(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_4037035
_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         'C12 H17 N4, F6 P'
_chemical_formula_sum            'C12 H17 F6 N4 P'
_chemical_formula_weight         362.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-10-22
_audit_creation_method
;
Olex2 1.2
(compiled 2014.08.28 svn.r2986 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.3080(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.96475(11)
_cell_length_b                   11.16288(14)
_cell_length_c                   15.67910(16)
_cell_measurement_reflns_used    8956
_cell_measurement_temperature    220.01(10)
_cell_measurement_theta_max      76.7030
_cell_measurement_theta_min      3.9830
_cell_volume                     1532.98(3)
_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      220.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6501
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
  1 omega  -49.00   28.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   37.0000 -180.0000 77

  2 omega -116.00   -5.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -19.0000    0.0000 111

  3 omega   54.00   89.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       42.6255 -125.0000 -180.0000 35

  4 omega   60.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000   60.0000 30

  5 omega   46.00   93.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000 -180.0000 47

  6 omega   75.00  136.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000    0.0000 61

  7 omega   38.00   83.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000 -150.0000 45

  8 omega   67.00  122.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000  150.0000 55

  9 omega   41.00   91.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000  -60.0000 50

 10 omega   38.00   91.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000  120.0000 53

 11 omega   41.00   87.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000    0.0000 46

 12 omega   38.00   63.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000 -180.0000 25

 13 omega   60.00  122.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -61.0000  120.0000 62

 14 omega   94.00  135.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -61.0000    0.0000 41

 15 omega   38.00   91.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000   30.0000 53

 16 omega   23.00   96.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       42.6255 -125.0000   30.0000 73

 17 omega   17.00  111.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       42.6255   57.0000  -90.0000 94

 18 omega   17.00  111.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       42.6255   57.0000 -180.0000 94

 19 omega   90.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   30.0000   30.0000 88

 20 omega   71.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000 -120.0000 107

 21 omega   41.00  122.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000    0.0000 81

 22 omega   85.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   61.0000   60.0000 93

 23 omega   81.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   77.0000  -90.0000 97

 24 omega   85.00  110.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   61.0000  150.0000 25

 25 omega   90.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   30.0000  120.0000 88
;
_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      0.1709929000
_diffrn_orient_matrix_UB_12      -0.0319768000
_diffrn_orient_matrix_UB_13      0.0244598000
_diffrn_orient_matrix_UB_21      -0.0143173000
_diffrn_orient_matrix_UB_22      -0.0256211000
_diffrn_orient_matrix_UB_23      0.0944726000
_diffrn_orient_matrix_UB_31      -0.0388001000
_diffrn_orient_matrix_UB_32      -0.1317572000
_diffrn_orient_matrix_UB_33      -0.0243035000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0235
_diffrn_reflns_av_unetI/netI     0.0132
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            15281
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.756
_diffrn_reflns_theta_min         4.902
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.257
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69433
_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    1.570
_exptl_crystal_description       plate
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.47
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.311
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         3195
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0516
_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^)+(0.0875P)^2^+0.4171P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1428
_refine_ls_wR_factor_ref         0.1464
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2961
_reflns_number_total             3195
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01330_si_002.cif
_cod_data_source_block           1b
_cod_database_code               4037035
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         C23H47N4O10
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H1B(0.061) H1A(0.061) H2AA(0.063) H2AB(0.063) H2BA(0.083)
 H2BB(0.083) H3AA(0.07) H3AB(0.07) H3BA(0.075) H3BB(0.075) H4BC(0.084)
 H4BD(0.084) H4AA(0.084) H4AB(0.084) H5BC(0.077) H5BD(0.077) H5AA(0.077)
 H5AB(0.077) H6AA(0.074) H6AB(0.074) H6BA(0.076) H6BB(0.076) H7AA(0.071)
 H7AB(0.071) H7BA(0.073) H7BB(0.073) H9(0.092) H10(0.103) H11(0.079) H12(0.065)
 Fixed X: H1B(-0.0225) H1A(-0.0117) H2AA(-0.2543) H2AB(-0.1624) H2BA(-0.253)
 H2BB(-0.2682) H3AA(-0.3479) H3AB(-0.2921) H3BA(-0.1634) H3BB(-0.3214) H4BC(-
 0.1353) H4BD(-0.1881) H4AA(-0.2143) H4AB(-0.1363) H5BC(0.0395) H5BD(0.1515)
 H5AA(0.0583) H5AB(0.1046) H6AA(0.319) H6AB(0.3211) H6BA(0.1667) H6BB(0.2874)
 H7AA(0.1812) H7AB(0.3504) H7BA(0.3511) H7BB(0.3767) H9(0.469) H10(0.5674)
 H11(0.4087) H12(0.1536)
 Fixed Y: H1B(0.3748) H1A(0.3947) H2AA(0.4502) H2AB(0.5715) H2BA(0.47)
 H2BB(0.4208) H3AA(0.5869) H3AB(0.4668) H3BA(0.6487) H3BB(0.6218) H4BC(0.6861)
 H4BD(0.6148) H4AA(0.5704) H4AB(0.6905) H5BC(0.6105) H5BD(0.6658) H5AA(0.569)
 H5AB(0.6795) H6AA(0.5822) H6AB(0.5535) H6BA(0.4304) H6BB(0.5316) H7AA(0.3747)
 H7AB(0.3745) H7BA(0.5366) H7BB(0.4067) H9(0.4029) H10(0.272) H11(0.1355)
 H12(0.1379)
 Fixed Z: H1B(0.08) H1A(0.0695) H2AA(0.0284) H2AB(0.0379) H2BA(0.0265)
 H2BB(0.1184) H3AA(0.1214) H3AB(0.1701) H3BA(0.0871) H3BB(0.1108) H4BC(0.1882)
 H4BD(0.2627) H4AA(0.2444) H4AB(0.2259) H5BC(0.3568) H5BD(0.3028) H5AA(0.3638)
 H5AB(0.3131) H6AA(0.2867) H6AB(0.3852) H6BA(0.3679) H6BB(0.4005) H7AA(0.335)
 H7AB(0.3201) H7BA(0.2631) H7BB(0.3023) H9(0.1839) H10(0.0958) H11(0.0102)
 H12(0.0121)
;
_olex2_submission_special_instructions 'No special instructions were received'