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_1550922
_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         'C2 H6 Hg6 Te12, 6(C10 H19 N2)'
_chemical_formula_sum            'C62 H120 Hg6 N12 Te12'
_chemical_formula_weight         3768.43
_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             2018-02-05
_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                75.961(5)
_cell_angle_beta                 83.155(4)
_cell_angle_gamma                83.555(5)
_cell_formula_units_Z            1
_cell_length_a                   10.0647(14)
_cell_length_b                   11.591(2)
_cell_length_c                   21.309(3)
_cell_measurement_reflns_used    9860
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      26.42
_cell_measurement_theta_min      2.57
_cell_volume                     2385.5(6)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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  0.0494
_diffrn_reflns_av_unetI/netI     0.0445
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            52343
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         2.186
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    13.253
_exptl_absorpt_correction_T_max  0.0249
_exptl_absorpt_correction_T_min  0.0050
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1505 before and 0.0628 after correction.
The Ratio of minimum to maximum transmission is 0.2008.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.623
_exptl_crystal_description       plate
_exptl_crystal_F_000             1680
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.01
_refine_diff_density_max         4.137
_refine_diff_density_min         -2.333
_refine_diff_density_rms         0.286
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     729
_refine_ls_number_reflns         10898
_refine_ls_number_restraints     1416
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0793
_refine_ls_R_factor_gt           0.0599
_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^)+(0.0321P)^2^+87.8679P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1398
_refine_ls_wR_factor_ref         0.1451
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8587
_reflns_number_total             10898
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01358j2.cif
_cod_data_source_block           cdx108q
_cod_original_cell_volume        2385.5(7)
_cod_database_code               1550922
_shelx_shelxl_version_number     2014/7
_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,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Hg1-Te3B \\sim Hg1-Te3A
 with sigma of 0.01
 Hg3-Te3B \\sim Hg3-Te3A
 with sigma of 0.02
 Te1A-C1A \\sim Te1B-C1B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N1_1 \\sim N2_1 \\sim C2_1 \\sim C3_1 \\sim C4_1 \\sim C5_1 \\sim C6_1 \\sim
C7_1 \\sim C10_1 \\sim C9_1 \\sim C11_1 \\sim C8_1: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
N1_2 \\sim N2_2 \\sim C2_2 \\sim C3_2 \\sim C4_2 \\sim C5_2 \\sim C6_2 \\sim
C7_2 \\sim C10_2 \\sim C9_2 \\sim C11_2 \\sim C8_2: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
N1_3 \\sim N2_3 \\sim C2_3 \\sim C3_3 \\sim C4_3 \\sim C5_3 \\sim C6_3 \\sim
C7_3 \\sim C10_3 \\sim C9_3 \\sim C11_3 \\sim C8_3: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
N1_4 \\sim N2_4 \\sim C2_4 \\sim C3_4 \\sim C4_4 \\sim C5_4 \\sim C6_4 \\sim
C7_4 \\sim C10_4 \\sim C9_4 \\sim C11_4 \\sim C8_4: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
N1_5 \\sim N2_5 \\sim C2_5 \\sim C3_5 \\sim C4_5 \\sim C5_5 \\sim C6_5 \\sim
C7_5 \\sim C10_5 \\sim C9_5 \\sim C11_5 \\sim C8_5: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
N1_6 \\sim N2_6 \\sim C2_6 \\sim C3_6 \\sim C4_6 \\sim C5_6 \\sim C6_6 \\sim
C7_6 \\sim C10_6 \\sim C9_6 \\sim C11_6 \\sim C8_6: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(N1_1) \\sim Ueq, Uanis(N2_1) \\sim Ueq, Uanis(C2_1) \\sim Ueq,
Uanis(C3_1) \\sim Ueq, Uanis(C4_1) \\sim Ueq, Uanis(C5_1) \\sim Ueq,
Uanis(C6_1) \\sim Ueq, Uanis(C7_1) \\sim Ueq, Uanis(C10_1) \\sim Ueq,
Uanis(C9_1) \\sim Ueq, Uanis(C11_1) \\sim Ueq, Uanis(C8_1) \\sim Ueq: with
sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N1_2) \\sim Ueq, Uanis(N2_2) \\sim Ueq, Uanis(C2_2) \\sim Ueq,
Uanis(C3_2) \\sim Ueq, Uanis(C4_2) \\sim Ueq, Uanis(C5_2) \\sim Ueq,
Uanis(C6_2) \\sim Ueq, Uanis(C7_2) \\sim Ueq, Uanis(C10_2) \\sim Ueq,
Uanis(C9_2) \\sim Ueq, Uanis(C11_2) \\sim Ueq, Uanis(C8_2) \\sim Ueq: with
sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N1_3) \\sim Ueq, Uanis(N2_3) \\sim Ueq, Uanis(C2_3) \\sim Ueq,
Uanis(C3_3) \\sim Ueq, Uanis(C4_3) \\sim Ueq, Uanis(C5_3) \\sim Ueq,
Uanis(C6_3) \\sim Ueq, Uanis(C7_3) \\sim Ueq, Uanis(C10_3) \\sim Ueq,
Uanis(C9_3) \\sim Ueq, Uanis(C11_3) \\sim Ueq, Uanis(C8_3) \\sim Ueq: with
sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N1_4) \\sim Ueq, Uanis(N2_4) \\sim Ueq, Uanis(C2_4) \\sim Ueq,
Uanis(C3_4) \\sim Ueq, Uanis(C4_4) \\sim Ueq, Uanis(C5_4) \\sim Ueq,
Uanis(C6_4) \\sim Ueq, Uanis(C7_4) \\sim Ueq, Uanis(C10_4) \\sim Ueq,
Uanis(C9_4) \\sim Ueq, Uanis(C11_4) \\sim Ueq, Uanis(C8_4) \\sim Ueq: with
sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C9_5) = Uanis(C10_5)
Uanis(N1_6) = Uanis(C10_6)
Uanis(N2_6) = Uanis(C9_6)
Uanis(C1A) = Uanis(Te1A)
Uanis(Te1B) = Uanis(C1B)
Uanis(C8_6) = Uanis(N1_6)
Uanis(C2_3) = Uanis(C3_3) = Uanis(C4_6)
Uanis(N2_3) = Uanis(C9_3)
Uanis(C9_3) = Uanis(N2_3)
4. Rigid body (RIGU) restrains
 N1_1, N2_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C10_1, C9_1, C11_1, C8_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1_2, N2_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C10_2, C9_2, C11_2, C8_2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1_3, N2_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3, C10_3, C9_3, C11_3, C8_3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1_4, N2_4, C2_4, C3_4, C4_4, C5_4, C6_4, C7_4, C10_4, C9_4, C11_4, C8_4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1_5, N2_5, C2_5, C3_5, C4_5, C5_5, C6_5, C7_5, C10_5, C9_5, C11_5, C8_5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1_6, N2_6, C2_6, C3_6, C4_6, C5_6, C6_6, C7_6, C10_6, C9_6, C11_6, C8_6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{N1_3, N2_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3, C10_3}
{N1_5, N2_5, C2_5, C3_5, C4_5, C5_5, C6_5, C7_5, C10_5}
{N1_6, N2_6, C2_6, C3_6, C4_6, C5_6, C6_6, C7_6, C10_6}
{N1_4, N2_4, C2_4, C3_4, C4_4, C5_4, C6_4, C7_4, C10_4}
{N1_2, N2_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C10_2}
as
{N1_1, N2_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C10_1} sigma for 1-2: 0.02
1-3: 0.04
6. Others
 Sof(N1)=Sof(N2)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C8)=Sof(H8)=1-FVAR(1)
 Sof(N1)=Sof(N2)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C8)=Sof(H8)=FVAR(1)
 Sof(N1)=Sof(N2)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C8)=Sof(H8)=1-FVAR(2)
 Sof(N1)=Sof(N2)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C8)=Sof(H8)=FVAR(2)
 Sof(N1)=Sof(N2)=Sof(C2)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C8)=Sof(H8)=1-FVAR(3)
 Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(H2D)=Sof(H2E)=Sof(H2F)=0.5*(1-FVAR(4))
 Sof(N1)=Sof(N2)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C10)=Sof(H10)=Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C8)=Sof(H8)=FVAR(3)
 Sof(Te3B)=Sof(Te1B)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=1-FVAR(4)
 Sof(Te1A)=Sof(Te3A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C3(H3A,H3B),
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C3(H3A,H3B), C4(H4A,H4B),
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B),
 C6(H6A,H6B), C7(H7A,H7B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B)
7.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C9(H9), C8(H8), C10(H10), C9(H9), C8(H8), C10(H10), C9(H9), C8(H8),
 C10(H10), C9(H9), C8(H8), C10(H10), C9(H9), C8(H8), C10(H10), C9(H9), C8(H8)
7.c Disordered Me refined with riding coordinates:
 C2(H2A,H2B,H2C,H2D,H2E,H2F)
7.d Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC), C2(H2A,H2B,H2C), C11(H11A,H11B,
 H11C), C11(H11A,H11B,H11C), C2(H2A,H2B,H2C), C11(H11A,H11B,H11C), C2(H2A,H2B,
 H2C), C11(H11A,H11B,H11C), C2(H2A,H2B,H2C), C11(H11A,H11B,H11C), C2(H2A,H2B,
 H2C), C11(H11A,H11B,H11C)
;
_olex2_submission_special_instructions 'No special instructions were received'