Diverse outcomes of CO2 fixation using alkali metal amides including formation of a heterobimetallic lithium‒sodium carbamato-anhydride via lithium‒sodium bis-hexamethyldisilazide
Gauld, Richard M.; Kennedy, Alan R.; McLellan, Ross; Barker, Jim; Reid, Jacqueline; Mulvey, Robert E.; Chemical Communications  (2019) –; doi:10.1039/C8CC08308H

data_7122840
_publ_section_title
;
 Diverse outcomes of CO2 fixation using alkali metal amides including
 formation of a heterobimetallic lithium--sodium carbamato-anhydride via
 lithium--sodium bis-hexamethyldisilazide
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C8CC08308H
_journal_year                    2019
_chemical_formula_moiety
;
C24 H54 Li N4 Na O8 Si4, 0.5(C4 H8 O), C1.75 H3.5 O0.5, 0.25(C)
;
_chemical_formula_sum            'C28 H62 Li N4 Na O9 Si4'
_chemical_formula_weight         741.10
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-07-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-10-12 deposited with the CCDC.
2018-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.116(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.2504(11)
_cell_length_b                   13.1969(5)
_cell_length_c                   17.7522(8)
_cell_measurement_reflns_used    4367
_cell_measurement_temperature    123
_cell_measurement_theta_max      69.394
_cell_measurement_theta_min      3.975
_cell_volume                     4829.2(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      123.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'OD Gemini S'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0400
_diffrn_reflns_av_unetI/netI     0.0509
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            11971
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        69.988
_diffrn_reflns_theta_max         69.988
_diffrn_reflns_theta_min         6.853
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    1.575
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51567
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.019
_exptl_crystal_description       block
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.679
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.108
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.27(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     487
_refine_ls_number_reflns         6709
_refine_ls_number_restraints     181
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.1023
_refine_ls_R_factor_gt           0.0891
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2416
_refine_ls_wR_factor_ref         0.2660
_reflns_Friedel_coverage         0.912
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                5340
_reflns_number_total             6709
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc08308h2.cif
_cod_data_source_block           rmg2_099
_cod_database_code               7122840
_shelx_shelxl_version_number     2018/1
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.738055
 0.261945
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Si2-C6 = Si2-C7 = Si2-C8
 1.85 with sigma of 0.01
 Si2A-C6A = Si2A-C7A = Si2A-C8A
 1.85 with sigma of 0.01
 O9-C28 = O9-C25 = O7-C20 = O7-C17 = O8A-C21A = O8A-C24A
 1.43 with sigma of 0.01
 O8-C21 = O8-C24 = O10-C32 = O10-C29 = O7A-C17A = O7A-C20A
 1.43 with sigma of 0.01
 C25-C26 = C26-C27 = C27-C28 = C17-C18 = C18-C19 = C19-C20
 1.53 with sigma of 0.01
 C21-C22 = C22-C23 = C23-C24 = C21A-C22A = C22A-C23A = C23A-C24A
 1.53 with sigma of 0.01
 C29-C30 = C30-C31 = C31-C32 = C17A-C18A = C18A-C19A = C19A-C20A
 1.53 with sigma of 0.01
 C20A-C17A = C18A-C20A = C24A-C22A = C21-C23 = O8-C23 = O8A-C22A
 2.35 with sigma of 0.02
 C21A-C24A
 2.25 with sigma of 0.02
 C23A-C21A = C24-C22
 2.3 with sigma of 0.02
4. Rigid bond restraints
 Si2, N2, C6, C7, C8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O9, C25, C26, C27, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O10, C29, C30, C31, C32
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O8A, C24A, C21A, C22A, C23A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O8, C24, C22, C21, C23
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O7A, C17A, C18A, C19A, C20A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
Si2 \\sim N2 \\sim C6 \\sim C7 \\sim C8: within 1.95A with sigma of 0.02 and
sigma for terminal atoms of 0.02
O9 \\sim C25 \\sim C26 \\sim C27 \\sim C28: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02
O10 \\sim C29 \\sim C30 \\sim C31 \\sim C32: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.02
O8A \\sim C24A \\sim C21A \\sim C22A \\sim C23A: within 1.7A with sigma of
0.005 and sigma for terminal atoms of 0.01
O8 \\sim C24 \\sim C22 \\sim C21 \\sim C23: within 1.7A with sigma of 0.005 and
sigma for terminal atoms of 0.01
O7A \\sim C17A \\sim C18A \\sim C19A \\sim C20A: within 1.7A with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Si2) = Uanis(Si2A)
Uanis(C6) = Uanis(C6A)
Uanis(C7) = Uanis(C7A)
Uanis(C8) = Uanis(C8A)
6. Others
 Sof(Si2A)=Sof(C8A)=Sof(H8Aa)=Sof(H8Ab)=Sof(H8Ac)=Sof(C7A)=Sof(H7Aa)=Sof(H7Ab)=
 Sof(H7Ac)=Sof(C6A)=Sof(H6Aa)=Sof(H6Ab)=Sof(H6Ac)=1-FVAR(1)
 Sof(Si2)=Sof(C6)=Sof(H6a)=Sof(H6b)=Sof(H6c)=Sof(C7)=Sof(H7a)=Sof(H7b)=
 Sof(H7c)=Sof(C8)=Sof(H8a)=Sof(H8b)=Sof(H8c)=FVAR(1)
 Fixed Sof: O7(0.65) C17(0.65) H17a(0.65) H17b(0.65) C18(0.65) H18a(0.65)
 H18b(0.65) C19(0.65) H19a(0.65) H19b(0.65) C20(0.65) H20a(0.65) H20b(0.65)
 O8(0.5) C24(0.5) H24a(0.5) H24b(0.5) C22(0.5) H22a(0.5) H22b(0.5) C21(0.5)
 H21a(0.5) H21b(0.5) C23(0.5) H23a(0.5) H23b(0.5) O9(0.5) C25(0.5) H25a(0.5)
 H25b(0.5) C26(0.5) H26a(0.5) H26b(0.5) C27(0.5) H27a(0.5) H27b(0.5) C28(0.5)
 H28a(0.5) H28b(0.5) O10(0.5) C29(0.5) H29a(0.5) H29b(0.5) C30(0.5) H30a(0.5)
 H30b(0.5) C31(0.25) H31a(0.25) H31b(0.25) C32(0.5) H32a(0.5) H32b(0.5)
 O7A(0.35) C17A(0.35) H17c(0.35) H17d(0.35) C18A(0.35) H18c(0.35) H18d(0.35)
 C19A(0.35) H19c(0.35) H19d(0.35) C20A(0.35) H20c(0.35) H20d(0.35) O8A(0.5)
 C24A(0.5) H24c(0.5) H24d(0.5) C21A(0.5) H21c(0.5) H21d(0.5) C22A(0.5)
 H22c(0.5) H22d(0.5) C23A(0.5) H23c(0.5) H23d(0.5) C31A(0.25)
7.a Secondary CH2 refined with riding coordinates:
 C17(H17a,H17b), C18(H18a,H18b), C19(H19a,H19b), C20(H20a,H20b), C24(H24a,
 H24b), C22(H22a,H22b), C21(H21a,H21b), C23(H23a,H23b), C25(H25a,H25b),
 C26(H26a,H26b), C27(H27a,H27b), C28(H28a,H28b), C29(H29a,H29b), C30(H30a,H30b),
  C31(H31a,H31b), C32(H32a,H32b), C17A(H17c,H17d), C18A(H18c,H18d), C19A(H19c,
 H19d), C20A(H20c,H20d), C24A(H24c,H24d), C21A(H21c,H21d), C22A(H22c,H22d),
 C23A(H23c,H23d)
7.b Me refined with riding coordinates:
 C6(H6a,H6b,H6c), C7(H7a,H7b,H7c), C8(H8a,H8b,H8c), C8A(H8Aa,H8Ab,H8Ac),
 C7A(H7Aa,H7Ab,H7Ac), C6A(H6Aa,H6Ab,H6Ac)
7.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N4(H4)
7.d Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C2(H2a,H2b,H2c), C3(H3a,H3b,H3c), C9(H9a,H9b,H9c), C10(H10a,
 H10b,H10c), C11(H11a,H11b,H11c), C14(H14a,H14b,H14c), C15(H15a,H15b,H15c),
 C16(H16a,H16b,H16c)
;
_olex2_submission_special_instructions 'No special instructions were received'