Silylation of Pyridine, Picolines, and Quinoline with a Zinc Catalyst
Prybil, Joshua W.; Wallace, Rodney; Warren, Alexandra; Klingman, Jordan; Vaillant, Romane; Hall, Michael B.; Yang, Xin; Brennessel, William W.; Chin, Robert M.; ACS Omega 5 (2020) 1528–1539; doi:10.1021/acsomega.9b03317

data_4517306
_publ_section_title
;
 Silylation of Pyridine, Picolines, and Quinoline with a Zinc Catalyst
;
_journal_issue                   3
_journal_name_full               'ACS Omega'
_journal_page_first              1528
_journal_page_last               1539
_journal_paper_doi               10.1021/acsomega.9b03317
_journal_volume                  5
_journal_year                    2020
_chemical_formula_moiety         '2(C11 H16.50 N1.50 O2 S0.50 Si0.50)'
_chemical_formula_sum            'C22 H33 N3 O4 S Si'
_chemical_formula_weight         463.66
_space_group_crystal_system      hexagonal
_space_group_IT_number           176
_space_group_name_Hall           '-P 6c'
_space_group_name_H-M_alt        'P 63/m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-05-29
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   23.6621(3)
_cell_length_b                   23.6621(3)
_cell_length_c                   7.5296(2)
_cell_measurement_reflns_used    19583
_cell_measurement_temperature    99.9(5)
_cell_measurement_theta_max      77.3760
_cell_measurement_theta_min      3.7620
_cell_volume                     3650.98(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -66.00 -41.00   0.50    1.12    --  -49.75 -57.00-120.00   50
  2  \w    -90.00 -64.00   0.50    4.50    --  -84.25 -77.00 -90.00   52
  3  \w    -90.00 -64.00   0.50    4.50    --  -84.25 -76.00 -64.60   52
  4  \w    -95.00 -70.00   0.50    4.50    --  -84.25 -61.00 -90.00   50
  5  \w   -109.00 -70.00   0.50    1.12    --  -49.75 -57.00-120.00   78
  6  \w   -118.00 -93.00   0.50    4.50    --  -84.25 -95.00 -88.00   50
  7  \w   -119.00 -37.00   0.50    1.12    --  -49.75 -57.00 -90.00  164
  8  \w   -121.00 -70.00   0.50    1.12    --  -49.75-125.00-120.00  102
  9  \w     -3.00  41.00   0.50    1.12    --   49.75 -95.00 -88.00   88
 10  \w     83.00 108.00   0.50    4.50    --  105.75 -95.00 -88.00   50
 11  \w     53.00  81.00   0.50    4.50    --  105.75 -45.00-150.00   56
 12  \w     38.00  67.00   0.50    4.50    --  105.75 -30.00-120.00   58
 13  \w     34.00  80.00   0.50    4.50    --  105.75 -15.00-150.00   92
 14  \w     98.00 137.00   0.50    4.50    --  105.75  30.00 -90.00   78
 15  \w    149.00 175.00   0.50    4.50    --  105.75  30.00 -90.00   52
 16  \w    133.00 174.00   0.50    4.50    --  105.75  74.00 -68.89   82
 17  \w    142.00 168.00   0.50    4.50    --  105.75  95.00  20.00   52
 18  \w    144.00 170.00   0.50    4.50    --  105.75 125.00  60.00   52
 19  \w    138.00 177.00   0.50    4.50    --  105.75  77.00 150.00   78
 20  \w    109.00 141.00   0.50    4.50    --  105.75  95.00  20.00   64
 21  \w     97.00 123.00   0.50    4.50    --  105.75 125.00  60.00   52
 22  \w     85.00 134.00   0.50    4.50    --  105.75  77.00 150.00   98
 23  \w     45.00  72.00   0.50    4.50    --  105.75 -15.00  90.00   54
 24  \w     46.00  71.00   0.50    4.50    --  105.75 -30.00 120.00   50
 25  \w     33.00  79.00   0.50    4.50    --  105.75 -15.00 150.00   92
 26  \w     35.00  63.00   0.50    4.50    --  105.75 -30.00 150.00   56
 27  \w     51.00  76.00   0.50    4.50    --  105.75 -94.00 120.00   50
 28  \w     84.00 109.00   0.50    4.50    --  105.75 -94.00 120.00   50
 29  \w     34.00  69.00   0.50    4.50    --  105.75 -30.00 -30.00   70
 30  \w     34.00  65.00   0.50    4.50    --  105.75 -30.00 -90.00   62
 31  \w     99.00 124.00   0.50    4.50    --  105.75  30.00 -60.00   50
 32  \w    120.00 177.00   0.50    4.50    --  105.75  30.00 -30.00  114
 33  \w    126.00 165.00   0.50    4.50    --  105.75  61.00-120.00   78
 34  \w     86.00 119.00   0.50    4.50    --  105.75  77.00-120.00   66
 35  \w     85.00 162.00   0.50    4.50    --  105.75  77.00 -90.00  154
 36  \w     92.00 138.00   0.50    4.50    --  105.75  61.00 -60.00   92
 37  \w     86.00 112.00   0.50    4.50    --  105.75  74.00 -68.89   52
 38  \w     53.00  90.00   0.50    1.12    --   49.75  38.00-120.00   74
 39  \w     34.00  59.00   0.50    4.50    --  105.75 -30.00-180.00   50
 40  \w     34.00  65.00   0.50    4.50    --  105.75 -30.00  30.00   62
 41  \w     37.00  70.00   0.50    4.50    --  105.75 -30.00  60.00   66
 42  \w    -79.00  -4.00   0.50    1.12    --  -49.75  95.00  20.00  150
 43  \w    -72.00 -47.00   0.50    4.50    --  -84.25  95.00  20.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0583714000
_diffrn_orient_matrix_UB_12      0.0116534000
_diffrn_orient_matrix_UB_13      -0.0126170000
_diffrn_orient_matrix_UB_21      0.0390411000
_diffrn_orient_matrix_UB_22      0.0646823000
_diffrn_orient_matrix_UB_23      0.1020794000
_diffrn_orient_matrix_UB_31      0.0267610000
_diffrn_orient_matrix_UB_32      0.0364796000
_diffrn_orient_matrix_UB_33      -0.1768974000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0615
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            44070
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         77.996
_diffrn_reflns_theta_min         2.156
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.919
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68539
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.265
_exptl_crystal_description       needle
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.126
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.062
_refine_diff_density_max         1.166
_refine_diff_density_min         -0.592
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.184
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         2807
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      1.189
_refine_ls_R_factor_all          0.1383
_refine_ls_R_factor_gt           0.1365
_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^)+(0.1581P)^2^+8.5611P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3691
_refine_ls_wR_factor_ref         0.3702
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2687
_reflns_number_total             2807
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao9b03317_si_002.cif
_cod_data_source_block           unimc43
_cod_depositor_comments
;Adding full bibliography for 4517306.cif.

 Adding full bibliography for 4517306.cif.
;
_cod_original_cell_volume        3650.98(13)
_cod_database_code               4517306
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.794
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 C10-C9 \\sim C10-C11 \\sim C10-C15 \\sim C12-C11 \\sim C12-C13 \\sim C12-C16
 with sigma of 0.01
 S1-O1 \\sim S1-O2
 with sigma of 0.01
 N1-O3 \\sim N1-O4
 with sigma of 0.01
 Si1-C17 \\sim Si1-C19 \\sim Si1-C21 \\sim Si1'-C17' \\sim Si1'-C19' \\sim
Si1'-C21'
 with sigma of 0.01
 C17-C19 \\sim C19-C21 \\sim C21-C17 \\sim C17'-C19' \\sim C19'-C21' \\sim
C21'-C17'
 with sigma of 0.02
 C17-C18 \\sim C19-C20 \\sim C21-C22 \\sim C17'-C18' \\sim C19'-C20' \\sim
C21'-C22'
 with sigma of 0.01
 Si1-C18 \\sim Si1-C20 \\sim Si1-C22 \\sim Si1'-C18' \\sim Si1'-C20' \\sim
Si1'-C22'
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si1 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04
Uanis(Si1) = Uanis(Si1')
Uiso(C17) = Uiso(C17')
Uiso(C18) = Uiso(C18')
Uiso(C19) = Uiso(C19')
Uiso(C20) = Uiso(C20')
Uiso(C21) = Uiso(C21')
Uiso(C22) = Uiso(C22')
4. Others
 Sof(Si1')=Sof(C17')=Sof(H17C)=Sof(H17D)=Sof(C18')=Sof(H18D)=Sof(H18E)=
 Sof(H18F)=Sof(C19')=Sof(H19C)=Sof(H19D)=Sof(C20')=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C21')=Sof(H21C)=Sof(H21D)=Sof(C22')=Sof(H22D)=Sof(H22E)=
 Sof(H22F)=0.5*(1-FVAR(2))
 Sof(Si1)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=
 Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=0.5*FVAR(2)
 Fixed Sof: S1(0.5) O1(0.5) O2(0.5) C1(0.5) C2(0.5) H2(0.5) C3(0.5) H3(0.5)
 C4(0.5) C5(0.5) H5(0.5) C6(0.5) H6(0.5) N1(0.5) O3(0.5) O4(0.5) N2(0.5)
 N3(0.5) C7(0.5) H7A(0.5) H7B(0.5) C8(0.5) H8(0.5) C9(0.5) H9A(0.5) H9B(0.5)
 C10(0.5) H10(0.5) C11(0.5) H11(0.5) C12(0.5) H12(0.5) C13(0.5) H13A(0.5)
 H13B(0.5) C14(0.5) H14A(0.5) H14B(0.5) C15(0.5) H15(0.5) C16(0.5) H16(0.5)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C10(H10), C11(H11), C12(H12), C15(H15), C16(H16)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C13(H13A,H13B), C14(H14A,H14B), C17(H17A,H17B),
 C19(H19A,H19B), C21(H21A,H21B), C17'(H17C,H17D), C19'(H19C,H19D), C21'(H21C,
 H21D)
5.c Me refined with riding coordinates:
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C18'(H18D,H18E,
 H18F), C20'(H20D,H20E,H20F), C22'(H22D,H22E,H22F)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6)
;
_shelx_res_checksum              68154
_shelx_hkl_checksum              51533
_olex2_submission_original_sample_id unimc43
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.739
_oxdiff_exptl_absorpt_empirical_full_min 0.674