Homogeneous hydrogenation of CO₂ to methyl formate utilizing switchable ionic liquids.
Yadav, Mahendra; Linehan, John C.; Karkamkar, Abhijeet J.; van der Eide, Edwin; Heldebrant, David J.; Inorganic chemistry 53 (2014) 9849–9854; doi:10.1021/ic501378w

data_4341032
_publ_section_title
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 Homogeneous hydrogenation of CO&#x2082; to methyl formate utilizing
 switchable ionic liquids.
;
_journal_issue                   18
_journal_name_full               'Inorganic chemistry'
_journal_page_first              9849
_journal_page_last               9854
_journal_paper_doi               10.1021/ic501378w
_journal_volume                  53
_journal_year                    2014
_chemical_formula_moiety         'C9 H17 N2, C H O2'
_chemical_formula_sum            'C10 H18 N2 O2'
_chemical_formula_weight         198.26
_chemical_name_common            '[DBU-H]+[HCO2]-'
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2013-06-08
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.9772(3)
_cell_length_b                   12.3164(6)
_cell_length_c                   14.0486(9)
_cell_measurement_reflns_used    2160
_cell_measurement_temperature    140
_cell_measurement_theta_max      28.20
_cell_measurement_theta_min      2.90
_cell_volume                     1034.22(10)
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      140.0
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0195
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5821
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.281
_diffrn_reflns_theta_min         2.199
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9235
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1047 before and 0.0363 after correction.
The Ratio of minimum to maximum transmission is 0.9235.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_description       plate
_exptl_crystal_F_000             432
_exptl_crystal_recrystallization_method
;
Grown from a supersaturated solution of the material in DBU, at room 
temperature.
;
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.228
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 865 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.5(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     130
_refine_ls_number_reflns         2520
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0365
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0453P)^2^+0.1200P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0840
_refine_ls_wR_factor_ref         0.0871
_reflns_Friedel_coverage         0.690
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                2258
_reflns_number_total             2520
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic501378w_si_001.cif
_cod_data_source_block           ee36dh_0m
_cod_depositor_comments          'Adding full bibliography for 4341032.cif.'
_cod_database_code               4341032
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 N1-H1
 0.88 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B)
3.b Aromatic/amide H refined with riding coordinates:
 C10(H10)
;
_shelx_hkl_checksum              13933
_shelx_res_checksum              2118
_shelxl_version_number           2013-2