The Long and the Short of It: Regiospecific Syntheses of Isomers of Dicarbomethoxydibenzo-27-crown-9 and Binding Abilities of Their Pyridyl Cryptands.
Pederson, Adam M.-P.; Price, Jr, Terry L; Slebodnick, Carla; Schoonover, Daniel V.; Gibson, Harry W.; The Journal of organic chemistry 82 (2017) 8489–8496; doi:10.1021/acs.joc.7b01242

data_4032722
_publ_section_title
;
 The Long and the Short of It: Regiospecific Syntheses of Isomers of
 Dicarbomethoxydibenzo-27-crown-9 and Binding Abilities of Their Pyridyl
 Cryptands.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8489
_journal_page_last               8496
_journal_paper_doi               10.1021/acs.joc.7b01242
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C35 H41 N O13, C12 H12 N2, 2(F6 P), C3 H6 O'
_chemical_formula_sum            'C50 H59 F12 N3 O14 P2'
_chemical_formula_weight         1215.94
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.9890(5)
_cell_length_b                   21.5927(6)
_cell_length_c                   23.4837(5)
_cell_measurement_reflns_used    6134
_cell_measurement_temperature    100.05(10)
_cell_measurement_theta_max      24.0830
_cell_measurement_theta_min      4.3270
_cell_volume                     10643.0(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0355
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \f      0.00  45.00   1.00   45.00   0.00 -26.00   0.00    --    45
  2  \w    -63.00  19.00   1.00   45.00    --  -26.00  86.00 120.00   82
  3  \f     45.00  90.00   1.00   45.00   0.00 -26.00   0.00    --    45
  4  \w    -64.00  17.00   1.00   45.00    --  -26.00  88.00   0.00   81
  5  \f     90.00 135.00   1.00   45.00   0.00 -26.00   0.00    --    45
  6  \w    -62.00  24.00   1.00   45.00    --  -26.00  84.00-120.00   86
  7  \f    135.00 180.00   1.00   45.00   0.00 -26.00   0.00    --    45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0002401000
_diffrn_orient_matrix_UB_12      0.0266467000
_diffrn_orient_matrix_UB_13      -0.0176697000
_diffrn_orient_matrix_UB_21      -0.0215428000
_diffrn_orient_matrix_UB_22      -0.0148916000
_diffrn_orient_matrix_UB_23      -0.0187881000
_diffrn_orient_matrix_UB_31      -0.0260302000
_diffrn_orient_matrix_UB_32      0.0121262000
_diffrn_orient_matrix_UB_33      0.0157321000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1081
_diffrn_reflns_av_unetI/netI     0.0617
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            74416
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         4.069
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.193
_exptl_absorpt_correction_T_max  0.984
_exptl_absorpt_correction_T_min  0.946
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.518
_exptl_crystal_description       rod
_exptl_crystal_F_000             5040
_exptl_crystal_size_max          0.376
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.089
_refine_diff_density_max         1.701
_refine_diff_density_min         -0.508
_refine_diff_density_rms         0.153
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.212
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     741
_refine_ls_number_reflns         10831
_refine_ls_number_restraints     225
_refine_ls_restrained_S_all      1.203
_refine_ls_R_factor_all          0.1744
_refine_ls_R_factor_gt           0.1245
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3188
_refine_ls_wR_factor_ref         0.3567
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6495
_reflns_number_total             10831
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01242_si_002.cif
_cod_data_source_block           amp006
_cod_database_code               4032722
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C47 H53 O13 N3 P2 F12'
_reflns_odcompleteness_completeness 99.40
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C46A \\sim C47A \\sim C46B \\sim C47B \\sim N2 \\sim N3: within 2A with sigma
of 0.02 and sigma for terminal atoms of 0.04
C23 \\sim O7 \\sim C22 \\sim C21B \\sim C21A \\sim O4B \\sim O4A \\sim C20B
\\sim C20A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
3. Rigid body (RIGU) restrains
 C46B, C46A, C47B, C47A, N3, N2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, O7, C22, C21B, C21A, O4B, O4A, C20B, C20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C46B)=Sof(H46C)=Sof(H46D)=Sof(C47B)=Sof(H47C)=Sof(H47D)=1-FVAR(1)
 Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(C47A)=Sof(H47A)=Sof(H47B)=FVAR(1)
 Sof(H19C)=Sof(H19D)=Sof(H22C)=Sof(H22D)=Sof(O4B)=Sof(C20B)=Sof(H20C)=
 Sof(H20D)=Sof(C21B)=Sof(H21C)=Sof(H21D)=1-FVAR(2)
 Sof(H19A)=Sof(H19B)=Sof(H22A)=Sof(H22B)=Sof(O4A)=Sof(C20A)=Sof(H20A)=
 Sof(H20B)=Sof(C21A)=Sof(H21A)=Sof(H21B)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,
 H17B), C18(H18A,H18B), C19(H19A,H19B), C19(H19C,H19D), C22(H22A,H22B),
 C22(H22C,H22D), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B),
  C27(H27A,H27B), C35(H35A,H35B), C46A(H46A,H46B), C47A(H47A,H47B), C46B(H46C,
 H46D), C47B(H47C,H47D), C20A(H20A,H20B), C21A(H21A,H21B), C20B(H20C,H20D),
 C21B(H21C,H21D)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C9(H9), C11(H11), C12(H12), C30(H30), C31(H31),
 C32(H32), C36(H36), C37(H37), C38(H38), C39(H39), C42(H42), C43(H43), C44(H44),
  C45(H45)
;
_olex2_date_sample_data_collection 2007-07-26
_olex2_date_sample_submission    2007-07-26
_olex2_submission_original_sample_id AMP006
_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 1.034
_oxdiff_exptl_absorpt_empirical_full_min 0.969