Influence of axle length on the rate and mechanism of shuttling in rigid H-shaped [2]rotaxanes
Gholami, Ghazale; Zhu, Kelong; Baggi, Giorgio; Schott, Eduardo; Zarate, Ximena; Loeb, Stephen J.; Chem. Sci.  (2017) –; doi:10.1039/C7SC03736H

data_1547340
_publ_section_title
;
 Influence of axle length on the rate and mechanism of shuttling in rigid
 H-shaped [2]rotaxanes
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC03736H
_journal_year                    2017
_chemical_formula_moiety
'C64 H66 N4, C24 H32 O8, 2(B F4), 3(C7 H8), H2 O'
_chemical_formula_sum            'C109 H124 B2 F8 N4 O9'
_chemical_formula_weight         1807.73
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_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
_audit_creation_date             2017-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-07-20 deposited with the CCDC.
2017-09-25 downloaded from the CCDC.
;
_cell_angle_alpha                97.249(3)
_cell_angle_beta                 100.114(3)
_cell_angle_gamma                108.536(3)
_cell_formula_units_Z            2
_cell_length_a                   14.2079(9)
_cell_length_b                   18.9576(11)
_cell_length_c                   20.1063(13)
_cell_measurement_reflns_used    9776
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      26.42
_cell_measurement_theta_min      2.73
_cell_volume                     4957.8(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_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)'
_diffrn_ambient_temperature      170.01
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0518
_diffrn_reflns_av_unetI/netI     0.0526
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            79916
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.475
_diffrn_reflns_theta_min         2.705
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6649
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0796 before and 0.0586 after correction.
The Ratio of minimum to maximum transmission is 0.8920.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_description       block
_exptl_crystal_F_000             1920
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.626
_refine_diff_density_min         -0.633
_refine_diff_density_rms         0.070
_refine_ls_extinction_coef       0.0026(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1400
_refine_ls_number_reflns         20185
_refine_ls_number_restraints     328
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.1744
_refine_ls_R_factor_gt           0.1057
_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^)+(0.0622P)^2^+10.8936P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2079
_refine_ls_wR_factor_ref         0.2555
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11452
_reflns_number_total             20185
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03736h2.cif
_cod_data_source_block           mo_gg025_0m
_cod_database_code               1547340
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.958
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4
 with sigma of 0.04
 B1-F1 \\sim B1-F2 \\sim B1-F3 \\sim B1-F4
 with sigma of 0.02
 C2T-C3T \\sim C2T-C4T \\sim C3T-C4T
 with sigma of 0.04
 C1T-C2T \\sim C1T-C3T \\sim C1T-C4T
 with sigma of 0.02
 C6T-C7T \\sim C6T-C8T \\sim C7T-C8T
 with sigma of 0.04
 C5T-C6T \\sim C5T-C7T \\sim C5T-C8T
 with sigma of 0.02
 C10T-C11T \\sim C10T-C12T \\sim C11T-C12T
 with sigma of 0.04
 C9T-C10T \\sim C9T-C11T \\sim C9T-C12T
 with sigma of 0.02
 C14T-C15T \\sim C14T-C16T \\sim C15T-C16T
 with sigma of 0.04
 C13T-C14T \\sim C13T-C15T \\sim C13T-C16T
 with sigma of 0.02
 C2-C13 \\sim C2-C5
 with sigma of 0.04
 C15-C1F \\sim C15-C1B
 with sigma of 0.04
 B3-F9 \\sim B3-F10 \\sim B3-F11 \\sim B3-F12
 with sigma of 0.02
 F9-F10 \\sim F10-F11 \\sim F11-F12 \\sim F12-F9 \\sim F10-F12 \\sim F9-F11
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(F12A) \\sim Ueq, Uanis(B3) \\sim Ueq, Uanis(F12B) \\sim Ueq, Uanis(F10)
\\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F9B) \\sim Ueq, Uanis(F11A) \\sim Ueq,
Uanis(F10A) \\sim Ueq, Uanis(F9A) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F11B)
\\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F10B) \\sim Ueq: with sigma of 0.05 and
sigma for terminal atoms of 0.1
Uanis(B1) = Uanis(B1A)
Uanis(F2) = Uanis(F2A)
Uanis(F4) = Uanis(F4A)
Uanis(C1W) = Uanis(C1X) = Uanis(C1Y)
Uanis(C2W) = Uanis(C2X) = Uanis(C2Y)
Uanis(C3W) = Uanis(C3X) = Uanis(C3Y)
Uanis(C4W) = Uanis(C4X) = Uanis(C4Y)
Uanis(C5W) = Uanis(C5X) = Uanis(C5Y)
Uanis(C6W) = Uanis(C6X) = Uanis(C6Y)
Uanis(C7W) = Uanis(C7X) = Uanis(C7Y)
Uanis(C13) = Uanis(C5)
Uanis(C9) = Uanis(C6)
Uanis(C1F) = Uanis(C1C)
Uanis(C1B) = Uanis(C1E)
Uanis(C1A) = Uanis(C1D)
4. Same fragment restrains
{C13T, C14U, C15U, C16U} sigma for 1-2: 0.02, 1-3: 0.02
as
{C13T, C14T, C15T, C16T}
{F1, B1A, F2A, F4A, F3} sigma for 1-2: 0.02, 1-3: 0.02
as
{F1, B1, F2, F4, F3}
{C9T, C10U, C11U, C12U} sigma for 1-2: 0.02, 1-3: 0.02
as
{C9T, C10T, C11T, C12T}
{C1Y, C2Y, C7Y, C6Y, C5Y, C4Y, C3Y} sigma for 1-2: 0.02, 1-3: 0.02
{C1X, C2X, C7X, C6X, C5X, C4X, C3X} sigma for 1-2: 0.02, 1-3: 0.02
as
{C1W, C2W, C7W, C6W, C5W, C4W, C3W}
{B3, F9A, F10A, F11A, F12A} sigma for 1-2: 0.02, 1-3: 0.02
{B3, F9B, F10B, F11B, F12B} sigma for 1-2: 0.02, 1-3: 0.02
as
{B3, F9, F10, F11, F12}
5. Others
 1*[Sof(F9)+Sof(F10)+Sof(F11)+Sof(F12)]+1*[Sof(F9A)+Sof(F10A)+Sof(F11A)+
 Sof(F12A)]+1*[Sof(F9B)+Sof(F10B)+Sof(F11B)+Sof(F12B)]=1 with esd of 0.001
 1*[Sof(C1W)+Sof(H1WA)+Sof(H1WB)+Sof(H1WC)+Sof(C2W)+Sof(C7W)+Sof(H7W)+Sof(C6W)+
 Sof(H6W)+Sof(C5W)+Sof(H5W)+Sof(C4W)+Sof(H4W)+Sof(C3W)+Sof(H3W)]+1*[Sof(C1X)+
 Sof(H1XA)+Sof(H1XB)+Sof(H1XC)+Sof(C2X)+Sof(C7X)+Sof(H7X)+Sof(C6X)+Sof(H6X)+
 Sof(C5X)+Sof(H5X)+Sof(C4X)+Sof(H4X)+Sof(C3X)+Sof(H3X)]+1*[Sof(C1Y)+Sof(H1YA)+
 Sof(H1YB)+Sof(H1YC)+Sof(C2Y)+Sof(C7Y)+Sof(H7Y)+Sof(C6Y)+Sof(H6Y)+Sof(C5Y)+
 Sof(H5Y)+Sof(C4Y)+Sof(H4Y)+Sof(C3Y)+Sof(H3Y)]=1 with esd of 0.001
 Sof(C10U)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11U)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=Sof(C12U)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(1)
 Sof(C10T)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11T)=Sof(H11A)=Sof(H11B)=
 Sof(H11C)=Sof(C12T)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
 Sof(C14U)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15U)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=Sof(C16U)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(2)
 Sof(C14T)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15T)=Sof(H15A)=Sof(H15B)=
 Sof(H15C)=Sof(C16T)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(2)
 Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(3)
 Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(4)
 Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=FVAR(5)
 Sof(B1A)=Sof(F2A)=Sof(F4A)=1-FVAR(6)
 Sof(B1)=Sof(F2)=Sof(F4)=FVAR(6)
 Sof(C1W)=Sof(H1WA)=Sof(H1WB)=Sof(H1WC)=Sof(C2W)=Sof(C7W)=Sof(H7W)=Sof(C6W)=
 Sof(H6W)=Sof(C5W)=Sof(H5W)=Sof(C4W)=Sof(H4W)=Sof(C3W)=Sof(H3W)=FVAR(7)
 Sof(C1X)=Sof(H1XA)=Sof(H1XB)=Sof(H1XC)=Sof(C2X)=Sof(C7X)=Sof(H7X)=Sof(C6X)=
 Sof(H6X)=Sof(C5X)=Sof(H5X)=Sof(C4X)=Sof(H4X)=Sof(C3X)=Sof(H3X)=FVAR(8)
 Sof(C1Y)=Sof(H1YA)=Sof(H1YB)=Sof(H1YC)=Sof(C2Y)=Sof(C7Y)=Sof(H7Y)=Sof(C6Y)=
 Sof(H6Y)=Sof(C5Y)=Sof(H5Y)=Sof(C4Y)=Sof(H4Y)=Sof(C3Y)=Sof(H3Y)=FVAR(9)
 Fixed Sof: C2(0.5) H2A(0.5) H2B(0.5) H2C(0.5) C3(0.5) C5(0.5) H5A(0.5)
 C6(0.5) H6A(0.5) C8(0.5) H8A(0.5) C9(0.5) H9(0.5) C13(0.5) H13(0.5) C15(0.5)
 H15G(0.5) H15H(0.5) H15I(0.5) C1A(0.5) C1F(0.5) H1F(0.5) C1E(0.5) H1E(0.5)
 C1D(0.5) H1D(0.5) C1C(0.5) H1C(0.5) C1B(0.5) H1B(0.5)
6.a Free rotating group:
 O1(H1A,H1G)
6.b Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C51(H51A,H51B), C53(H53A,H53B), C55(H55A,H55B), C58(H58A,
 H58B), C60(H60A,H60B), C63(H63A,H63B), C72(H72A,H72B), C78(H78A,H78B),
 C86(H86A,H86B), C100(H10G,H10H), C108(H10I,H10J)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N5(H5), N6(H6), N8(H8), C11(H11), C19(H19), C20(H20), C24(H24),
 C27(H27), C31(H31), C32(H32), C34(H34), C39(H39), C41(H41), C45(H45), C46(H46),
  C47(H47), C54(H54), C57(H57), C64(H64), C65(H65), C67(H67), C69(H69),
 C73(H73), C75(H75), C76(H76), C77(H77), C83(H83), C84(H84), C103(H103),
 C66(H66), C82(H82), C88(H88), C91(H91), C95(H95), C99(H99), C101(H101),
 C104(H104), C74(H74), C80(H80), C89(H89), C97(H97), C109(H109), C7W(H7W),
 C6W(H6W), C5W(H5W), C4W(H4W), C3W(H3W), C5(H5A), C6(H6A), C8(H8A), C9(H9),
 C13(H13), C1F(H1F), C1E(H1E), C1D(H1D), C1C(H1C), C1B(H1B), C7X(H7X), C6X(H6X),
  C5X(H5X), C4X(H4X), C3X(H3X), C7Y(H7Y), C6Y(H6Y), C5Y(H5Y), C4Y(H4Y), C3Y(H3Y)
6.d Fitted hexagon refined as free rotating group:
 C2W(C7W,C6W,C5W,C4W,C3W), C3(C5,C6,C8,C9,C13), C1A(C1F,C1E,C1D,C1C,C1B)
6.e Idealised Me refined as rotating group:
 C8T(H8TA,H8TB,H8TC), C2T(H2TA,H2TB,H2TC), C3T(H3TA,H3TB,H3TC), C14T(H14A,H14B,
 H14C), C15T(H15A,H15B,H15C), C16T(H16A,H16B,H16C), C4T(H4TA,H4TB,H4TC),
 C6T(H6TA,H6TB,H6TC), C7T(H7TA,H7TB,H7TC), C14(H14G,H14H,H14I), C10T(H10A,H10B,
 H10C), C11T(H11A,H11B,H11C), C12T(H12A,H12B,H12C), C1W(H1WA,H1WB,H1WC),
 C10U(H10D,H10E,H10F), C11U(H11D,H11E,H11F), C12U(H12D,H12E,H12F), C14U(H14D,
 H14E,H14F), C15U(H15D,H15E,H15F), C16U(H16D,H16E,H16F), C2(H2A,H2B,H2C),
 C15(H15G,H15H,H15I), C1X(H1XA,H1XB,H1XC), C1Y(H1YA,H1YB,H1YC)
;
_olex2_submission_special_instructions 'No special instructions were received'