Carboxylation of terminal alkynes with CO2 catalyzed by imidazolium-bridged bis(phenolato) rare-earth metal complexes
Shi, Kai; Lu, Chengrong; Zhao, Bei; New Journal of Chemistry 46 (2022) 16998–17003; doi:10.1039/D2NJ03130B

data_7061717
_publ_section_title
;
 Carboxylation of terminal alkynes with CO2 catalyzed by
 imidazolium-bridged bis(phenolato) rare-earth metal complexes
;
_journal_issue                   35
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              16998
_journal_page_last               17003
_journal_paper_doi               10.1039/D2NJ03130B
_journal_volume                  46
_journal_year                    2022
_chemical_formula_moiety         'C99 H141 Cl3 N6 Nd2 O6'
_chemical_formula_sum            'C121 H185 Cl3 N6 Nd2 O11.5'
_chemical_formula_weight         2302.57
_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
_audit_creation_date             2022-06-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-06-16 deposited with the CCDC.	2022-08-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.453(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.000(2)
_cell_length_b                   21.841(2)
_cell_length_c                   32.617(4)
_cell_measurement_reflns_used    9516
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      27.34
_cell_measurement_theta_min      2.32
_cell_volume                     12034(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0982
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            267931
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.513
_diffrn_reflns_theta_min         1.699
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.978
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5558
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1444 before and 0.0916 after correction.
The Ratio of minimum to maximum transmission is 0.7454.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             4864
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.321
_refine_diff_density_min         -1.297
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1081
_refine_ls_number_reflns         27573
_refine_ls_number_restraints     2343
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0548
_refine_ls_R_factor_gt           0.0389
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0466P)^2^+25.8784P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21868
_reflns_number_total             27573
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj03130b2.cif
_cod_data_source_block           mo_b220614c_0m_a
_cod_depositor_comments
'Adding full bibliography for 7061714--7061717.cif.'
_cod_original_formula_sum        'C121 H185 Cl3 N6 Nd2 O11.50'
_cod_database_code               7061717
_shelx_shelxl_version_number     2018/3
_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. Rigid bond restraints
 C02O, C03M, C03H
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C02O, C03M
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
C02O \\sim C03M \\sim C03O: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C00J \\sim C00K \\sim C00L \\sim C00M \\sim C00N \\sim C00O \\sim C00P \\sim
C00Q \\sim C2 \\sim C00S \\sim C00T \\sim C00U \\sim C00V \\sim C00W \\sim C00X
\\sim C00Y \\sim C00Z \\sim C010 \\sim C011 \\sim C012 \\sim C013 \\sim C014
\\sim C1 \\sim C016 \\sim C017 \\sim C018 \\sim C019 \\sim C01A \\sim C01B
\\sim C01C \\sim C01D \\sim C01E \\sim C01F \\sim C01G \\sim C01H \\sim C01J
\\sim C01K \\sim C01L \\sim C01M \\sim C01N \\sim C01O \\sim C01P \\sim C01Q
\\sim C01R \\sim C01S \\sim C01T \\sim C01U \\sim C01V \\sim C01W \\sim C01X
\\sim C01Y \\sim C01Z \\sim C020 \\sim C021 \\sim C022 \\sim C024 \\sim C025
\\sim C026 \\sim C027 \\sim C028 \\sim C3 \\sim C02A \\sim C02B \\sim C02C
\\sim C02D \\sim C02E \\sim C02F \\sim C02G \\sim C02H \\sim C02I \\sim C02J
\\sim C02K \\sim C02L \\sim C02M \\sim C02N \\sim C02O \\sim C02P \\sim C02Q
\\sim C02R \\sim C02S \\sim C02T \\sim C02U \\sim C02V \\sim C02W \\sim C02Y
\\sim C02Z \\sim C030 \\sim C032 \\sim C033 \\sim C035 \\sim C036 \\sim C037
\\sim C038 \\sim C03C \\sim C03G \\sim C03H \\sim C03J \\sim C03M \\sim C03O:
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
Uanis(C03M) \\sim Ueq, Uanis(C03O) \\sim Ueq, Uanis(C03H) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
4.a Secondary CH2 refined with riding coordinates:
 C00L(H00A,H00B), C00Y(H00C,H00D), C011(H01A,H01B), C01C(H01C,H01D), C01W(H01,
 H), C02A(H02G,H02H)
4.b Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C00N(H00N), C00Q(H00Q), C2(H2), C012(H012), C1(H1), C019(H019),
 C01J(H01K), C01K(H01L), C01M(H01P), C01O(H01Q), C01S(H01X), C01T(H01Y),
 C01U(H01Z), C01Z(H5), C021(H021), C022(H022), C024(H024), C3(H3A), C02C(H02L),
 C02I(H02V)
4.c Idealised Me refined as rotating group:
 C01E(H01E,H01F,H01G), C01G(H01H,H01I,H01J), C01L(H01M,H01N,H01O), C01P(H01R,
 H01S,H01T), C01Q(H01U,H01V,H01W), C01X(H3,HA,HB), C01Y(H4,HC,HD), C020(H02A,
 H02B,H02C), C025(H02D,H02E,H02F), C02B(H02I,H02J,H02K), C02D(H02M,H02N,H02O),
 C02E(H02P,H02Q,H02R), C02F(H02S,H02T,H02U), C02J(H02W,H02X,H02Y), C02L(H02Z,HE,
 HF), C02M(H02,HG,HH), C02N(H6,HI,HJ), C02P(H7,HK,HL), C02Q(H8,HM,HN), C02R(H9,
 HO,HP), C02U(H10,HQ,HR), C02V(H11,HS,HT), C02Y(H12,HU,HV), C02Z(H13,HW,HX),
 C030(H03A,H03B,H03C), C033(H03D,H03E,H03F), C035(H03G,H03H,H03I), C036(H03J,
 H03K,H03L), C037(H03M,H03N,H03O), C038(H03P,H03Q,H03R), C03C(H03S,H03T,H03U),
 C03G(H03V,H03W,H03X), C03H(H03Y,HY,HZ), C03J(H03Z,H15,H16), C03M(H03,H17,H18),
 C03O(H14,H19,H20)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 912 electrons were 
found in a volume of 4128\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
5.5[C4H8O] per Asymmetric Unit 
which account for 880 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              90803
_shelx_fab_checksum              29841
_olex2_submission_special_instructions 'No special instructions were received'