(15)N NMR Spectroscopy, X-ray and Neutron Diffraction, Quantum-Chemical Calculations, and UV/vis-Spectrophotometric Titrations as Complementary Techniques for the Analysis of Pyridine-Supported Bicyclic Guanidine Superbases.
Schwamm, Ryan J.; Vianello, Robert; Maršavelski, Aleksandra; García, M Ángeles; Claramunt, Rosa M.; Alkorta, Ibon; Saame, Jaan; Leito, Ivo; Fitchett, Christopher M.; Edwards, Alison J.; Coles, Martyn P.; The Journal of organic chemistry 81 (2016) 7612–7625; doi:10.1021/acs.joc.6b01330

data_4037036
_publ_section_title
;
 (15)N NMR Spectroscopy, X-ray and Neutron Diffraction, Quantum-Chemical
 Calculations, and UV/vis-Spectrophotometric Titrations as Complementary
 Techniques for the Analysis of Pyridine-Supported Bicyclic Guanidine
 Superbases.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7612
_journal_page_last               7625
_journal_paper_doi               10.1021/acs.joc.6b01330
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C15 H28 N7, C24 H20 B'
_chemical_formula_sum            'C43 H48 B N7'
_chemical_formula_weight         673.69
_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     direct
_audit_creation_date             2014-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.18 svn.r2945 for OlexSys, GUI svn.r4846)
;
_cell_angle_alpha                97.607(3)
_cell_angle_beta                 99.959(3)
_cell_angle_gamma                113.378(4)
_cell_formula_units_Z            2
_cell_length_a                   10.4939(4)
_cell_length_b                   10.7181(4)
_cell_length_c                   17.7859(7)
_cell_measurement_reflns_used    10348
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      76.5960
_cell_measurement_theta_min      4.6050
_cell_volume                     1763.31(14)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2013)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6501
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_details
;
  1 omega  -24.00   18.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   37.0000    0.0000 42

  2 omega  -45.00   11.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   37.0000 -150.0000 56

  3 omega -100.00   39.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000    0.0000  -30.0000 139

  4 omega   62.00   88.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       42.6255 -125.0000    0.0000 26

  5 omega   32.00   86.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       42.6255 -125.0000  -60.0000 54

  6 omega   78.00  140.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -77.0000 -150.0000 62

  7 omega   73.00   98.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000  -30.0000 25

  8 omega  106.00  174.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000  -30.0000 68

  9 omega  130.00  176.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000   30.0000 46

 10 omega  126.00  151.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -15.0000   30.0000 25

 11 omega  108.00  144.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   61.0000    0.0000 36

 12 omega   90.00  131.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000 -150.0000 41

 13 omega  150.00  176.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000 -150.0000 26

 14 omega   65.00   91.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000 -150.0000 26

 15 omega   66.00   98.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000  -60.0000 32

 16 omega   49.00   75.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000   30.0000 26

 17 omega   48.00   75.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000   90.0000 27

 18 omega   59.00   86.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -77.0000  150.0000 27

 19 omega   43.00   69.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000   90.0000 26

 20 omega   53.00  109.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000   60.0000 56

 21 omega   94.00  122.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000    0.0000 28

 22 omega   65.00   94.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000 -120.0000 29

 23 omega   44.00  122.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000 -150.0000 78

 24 omega   65.00   91.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000    0.0000 26

 25 omega   42.00  122.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000  -90.0000 80

 26 omega   44.00   89.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000 -150.0000 45

 27 omega   38.00   66.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000  -90.0000 28

 28 omega   53.00   91.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000  -30.0000 38

 29 omega   32.00  103.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000    0.0000 71

 30 omega   38.00   86.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       42.6255 -125.0000  120.0000 48

 31 omega   33.00   96.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  120.0000 63

 32 omega   32.00   93.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -15.0000   30.0000 61
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0762531000
_diffrn_orient_matrix_UB_12      0.1496611000
_diffrn_orient_matrix_UB_13      0.0505953000
_diffrn_orient_matrix_UB_21      0.0090384000
_diffrn_orient_matrix_UB_22      0.0581639000
_diffrn_orient_matrix_UB_23      -0.0745930000
_diffrn_orient_matrix_UB_31      -0.1461392000
_diffrn_orient_matrix_UB_32      0.0036941000
_diffrn_orient_matrix_UB_33      -0.0034642000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0227
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            16420
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.719
_diffrn_reflns_theta_min         4.610
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.584
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94931
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
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    1.269
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.43
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.250
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     464
_refine_ls_number_reflns         7319
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0578P)^2^+0.5203P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1040
_refine_ls_wR_factor_ref         0.1060
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6872
_reflns_number_total             7319
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01330_si_002.cif
_cod_data_source_block           2
_cod_original_cell_volume        1763.30(13)
_cod_database_code               4037036
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         C1H22N4Cl2O2P1F6Co1
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H2A(0.039) H2B(0.039) H3A(0.042) H3B(0.042) H4A(0.036) H4B(0.036)
 H5A(0.031) H5B(0.031) H6A(0.029) H6B(0.029) H7A(0.026) H7B(0.026) H9A(0.027)
 H9B(0.027) H10A(0.034) H10B(0.034) H11A(0.041) H11B(0.041) H12A(0.035)
 H12B(0.035) H13A(0.03) H13B(0.03) H14A(0.031) H14B(0.031) H16(0.029) H17(0.03)
 H18(0.026) H21(0.025) H22(0.029) H23(0.031) H24(0.033) H25(0.03) H27(0.024)
 H28(0.026) H29(0.029) H30(0.031) H31(0.027) H33(0.026) H34(0.029) H35(0.03)
 H36(0.03) H37(0.026) H39(0.032) H40(0.039) H41(0.033) H42(0.03) H43(0.027)
 Fixed X: H2A(0.6442) H2B(0.6691) H3A(0.4208) H3B(0.4537) H4A(0.2637)
 H4B(0.3875) H5A(0.2226) H5B(0.1971) H6A(0.2474) H6B(0.3902) H7A(0.3376)
 H7B(0.4534) H9A(0.9715) H9B(0.9549) H10A(0.7672) H10B(0.8699) H11A(0.7181)
 H11B(0.6046) H12A(0.4788) H12B(0.5988) H13A(0.4936) H13B(0.6605) H14A(0.5542)
 H14B(0.4532) H16(0.8769) H17(1.0765) H18(1.0504) H21(0.5185) H22(0.2762)
 H23(0.1876) H24(0.3459) H25(0.5886) H27(0.7061) H28(0.7291) H29(0.815)
 H30(0.8687) H31(0.8447) H33(0.9918) H34(1.0595) H35(0.9118) H36(0.6949)
 H37(0.625) H39(0.9314) H40(1.0726) H41(1.0878) H42(0.9625) H43(0.8246)
 Fixed Y: H2A(0.3364) H2B(0.4881) H3A(0.413) H3B(0.3802) H4A(0.1851)
 H4B(0.1501) H5A(-0.0264) H5B(0.0588) H6A(-0.116) H6B(-0.0661) H7A(0.086)
 H7B(0.0271) H9A(0.7459) H9B(0.6626) H10A(0.7776) H10B(0.8302) H11A(0.6709)
 H11B(0.6472) H12A(0.3976) H12B(0.4376) H13A(0.1943) H13B(0.2636) H14A(0.1304)
 H14B(0.205) H16(0.4682) H17(0.6082) H18(0.6457) H21(-0.3044) H22(-0.3948) H23(-
 0.2966) H24(-0.1033) H25(-0.0106) H27(0.0828) H28(0.1355) H29(0.017) H30(-
 0.1585) H31(-0.2108) H33(-0.1573) H34(-0.3216) H35(-0.4904) H36(-0.4907) H37(-
 0.3302) H39(0.1901) H40(0.3757) H41(0.3465) H42(0.1257) H43(-0.0591)
 Fixed Z: H2A(0.1416) H2B(0.1792) H3A(0.1619) H3B(0.0805) H4A(0.1043)
 H4B(0.0843) H5A(0.1534) H5B(0.2234) H6A(0.2672) H6B(0.2392) H7A(0.3633)
 H7B(0.3722) H9A(0.5503) H9B(0.6173) H10A(0.5589) H10B(0.6434) H11A(0.6878)
 H11B(0.6111) H12A(0.6219) H12B(0.6989) H13A(0.6409) H13B(0.6512) H14A(0.5239)
 H14B(0.5103) H16(0.2413) H17(0.3442) H18(0.4712) H21(0.2048) H22(0.1504)
 H23(0.0573) H24(0.023) H25(0.0798) H27(0.2863) H28(0.4189) H29(0.5001)
 H30(0.4443) H31(0.3113) H33(0.2272) H34(0.1738) H35(0.0615) H36(0.0044)
 H37(0.0605) H39(0.2564) H40(0.211) H41(0.0815) H42(-0.0006) H43(0.0458)
;
_olex2_submission_special_instructions 'No special instructions were received'