Large Transition State Stabilization from a Weak Hydrogen Bond
Vik, Erik C.; Li, Ping; Maier, Josef M.; Madukwe, Daniel O.; Rassolov, Vitaly A.; Pellechia, Perry J.; Masson, Eric; Shimizu, Ken D.; Chemical Science  (2020) –; doi:10.1039/D0SC02806A

data_1558479
_publ_section_title
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 Large Transition State Stabilization from a Weak Hydrogen Bond
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_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02806A
_journal_year                    2020
_chemical_formula_moiety         'C15 H12 Cl N O3'
_chemical_formula_sum            'C15 H12 Cl N O3'
_chemical_formula_weight         289.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-02-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2020-05-11 deposited with the CCDC.	2020-07-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.5700(16)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.4699(12)
_cell_length_b                   6.8917(5)
_cell_length_c                   22.137(2)
_cell_measurement_reflns_used    9909
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.70
_cell_measurement_theta_min      2.40
_cell_volume                     2590.8(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEX3 v2016.5-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON-100 area detector'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0153
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            49286
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        27.723
_diffrn_reflns_theta_max         27.723
_diffrn_reflns_theta_min         2.399
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.301
_exptl_absorpt_correction_T_max  0.8621
_exptl_absorpt_correction_T_min  0.8136
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1270 before and 0.0579 after correction.
The Ratio of minimum to maximum transmission is 0.9437.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.485
_exptl_crystal_description       plate
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.350
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.062
_refine_ls_extinction_coef       0.0013(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.301
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3036
_refine_ls_number_restraints     64
_refine_ls_restrained_S_all      1.294
_refine_ls_R_factor_all          0.0557
_refine_ls_R_factor_gt           0.0524
_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^)+(0.0277P)^2^+7.6465P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1264
_refine_ls_wR_factor_ref         0.1277
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2832
_reflns_number_total             3036
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02806a2.cif
_cod_data_source_block           ecv1_125_a
_cod_database_code               1558479
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.920
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 N1B-C10B \\sim N1-C10
 with sigma of 0.01
 O3A-C11 \\sim O3C-C15 \\sim O3D-C15B \\sim O3C-C11B
 with sigma of 0.01
3. Restrained planarity
 C12B, C13B, C14B, C15B, C10B, C11B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C3) = Uanis(C6B)
Uanis(C12) = Uanis(C12B)
Uanis(Cl1) = Uanis(Cl1B)
Uanis(N1) = Uanis(N1B)
5. Same fragment restrains
{O1, O2, N1, C1, C2, C3, C4, C5, C6, C7, C8, C9} sigma for 1-2: 0.015, 1-3: 0.04
as
{O1B, O2B, N1B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B}
{Cl1, O3A, O3C, C10, C11, C12, C13, C14, C15} sigma for 1-2: 0.015, 1-3: 0.04
as
{Cl1B, O3B, O3D, C10B, C11B, C12B, C13B, C14B, C15B}
6. Others
 Sof(O1B)=Sof(O2B)=Sof(N1B)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C2B)=Sof(H2B)=
 Sof(C3B)=Sof(H3BA)=Sof(C4B)=Sof(C5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=
 Sof(C8B)=Sof(H8B)=Sof(C9B)=Sof(H9B)=Sof(Cl1B)=Sof(C10B)=Sof(C11B)=Sof(C12B)=
 Sof(H12B)=Sof(C13B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=1-FVAR(1)
 Sof(O3B)=Sof(H15B)=0.6*(1-FVAR(2))
 Sof(O3D)=Sof(H11B)=0.4*(1-FVAR(2))
 Sof(O3A)=Sof(O3C)=Sof(H11)=Sof(H15)=0.5*FVAR(2)
 Sof(O1)=Sof(O2)=Sof(N1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2)=Sof(C3)=
 Sof(H3)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=
 Sof(C9)=Sof(H9)=Sof(Cl1)=Sof(C10)=Sof(C11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(C14)=
 Sof(H14)=Sof(C15)=FVAR(1)
7.a Riding coordinates:
 C11(H11), C15(H15), C11B(H11B), C15B(H15B)
7.b Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C2B(H2B), C3B(H3BA), C6B(H6B), C7B(H7B)
7.c Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1B(H1BA,H1BB)
7.d Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C8B(H8B), C9B(H9B), C12(H12), C14(H14), C12B(H12B), C14B(H14B)
;
_shelx_res_checksum              37862
_olex2_submission_special_instructions 'No special instructions were received'