Rotaxane-Based Transition Metal Complexes: Effect of the Mechanical Bond on Structure and Electronic Properties.
Cirulli, Martina; Kaur, Amanpreet; Lewis, James E. M.; Zhang, Zhihui; Kitchen, Jonathan A.; Goldup, Stephen M.; Roessler, Maxie M.; Journal of the American Chemical Society 141 (2019) 879–889; doi:10.1021/jacs.8b09715

data_4133337
_publ_section_title
;
 Rotaxane-Based Transition Metal Complexes: Effect of the Mechanical Bond
 on Structure and Electronic Properties.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              879
_journal_page_last               889
_journal_paper_doi               10.1021/jacs.8b09715
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C67 H80 Cl Cu N3 O6, Cl O4, 0.25(C4 H10 O)'
_chemical_formula_sum            'C68 H82.5 Cl2 Cu N3 O10.25'
_chemical_formula_weight         1282.33
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-18
_audit_creation_method
;
Olex2 1.2
(compiled Nov 22 2016 11:51:51 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                91.0610(10)
_cell_angle_beta                 98.6940(10)
_cell_angle_gamma                109.472(2)
_cell_formula_units_Z            4
_cell_length_a                   17.2694(3)
_cell_length_b                   18.7541(3)
_cell_length_c                   23.8381(4)
_cell_measurement_reflns_used    33992
_cell_measurement_temperature    100
_cell_measurement_theta_max      67.4630
_cell_measurement_theta_min      4.2280
_cell_volume                     7175.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_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      100.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.9936
_diffrn_measured_fraction_theta_max 0.9772
_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    -84.00  94.00   0.50   12.00    --    5.00  29.00  49.00  356
  2  \w   -179.00  -1.00   0.50   12.00    --  -90.00  29.00  49.00  356
  3  \w    -89.00  89.00   0.50    2.00    --    0.00  60.00-180.00  356
  4  \w    -89.00  89.00   0.50    2.00    --    0.00  29.00  49.00  356
  5  \w   -179.00  -1.00   0.50   12.00    --  -90.00  60.00-120.00  356
  6  \w   -179.00  -1.00   0.50   12.00    --  -90.00  60.00 150.00  356
  7  \w   -179.00  -1.00   0.50   12.00    --  -90.00  60.00 150.00  356
  8  \w   -179.00  -1.00   0.50   12.00    --  -90.00  60.00 -30.00  356
  9  \w   -179.00  -1.00   0.50   12.00    --  -90.00  60.00  90.00  356
 10  \w   -179.00  -1.00   0.50   12.00    --  -90.00  60.00 -60.00  356
 11  \w   -179.00 -65.00   0.50   12.00    --  -90.00  60.00  30.00  228
 12  \w   -178.00  -1.00   0.50   12.00    --  -90.00  14.00-180.00  354
 13  \w    -96.00 -69.00   0.50   12.00    --  -90.00  57.00 -60.00   54
 14  \w   -138.00-108.00   0.50   12.00    --  -90.00  43.00 150.00   60
 15  \w   -178.00  -2.00   0.50   12.00    --  -90.00  60.00   0.00  352
 16  \w   -178.00  -2.00   0.50   12.00    --  -90.00  29.00 -90.00  352
 17  \w    -74.00 -47.00   0.50   12.00    --  -90.00  60.00  60.00   54
 18  \w   -179.00-108.00   0.50   12.00    --  -90.00  60.00-150.00  142
 19  \w    -57.00 -29.00   0.50   12.00    --  -90.00  60.00-150.00   56
 20  \w   -177.00-149.00   0.50   12.00    --  -90.00  43.00  30.00   56
 21  \w    -87.00 -60.00   0.50   12.00    --  -90.00  43.00  30.00   54
 22  \w    -43.00 -12.00   0.50   12.00    --  -90.00  43.00  30.00   62
 23  \w   -179.00-149.00   0.50   12.00    --  -90.00  60.00-180.00   60
 24  \w   -144.00 -80.00   0.50   12.00    --  -90.00  60.00-180.00  128
 25  \w    -34.00  -7.00   0.50   12.00    --  -90.00  60.00-180.00   54
 26  \w   -163.00-133.00   0.50   12.00    --  -90.00  60.00 120.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0238728000
_diffrn_orient_matrix_UB_12      -0.0651717000
_diffrn_orient_matrix_UB_13      -0.0240291000
_diffrn_orient_matrix_UB_21      0.0927631000
_diffrn_orient_matrix_UB_22      0.0451940000
_diffrn_orient_matrix_UB_23      0.0211227000
_diffrn_orient_matrix_UB_31      -0.0058671000
_diffrn_orient_matrix_UB_32      -0.0366509000
_diffrn_orient_matrix_UB_33      0.0572199000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0560
_diffrn_reflns_av_unetI/netI     0.0370
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            153610
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.249
_diffrn_reflns_theta_max         70.51
_diffrn_reflns_theta_min         3.76
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.576
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49039
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'bluish green'
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.187
_exptl_crystal_description       block
_exptl_crystal_F_000             2710
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.21
_refine_diff_density_max         1.820
_refine_diff_density_min         -1.467
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1647
_refine_ls_number_reflns         25597
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.1006
_refine_ls_R_factor_gt           0.0857
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1333P)^2^+12.9659P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2377
_refine_ls_wR_factor_ref         0.2517
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20294
_reflns_number_total             25597
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09715_si_005.cif
_cod_data_source_block           5-Cu(II)
_cod_original_formula_sum        'C68 H82.50 Cl2 Cu N3 O10.25'
_cod_database_code               4133337
_chemical_oxdiff_formula         C76H76N3Cl2O8Cu
_chemical_oxdiff_usercomment     'purple crystal'
_shelx_estimated_absorpt_t_max   0.733
_shelx_estimated_absorpt_t_min   0.694
_diffrn_oxdiff_ac3_digest_frames
;
019814ecc815943c8d90196499ff933e09000259a6c
;
_diffrn_oxdiff_ac3_digest_hkl
;
018cbe17044e2495755ee1cfe06d9329cf1f87
;
_reflns_odcompleteness_completeness 99.36
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H17M,H17N,H17O} of C175, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups, {H62A,H62B,H62C} of C62, {H65A,H65B,H65C} of C65,
   {H66A,H66B,H66C} of C66, {H67A,H67B,H67C} of C67, {H53A,H53B,H53C} of C53,
  {H51A,H51B,H51C} of C51, {H63A,H63B,H63C} of C63, {H61A,H61B,H61C} of C61,
  {H52A,H52B,H52C} of C52, {H47A,H47B,H47C} of C47, {H14A,H14B,H14C} of C147,
  {H49A,H49B,H49C} of C49, {H14D,H14E,H14F} of C149, {H14G,H14H,H14I} of C148,
  {H48A,H48B,H48C} of C48, {H15A,H15B,H15C} of C151, {H15D,H15E,H15F} of C152,
  {H17A,H17B,H17C} of C170, {H16A,H16B,H16C} of C169, {H15G,H15H,H15I} of C153,
  {H20G,H20H,H20I} of C201, {H16D,H16E,H16F} of C168, {H20L,H20M,H20N} of C204,
  {H16G,H16H,H16I} of C166, {H16J,H16K,H16L} of C167, {H16M,H16N,H16O} of C165,
  {H16V,H16W,H16X} of C162, {H16Y,H,HA} of C163, {H17D,H17E,H17F} of C172,
  {H17G,H17H,H17I} of C171, {H17J,H17K,H17L} of C173, {H17P,H17Q,H17R} of C174
2. Restrained distances
 C175-C164
 1.5 with sigma of 0.005
 C175-C173
 2.5 with sigma of 0.005
3. Others
 Fixed Sof: C21(0.6) H21A(0.6) H21B(0.6) C20A(0.4) H20A(0.4) H20B(0.4)
 C23(0.6) H23A(0.6) H23B(0.6) C22(0.6) H22A(0.6) H22B(0.6) C151(0.5) H15A(0.5)
 H15B(0.5) H15C(0.5) C152(0.5) H15D(0.5) H15E(0.5) H15F(0.5) O201(0.5)
 C203(0.5) H20E(0.5) H20F(0.5) C170(0.5) H17A(0.5) H17B(0.5) H17C(0.5)
 C169(0.5) H16A(0.5) H16B(0.5) H16C(0.5) C153(0.5) H15G(0.5) H15H(0.5)
 H15I(0.5) C201(0.5) H20G(0.5) H20H(0.5) H20I(0.5) C168(0.5) H16D(0.5)
 H16E(0.5) H16F(0.5) C202(0.5) H20J(0.5) H20K(0.5) C204(0.5) H20L(0.5)
 H20M(0.5) H20N(0.5) C21A(0.4) H21C(0.4) H21D(0.4) C22A(0.4) H22C(0.4)
 H22D(0.4) C23A(0.4) H23C(0.4) H23D(0.4) C20(0.6) H20C(0.6) H20D(0.6)
 C166(0.75) H16G(0.75) H16H(0.75) H16I(0.75) C167(0.75) H16J(0.75) H16K(0.75)
 H16L(0.75) C165(0.75) H16M(0.75) H16N(0.75) H16O(0.75) C160(0.6) H16P(0.6)
 H16Q(0.6) H16R(0.6) H16S(0.4) H16T(0.4) H16U(0.4) C162(0.6) H16V(0.6)
 H16W(0.6) H16X(0.6) C163(0.6) H16Y(0.6) H(0.6) HA(0.6) C172(0.4) H17D(0.4)
 H17E(0.4) H17F(0.4) C171(0.4) H17G(0.4) H17H(0.4) H17I(0.4) C173(0.25)
 H17J(0.25) H17K(0.25) H17L(0.25) C175(0.25) H17M(0.25) H17N(0.25) H17O(0.25)
 C1H(0.4) C174(0.25) H17P(0.25) H17Q(0.25) H17R(0.25)
4.a Secondary CH2 refined with riding coordinates:
 C11(H11G,H11H), C32(H32A,H32B), C30(H30A,H30B), C12(H12I,H12J), C31(H31A,
 H31B), C111(H11A,H11B), C13(H13G,H13H), C112(H11C,H11D), C132(H13A,H13B),
 C113(H11E,H11F), C131(H13C,H13D), C120(H12A,H12B), C21(H21A,H21B), C130(H13E,
 H13F), C122(H12C,H12D), C123(H12E,H12F), C121(H12G,H12H), C20A(H20A,H20B),
 C23(H23A,H23B), C22(H22A,H22B), C203(H20E,H20F), C202(H20J,H20K), C21A(H21C,
 H21D), C22A(H22C,H22D), C23A(H23C,H23D), C20(H20C,H20D)
4.b Me refined with riding coordinates:
 C161(H16P,H16Q,H16R), C161(H16S,H16T,H16U), C173(H17J,H17K,H17L), C175(H17M,
 H17N,H17O)
4.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C136(H136), C59(H59), C37(H37), C9(H9), C36(H36), C55(H55),
 C138(H138), C4(H4), C45(H45), C18(H18), C145(H145), C38(H38), C137(H137),
 C141(H141), C57(H57), C19(H19), C109(H109), C104(H104), C28(H28), C8(H8),
 C7(H7), C41(H41), C102(H102), C103(H103), C108(H108), C2(H2), C143(H143),
 C119(H119), C107(H107), C16(H16), C3(H3), C29(H29), C26(H26), C15(H15),
 C118(H118), C133(H133), C25(H25), C43(H43), C126(H126), C125(H125), C159(H159),
  C115(H115), C116(H116), C129(H129), C157(H157), C128(H128), C155(H155)
4.d Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,
 H67C), C53(H53A,H53B,H53C), C51(H51A,H51B,H51C), C63(H63A,H63B,H63C), C61(H61A,
 H61B,H61C), C52(H52A,H52B,H52C), C47(H47A,H47B,H47C), C147(H14A,H14B,H14C),
 C49(H49A,H49B,H49C), C149(H14D,H14E,H14F), C148(H14G,H14H,H14I), C48(H48A,H48B,
 H48C), C151(H15A,H15B,H15C), C152(H15D,H15E,H15F), C170(H17A,H17B,H17C),
 C169(H16A,H16B,H16C), C153(H15G,H15H,H15I), C201(H20G,H20H,H20I), C168(H16D,
 H16E,H16F), C204(H20L,H20M,H20N), C166(H16G,H16H,H16I), C167(H16J,H16K,H16L),
 C165(H16M,H16N,H16O), C162(H16V,H16W,H16X), C163(H16Y,H,HA), C172(H17D,H17E,
 H17F), C171(H17G,H17H,H17I), C174(H17P,H17Q,H17R)
;
_shelx_fab_checksum              17400
_shelx_shelxl_version_number     2018/1
_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 1.881
_oxdiff_exptl_absorpt_empirical_full_min 0.530