01358J
_journal_year                    2019
_chemical_formula_moiety         '6(C12 H23 N2), C2 H6 Hg6 Te12'
_chemical_formula_sum            'C74 H144 Hg6 N12 Te12'
_chemical_formula_weight         3936.74
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2019-03-13 deposited with the CCDC.    2019-04-22 downloaded from the CCDC.
;
_cell_angle_alpha                89.172(3)
_cell_angle_beta                 85.585(3)
_cell_angle_gamma                83.936(2)
_cell_formula_units_Z            1
_cell_length_a                   10.0664(8)
_cell_length_b                   11.5576(9)
_cell_length_c                   24.550(2)
_cell_measurement_reflns_used    9772
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      28.598
_cell_measurement_theta_min      2.425
_cell_volume                     2831.8(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            88604
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.998
_diffrn_reflns_theta_min         2.261
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    11.170
_exptl_absorpt_correction_T_max  0.0277
_exptl_absorpt_correction_T_min  0.0074
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1499 before and 0.0743 after correction.
The Ratio of minimum to maximum transmission is 0.2671.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.309
_exptl_crystal_description       plate
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.095
_refine_diff_density_min         -1.528
_refine_diff_density_rms         0.224
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     632
_refine_ls_number_reflns         13672
_refine_ls_number_restraints     2296
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0804
_refine_ls_R_factor_gt           0.0499
_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^)+(0.0427P)^2^+38.5605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1187
_refine_ls_wR_factor_ref         0.1292
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9797
_reflns_number_total             13672
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01358j2.cif
_cod_data_source_block           cdx109
_cod_original_cell_volume        2831.7(4)
_cod_database_code               1550923
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.584
_shelx_estimated_absorpt_t_min   0.140
_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, All C(H,H,H,H,H,
  H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C3B-C2B \\sim C3A-C2A \\sim C4A-C3A \\sim C4B-C3B \\sim C5A-C4A \\sim C5B-C4B
\\sim C6B-C5B \\sim C6A-C5A
 \\sim C7-C6A \\sim C7-C6B \\sim C8-C7 \\sim C9-C8 \\sim C15A-C14A \\sim
C15B-C14B \\sim C16A-C15A \\sim C16B-
 C15B \\sim C17B-C16B \\sim C17A-C16A \\sim C18B-C17B \\sim C18A-C17A \\sim
C19-C18A \\sim C19-C18B ~
 C20-C19 \\sim C21-C20 \\sim C27A-C26A \\sim C27B-C26B \\sim C28A-C27A \\sim
C29A-C28A \\sim C28B-C27B
 \\sim C30A-C29A \\sim C29B-C28B \\sim C31A-C30A \\sim C30B-C29B \\sim
C32A-C31A \\sim C31B-C30B \\sim C32B-
 C31B \\sim C33-C32A \\sim C33-C32B
 with sigma of 0.02
 C26A-C28A \\sim C30A-C32A \\sim C27A-C29A \\sim C31A-C33 \\sim C26B-C28B \\sim
C27B-C29B \\sim C30B-
 C32B \\sim C31B-C33 \\sim C28A-C30A \\sim C29A-C31A \\sim C28B-C30B \\sim
C29B-C31B \\sim C18A-C20 ~
 C14B-C16B \\sim C15B-C17B \\sim C18B-C20 \\sim C14A-C16A \\sim C15A-C17A \\sim
C16B-C18B \\sim C17B-
 C19 \\sim C16A-C18A \\sim C17A-C19 \\sim C2A-C4A \\sim C3A-C5A \\sim C6A-C8
\\sim C2B-C4B \\sim C3B-C5B ~
 C6B-C8 \\sim C4B-C6B \\sim C6A-C4A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C37 \\sim C36 \\sim C35 \\sim N6 \\sim C34 \\sim N5 \\sim C33 \\sim C32B \\sim
C32A \\sim C31B \\sim C31A \\sim C30B \\sim C30A \\sim C29B \\sim C29A \\sim
C28B \\sim C28A \\sim C27B \\sim C27A \\sim C26B \\sim C26A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C25 \\sim C24 \\sim C23 \\sim N4 \\sim C22 \\sim N3 \\sim C21 \\sim C20 \\sim
C19 \\sim C18B \\sim C18A \\sim C17B \\sim C17A \\sim C16B \\sim C16A \\sim
C15B \\sim C15A \\sim C14B \\sim C14A: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
C13 \\sim C12 \\sim C11 \\sim N2 \\sim C10 \\sim N1 \\sim C9 \\sim C8 \\sim C7
\\sim C6B \\sim C6A \\sim C5B \\sim C5A \\sim C4B \\sim C4A \\sim C3B \\sim C3A
\\sim C2B \\sim C2A: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
Uanis(C37) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(N6)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(N5) \\sim Ueq, Uanis(C33) \\sim Ueq,
Uanis(C32B) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C31B) \\sim Ueq,
Uanis(C31A) \\sim Ueq, Uanis(C30B) \\sim Ueq, Uanis(C30A) \\sim Ueq,
Uanis(C29B) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C28B) \\sim Ueq,
Uanis(C28A) \\sim Ueq, Uanis(C27B) \\sim Ueq, Uanis(C27A) \\sim Ueq,
Uanis(C26B) \\sim Ueq, Uanis(C26A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(N4)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18B) \\sim Ueq, Uanis(C18A)
\\sim Ueq, Uanis(C17B) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C16B) \\sim Ueq,
Uanis(C16A) \\sim Ueq, Uanis(C15B) \\sim Ueq, Uanis(C15A) \\sim Ueq,
Uanis(C14B) \\sim Ueq, Uanis(C14A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 C37, C36, C35, N6, C34, N5, C33, C32B, C32A, C31B, C31A, C30B, C30A, C29B,
 C29A, C28B, C28A, C27B, C27A, C26B, C26A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25, C24, C23, N4, C22, N3, C21, C20, C19, C18B, C18A, C17B, C17A, C16B, C16A,
  C15B, C15A, C14B, C14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C12, C11, N2, C10, N1, C9, C8, C7, C6B, C6A, C5B, C5A, C4B, C4A, C3B,
 C3A, C2B, C2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H19C)=Sof(H19D)=Sof(C14B)=Sof(C15B)=Sof(H15C)=Sof(H15D)=Sof(C16B)=
 Sof(H16C)=Sof(H16D)=Sof(C17B)=Sof(H17C)=Sof(H17D)=Sof(C18B)=Sof(H18C)=
 Sof(H18D)=1-FVAR(1)
 Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(H14G)=Sof(H14H)=Sof(H14I)=0.5*(1-FVAR(2))
 Sof(H19A)=Sof(H19B)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15A)=
 Sof(H15A)=Sof(H15B)=Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(C17A)=Sof(H17A)=
 Sof(H17B)=Sof(C18A)=Sof(H18A)=Sof(H18B)=FVAR(1)
 Sof(H7BC)=Sof(H7BD)=Sof(C2B)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(C4B)=Sof(H4BA)=
 Sof(H4BB)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(C6B)=Sof(H6BA)=Sof(H6BB)=1-FVAR(2)
 Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=Sof(H2BD)=Sof(H2BE)=Sof(H2BF)=0.5*(1-FVAR(3))
 Sof(H7AA)=Sof(H7AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C3A)=Sof(H3AA)=
 Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=
 Sof(H6AA)=Sof(H6AB)=FVAR(2)
 Sof(H33C)=Sof(H33D)=Sof(C26A)=Sof(H26G)=Sof(H26H)=Sof(H26I)=Sof(C27A)=
 Sof(H27C)=Sof(H27D)=Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C29A)=Sof(H29C)=
 Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=Sof(H31C)=Sof(H31D)=
 Sof(C32A)=Sof(H32C)=Sof(H32D)=1-FVAR(3)
 Sof(H26A)=Sof(H26C)=Sof(H26E)=Sof(H26D)=Sof(H26F)=Sof(H26B)=0.5*FVAR(4)
 Sof(H33A)=Sof(H33B)=Sof(C26B)=Sof(C27B)=Sof(H27A)=Sof(H27B)=Sof(C28B)=
 Sof(H28A)=Sof(H28B)=Sof(C29B)=Sof(H29A)=Sof(H29B)=Sof(C30B)=Sof(H30A)=
 Sof(H30B)=Sof(C31B)=Sof(H31A)=Sof(H31B)=Sof(C32B)=Sof(H32A)=Sof(H32B)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C7(H7AA,H7AB), C7(H7BC,H7BD), C8(H8A,H8B), C9(H9A,H9B), C3A(H3AA,H3AB),
 C4A(H4AA,H4AB), C5A(H5AA,H5AB), C6A(H6AA,H6AB), C3B(H3BA,H3BB), C4B(H4BA,H4BB),
  C5B(H5BA,H5BB), C6B(H6BA,H6BB), C19(H19A,H19B), C19(H19C,H19D), C20(H20A,
 H20B), C21(H21A,H21B), C15A(H15A,H15B), C16A(H16A,H16B), C17A(H17A,H17B),
 C18A(H18A,H18B), C15B(H15C,H15D), C16B(H16C,H16D), C17B(H17C,H17D), C18B(H18C,
 H18D), C33(H33A,H33B), C33(H33C,H33D), C27B(H27A,H27B), C28B(H28A,H28B),
 C29B(H29A,H29B), C30B(H30A,H30B), C31B(H31A,H31B), C32B(H32A,H32B), C27A(H27C,
 H27D), C28A(H28C,H28D), C29A(H29C,H29D), C30A(H30C,H30D), C31A(H31C,H31D),
 C32A(H32C,H32D)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C22(H22), C23(H23), C24(H24), C34(H34),
 C35(H35), C36(H36)
6.c Disordered Me refined with riding coordinates:
 C2B(H2BA,H2BB,H2BC,H2BD,H2BE,H2BF), C14B(H14D,H14E,H14F,H14G,H14H,H14I),
 C26B(H26A,H26C,H26E,H26D,H26F,H26B)
6.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C2A(H2AA,H2AB,H2AC), C25(H25A,H25B,H25C), C14A(H14A,H14B,
 H14C), C37(H37A,H37B,H37C), C26A(H26G,H26H,H26I), C1(H1A,H1B,H1C)
;
_olex2_submission_special_instructions 'No special instructions were received'