Fluoride binding by an anionic receptor: tuning the acidity of amide NH groups for basic anion hydrogen bonding and recognition
Caltagirone, Claudia; Montis, Riccardo; Lippolis, Vito; Bencini, Andrea; Conti, Luca; Giorgi, Claudia; Horton, Peter; Coles, Simon; Mapp, Lucy K.; Gale, Philip A.; Fusaro, Luca; Chemical Communications  (2019) –; doi:10.1039/C8CC09962F

data_7122835
_publ_section_title
;
 Fluoride binding by an anionic receptor: tuning the acidity of amide NH
 groups for basic anion hydrogen bonding and recognition
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C8CC09962F
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         '1(C29 H24 N5 O6), C16 H36 N, 0.86(H2 O)'
_chemical_formula_sum            'C45 H61.72 N6 O6.86'
_chemical_formula_weight         796.40
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-07-09 deposited with the CCDC.
2019-01-14 downloaded from the CCDC.
;
_cell_angle_alpha                84.157(4)
_cell_angle_beta                 88.236(4)
_cell_angle_gamma                85.515(3)
_cell_formula_units_Z            2
_cell_length_a                   9.4112(3)
_cell_length_b                   14.2754(5)
_cell_length_c                   16.4708(10)
_cell_measurement_reflns_used    11205
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.0190
_cell_measurement_theta_min      1.9960
_cell_volume                     2194.01(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection
'CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)'
_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, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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   -107.00  22.00   1.00   60.00    --  -17.00 -72.00  36.00  129
  2  \w   -107.00  20.00   1.00   60.00    --  -17.00   0.00-108.00  127
  3  \w    -85.00  21.00   1.00   60.00    --  -17.00 -72.00-108.00  106
  4  \w    -39.00  -3.00   1.00   60.00    --  -17.00  72.00-180.00   36
  5  \w   -107.00  47.00   1.00   60.00    --  -17.00   0.00-180.00  154
;
_diffrn_measurement_device       'four-circle \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with HF Varimax confocal mirrors and an AFC12 goniometer and HG Saturn 724+ detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0089596000
_diffrn_orient_matrix_UB_12      -0.0069160000
_diffrn_orient_matrix_UB_13      0.0430545000
_diffrn_orient_matrix_UB_21      0.0738554000
_diffrn_orient_matrix_UB_22      -0.0134665000
_diffrn_orient_matrix_UB_23      0.0036985000
_diffrn_orient_matrix_UB_31      0.0135433000
_diffrn_orient_matrix_UB_32      0.0477470000
_diffrn_orient_matrix_UB_33      0.0027486000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, HF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0599
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            23844
_diffrn_reflns_point_group_measured_fraction_full 0.783
_diffrn_reflns_point_group_measured_fraction_max 0.783
_diffrn_reflns_theta_full        25.028
_diffrn_reflns_theta_max         25.028
_diffrn_reflns_theta_min         1.993
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    0.082
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80788
_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    1.206
_exptl_crystal_description       plate
_exptl_crystal_F_000             857
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 2813 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.4(6)
_refine_ls_extinction_coef       0.0086(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1202
_refine_ls_number_reflns         12127
_refine_ls_number_restraints     1238
_refine_ls_restrained_S_all      0.971
_refine_ls_R_factor_all          0.0826
_refine_ls_R_factor_gt           0.0540
_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^)+(0.0604P)^2^+0.6247P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1122
_refine_ls_wR_factor_ref         0.1249
_reflns_Friedel_coverage         0.568
_reflns_Friedel_fraction_full    0.567
_reflns_Friedel_fraction_max     0.567
_reflns_number_gt                9130
_reflns_number_total             12127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc09962f2.cif
_cod_data_source_block           TBA_HL1-
_cod_database_code               7122835
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C29 H24 N5 O6 C16 H36 N H2O'
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.993
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O4-H40A
 1.9 with sigma of 0.03
 H40B-O33
 1.9 with sigma of 0.03
 H40D-O36_$1
 1.9 with sigma of 0.02
 N35-C52 \\sim N35A-C52A
 with sigma of 0.02
 N35-C59 \\sim N35A-C59A
 with sigma of 0.02
 C50-C51 \\sim C50-C51A
 with sigma of 0.02
 C51-C53 \\sim C51A-C53A
 with sigma of 0.02
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C54-C55 \\sim C54A-C55A
 with sigma of 0.02
 C54-C59 \\sim C54A-C59A
 with sigma of 0.02
 C55-C56 \\sim C55A-C56A
 with sigma of 0.02
 C56-C57 \\sim C56A-C57A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C58-C59 \\sim C58A-C59A
 with sigma of 0.02
 N35-C53 \\sim N35A-C53A
 with sigma of 0.04
 N35-C54 \\sim N35A-C54A
 with sigma of 0.04
 N35-C58 \\sim N35A-C58A
 with sigma of 0.04
 C50-C53 \\sim C50-C53A
 with sigma of 0.04
 C51-C52 \\sim C51A-C52A
 with sigma of 0.04
 C51-C54 \\sim C51A-C54A
 with sigma of 0.04
 C52-C54 \\sim C52A-C54A
 with sigma of 0.04
 C52-C59 \\sim C52A-C59A
 with sigma of 0.04
 C53-C55 \\sim C53A-C55A
 with sigma of 0.04
 C53-C59 \\sim C53A-C59A
 with sigma of 0.04
 C54-C56 \\sim C54A-C56A
 with sigma of 0.04
 C54-C58 \\sim C54A-C58A
 with sigma of 0.04
 C55-C57 \\sim C55A-C57A
 with sigma of 0.04
 C55-C59 \\sim C55A-C59A
 with sigma of 0.04
 C56-C58 \\sim C56A-C58A
 with sigma of 0.04
 C57-C59 \\sim C57A-C59A
 with sigma of 0.04
 C51A-C50 \\sim C51-C50
 with sigma of 0.02
 C215-C214 \\sim C214-C315
 with sigma of 0.02
 C316-C315 \\sim C216-C215
 with sigma of 0.02
 C205-C306 \\sim C206-C205
 with sigma of 0.02
 C306-C307 \\sim C207-C206
 with sigma of 0.02
 C308-C307 \\sim C207-C208
 with sigma of 0.02
3. Rigid bond restraints
 N201, C201, C202, C203, C204, C205, C209, C210, C211, C212, C213, C214, C206,
 C207, C208, C215, C216, C306, C307, C308, C315, C316
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
N201 \\sim C201 \\sim C202 \\sim C203 \\sim C204 \\sim C205 \\sim C209 \\sim
C210 \\sim C211 \\sim C212 \\sim C213 \\sim C214 \\sim C206 \\sim C207 \\sim
C208 \\sim C215 \\sim C216 \\sim C306 \\sim C307 \\sim C308 \\sim C315 \\sim
C316: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H50A)=Sof(N35A)=Sof(H35B)=Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(C52A)=
 Sof(H52A)=Sof(C53A)=Sof(C54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56A)=
 Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=1-FVAR(1)
 Sof(H50)=Sof(N35)=Sof(H35A)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52)=
 Sof(C53)=Sof(C54)=Sof(C55)=Sof(H55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=
 Sof(C58)=Sof(H58)=Sof(C59)=Sof(O402)=Sof(H40C)=Sof(H40D)=FVAR(1)
 Sof(H20L)=Sof(H20M)=Sof(C306)=Sof(H30A)=Sof(H30B)=Sof(C307)=Sof(H30C)=
 Sof(H30D)=Sof(C308)=Sof(H30E)=Sof(H30F)=Sof(H30G)=1-FVAR(2)
 Sof(H20J)=Sof(H20K)=Sof(C206)=Sof(H20P)=Sof(H20Q)=Sof(C207)=Sof(H20R)=
 Sof(H20S)=Sof(C208)=Sof(H20T)=Sof(H20U)=Sof(H20V)=FVAR(2)
 Sof(H21L)=Sof(H21M)=Sof(C315)=Sof(H31A)=Sof(H31B)=Sof(C316)=Sof(H31C)=
 Sof(H31D)=Sof(H31E)=1-FVAR(3)
 Sof(H21J)=Sof(H21K)=Sof(C215)=Sof(H21N)=Sof(H21O)=Sof(C216)=Sof(H21P)=
 Sof(H21Q)=Sof(H21R)=FVAR(3)
7.a Free rotating group:
 O401(H40A,H40B), O402(H40C,H40D)
7.b Ternary CH refined with riding coordinates:
 C40(H40), C50(H50), C50(H50A), C10(H10), C19(H19)
7.c Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C51(H51A,H51B), C51A(H51C,H51D), C201(H20A,H20B), C202(H20C,
 H20D), C203(H20E,H20F), C205(H20J,H20K), C205(H20L,H20M), C209(H20N,H20O),
 C210(H21A,H21B), C211(H21C,H21D), C213(H21H,H21I), C214(H21L,H21M), C214(H21J,
 H21K), C206(H20P,H20Q), C207(H20R,H20S), C215(H21N,H21O), C306(H30A,H30B),
 C307(H30C,H30D), C315(H31A,H31B), C9(H9A,H9B), C21(H21S,H21T), C101(H10A,H10B),
  C102(H10C,H10D), C103(H10E,H10F), C105(H10J,H10K), C106(H10L,H10M), C107(H10N,
 H10O), C109(H10S,H10T), C110(H11A,H11B), C111(H11C,H11D), C113(H11H,H11I),
 C114(H11J,H11K), C115(H11L,H11M)
7.d Aromatic/amide H refined with riding coordinates:
 N31(H31), N32(H32A), C32(H32B), C33(H33), N34(H34), C34(H34A), C35(H35),
 C38(H38), C44(H44), C45(H45), C46(H46), N35(H35A), C52(H52), C55(H55),
 C56(H56), C57(H57), C58(H58), N35A(H35B), C52A(H52A), C55A(H55A), C56A(H56A),
 C57A(H57A), C58A(H58A), N1(H1), N2(H2), C2(H2A), C3(H3), N4(H4), C4(H4A),
 N5(H5A), C5(H5B), C8(H8), C14(H14), C15(H15), C16(H16), C22(H22), C25(H25),
 C26(H26), C27(H27), C28(H28)
7.e Idealised Me refined as rotating group:
 C204(H20G,H20H,H20I), C212(H21E,H21F,H21G), C208(H20T,H20U,H20V), C216(H21P,
 H21Q,H21R), C308(H30E,H30F,H30G), C316(H31C,H31D,H31E), C104(H10G,H10H,H10I),
 C108(H10P,H10Q,H10R), C112(H11E,H11F,H11G), C116(H11N,H11O,H11P)
7.f Idealised tetrahedral OH refined as rotating group:
 O32(H32), O5(H5)
;
_shelx_res_checksum              49423
_shelx_hkl_checksum              16861
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.269
_oxdiff_exptl_absorpt_empirical_full_min 0.734