Thermally stable zinc hydride catalyst for hydrosilylation of CO2 to silyl formate at atmospheric pressure
Baalbaki, Hassan A.; Shu, Julia; Nyamayaro, Kudzanai; Jung, Hyuk-Joon; Mehrkhodavandi, Parisa; Chemical Communications  (2022) –; doi:10.1039/D2CC01498J

data_7130049
_publ_section_title
;
 Thermally stable zinc hydride catalyst for hydrosilylation of CO2 to
 silyl formate at atmospheric pressure
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01498J
_journal_year                    2022
_chemical_formula_moiety         '2(C58 H65 N2 O2 P Si Zn), C4 H10 O, C6 H14'
_chemical_formula_sum            'C126 H154 N4 O5 P2 Si2 Zn2'
_chemical_formula_weight         2053.38
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-03-07 deposited with the CCDC.	2022-04-26 downloaded from the CCDC.
;
_cell_angle_alpha                80.978(7)
_cell_angle_beta                 87.207(6)
_cell_angle_gamma                69.507(6)
_cell_formula_units_Z            1
_cell_length_a                   11.048(2)
_cell_length_b                   14.012(3)
_cell_length_c                   19.725(4)
_cell_measurement_reflns_used    9672
_cell_measurement_temperature    90
_cell_measurement_theta_max      30.70
_cell_measurement_theta_min      2.23
_cell_volume                     2824.8(10)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      90
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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  0.0398
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            64816
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.719
_diffrn_reflns_theta_min         1.045
_diffrn_source_current           30.0
_diffrn_source_power             1.35
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.529
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6728
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0760 before and 0.0632 after correction.
The Ratio of minimum to maximum transmission is 0.9018.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.207
_exptl_crystal_description       block
_exptl_crystal_F_000             1096
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.974
_refine_diff_density_min         -0.667
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     699
_refine_ls_number_reflns         17360
_refine_ls_number_restraints     147
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0424
_refine_ls_R_factor_gt           0.0370
_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^)+(0.0543P)^2^+1.5079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1022
_refine_ls_wR_factor_ref         0.1061
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15471
_reflns_number_total             17360
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01498j2.cif
_cod_data_source_block           mo_pm291_0m
_cod_original_cell_volume        2824.8(11)
_cod_database_code               7130049
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.888
_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. Restrained distances
 C51-C52
 1.54 with sigma of 0.01
 C54-C53
 1.54 with sigma of 0.01
 C52-C51 \\sim C50-C51 \\sim C49-C50 \\sim C49-C48 \\sim C47-C48
 with sigma of 0.01
 O3-C54 \\sim O3-C55
 with sigma of 0.01
 C54-C53 \\sim C56-C55
 with sigma of 0.01
 C56-O3 \\sim O3-C53
 with sigma of 0.01
 C52-C50 \\sim C51-C49 \\sim C50-C48 \\sim C49-C47
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O3 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C47 \\sim C48 \\sim C49 \\sim
C50 \\sim C51 \\sim C52: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 O3, C53, C54, C55, C56, C47, C48, C49, C50, C51, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O3(0.5) C53(0.5) H53A(0.5) H53B(0.5) H53C(0.5) C54(0.5) H54A(0.5)
 H54B(0.5) C55(0.5) H55A(0.5) H55B(0.5) C56(0.5) H56A(0.5) H56B(0.5) H56C(0.5)
 C47(0.5) H47A(0.5) H47B(0.5) H47C(0.5) C48(0.5) H48A(0.5) H48B(0.5) C49(0.5)
 H49A(0.5) H49B(0.5) C50(0.5) H50A(0.5) H50B(0.5) C51(0.5) H51A(0.5) H51B(0.5)
 C52(0.5) H52A(0.5) H52B(0.5) H52C(0.5)
6.a Ternary CH refined with riding coordinates:
 C16(H16), C17(H17)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,
 H21B), C22(H22A,H22B), C54(H54A,H54B), C55(H55A,H55B), C48(H48A,H48B),
 C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B)
6.c Me refined with riding coordinates:
 C53(H53A,H53B,H53C), C56(H56A,H56B,H56C), C47(H47A,H47B,H47C), C52(H52A,H52B,
 H52C)
6.d Aromatic/amide H refined with riding coordinates:
 C36(H36), C32(H32), C30(H30), C31(H31), C34(H34), C37(H37), C39(H39),
 C38(H38), C6(H6), C8(H8), C33(H33), C40(H40), C25(H25), C26(H26), C27(H27),
 C28(H28), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C64(H64), C65(H65),
  C66(H66), C67(H67), C68(H68), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46)
6.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              10803
_olex2_submission_special_instructions 'No special instructions were received'