π-Metalated [1<sub>5</sub>]Paracyclophanes: Synthesis and Binding to Oxo-Anions via Anion-π Interactions.
Zeng, Hong; Liu, Peiren; Feng, Guoqin; Huang, Feihe; Journal of the American Chemical Society 141 (2019) 16501–16511; doi:10.1021/jacs.9b09582

data_4127660
_publ_section_title
;
 \p-Metalated [1<sub>5</sub>]Paracyclophanes: Synthesis and Binding to
 Oxo-Anions via Anion-\p Interactions.
;
_journal_issue                   41
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16501
_journal_page_last               16511
_journal_paper_doi               10.1021/jacs.9b09582
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C65 H72 Ru3, 6(N O3)'
_chemical_formula_sum            'C65 H72 N6 O18 Ru3'
_chemical_formula_weight         1528.49
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                89.892(5)
_cell_angle_beta                 76.000(5)
_cell_angle_gamma                86.719(5)
_cell_formula_units_Z            4
_cell_length_a                   18.2780(14)
_cell_length_b                   20.6817(18)
_cell_length_c                   22.704(2)
_cell_measurement_reflns_used    9990
_cell_measurement_temperature    160(2)
_cell_measurement_theta_max      42.89
_cell_measurement_theta_min      3.13
_cell_volume                     8313.3(12)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      160.62
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_unetI/netI     0.1484
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            31007
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.433
_diffrn_reflns_theta_min         2.942
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.280
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.4061
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.

Final HKLF 4 output contains 133912 reflections, Rint = 0.1256
 (27451 with I > 3sig(I), Rint = 0.0892)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.221
_exptl_crystal_description       block
_exptl_crystal_F_000             3120
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.274
_refine_diff_density_min         -0.800
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     1568
_refine_ls_number_reflns         31007
_refine_ls_number_restraints     619
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.2437
_refine_ls_R_factor_gt           0.1376
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3663
_refine_ls_wR_factor_ref         0.4491
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10140
_reflns_number_total             31007
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09582_si_002.cif
_cod_data_source_block           190523zh_0m_sq
_cod_original_cell_volume        8313.4(12)
_cod_database_code               4127660
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.853
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.453(3)
 0.547(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C53-C54
 1.53 with sigma of 0.02
 C125-C128 = C130-C128 = C129-C128
 1.53 with sigma of 0.02
 C118-C115
 1.5 with sigma of 0.02
 C118-C120
 1.53 with sigma of 0.02
 C55-C53
 1.53 with sigma of 0.02
 C54-C53
 1.53 with sigma of 0.02
 C54-C49
 2.4 with sigma of 0.02
 C44-C43 = C45-C43
 1.53 with sigma of 0.02
 C110-C108
 1.53 with sigma of 0.02
 C109-C108
 1.53 with sigma of 0.02
 C46-C52
 2.33 with sigma of 0.02
 C46-C47
 1.5 with sigma of 0.02
 C51-C53
 2.33 with sigma of 0.02
 C54-C50
 2.45 with sigma of 0.02
 C53-C50
 1.5 with sigma of 0.02
 C55-C50
 2.5 with sigma of 0.02
 C43-C39
 2.35 with sigma of 0.02
 C43-C40
 1.5 with sigma of 0.02
 O29-N10 = O28-N10 = O30-N10
 1.28 with sigma of 0.02
 C56-C57
 1.5 with sigma of 0.02
 O1-N1 = O3-N1 = O2-N1
 1.28 with sigma of 0.02
 C36-C37
 1.5 with sigma of 0.02
 O20-N7 = O21-N7 = O19-N7
 1.28 with sigma of 0.02
 C120-C119
 2.44 with sigma of 0.02
 C118-C116
 2.35 with sigma of 0.02
 O33-N11 = O31-N11 = O32-N11
 1.28 with sigma of 0.02
 C63-C60
 1.5 with sigma of 0.02
 C63-C64
 1.53 with sigma of 0.02
 C65-C63
 1.53 with sigma of 0.02
 C118-C119
 1.53 with sigma of 0.02
 O15-N5 = O13-N5 = O14-N5
 1.28 with sigma of 0.02
 O16-O18
 2.1 with sigma of 0.02
 O17-O18
 2.1 with sigma of 0.02
 O24-N8 = O22-N8 = O23-N8
 1.28 with sigma of 0.02
 O4-O6
 2.1 with sigma of 0.02
 O5-O6
 2.1 with sigma of 0.02
 O11-O12
 2.1 with sigma of 0.02
 O10-O12
 2.1 with sigma of 0.02
 O11-O10
 2.1 with sigma of 0.02
 O8-O9
 2.1 with sigma of 0.02
 O8-N3 = O9-N3 = O7-N3
 1.28 with sigma of 0.02
 O35-C110
 3.5 with sigma of 0.02
 O36-O35
 2.1 with sigma of 0.02
 C110-C109
 2.44 with sigma of 0.02
 C108-C105
 1.5 with sigma of 0.02
 O34-O36
 2.1 with sigma of 0.02
 C116-C120
 2.8 with sigma of 0.02
 C114-C119
 2.7 with sigma of 0.02
 H114-H11I
 2.1 with sigma of 0.02
 O36-N12 = O35-N12 = O34-N12
 1.3 with sigma of 0.02
 N6-O17
 1.3 with sigma of 0.02
 O18-N6
 1.3 with sigma of 0.02
 O17-N6 = O16-N6 = O18-N6
 1.3 with sigma of 0.02
 O5-N2 = O4-N2 = O6-N2
 1.3 with sigma of 0.02
 O11-N4
 1.3 with sigma of 0.02
 N4-O12
 1.3 with sigma of 0.02
 H54C-H49
 2.1 with sigma of 0.02
 C49-C54
 2.8 with sigma of 0.02
 C48-C46 \\sim C46-C52
 with sigma of 0.02
 O31-O33 \\sim O33-O32
 with sigma of 0.02
 O33-O32 \\sim O32-O31
 with sigma of 0.02
 O14-O15 \\sim O15-O13
 with sigma of 0.02
 O13-O14 \\sim O14-O15
 with sigma of 0.02
4. Restrained planarity
 C46, C47, C48, C52
 with sigma of 0.1
 C49, C50, C51, C53
 with sigma of 0.1
 O19, O20, O21, N7
 with sigma of 0.1
 O31, O32, O33, N11
 with sigma of 0.1
 O13, O14, O15, N5
 with sigma of 0.1
 O22, O23, O24, N8
 with sigma of 0.1
 O7, O8, O9, N3
 with sigma of 0.1
 O34, O35, O36, N12
 with sigma of 0.1
 O16, O17, O18, N6
 with sigma of 0.1
 O4, O5, O6, N2
 with sigma of 0.1
 O10, O11, O12, N4
 with sigma of 0.1
5. Rigid bond restraints
 C60, C63, C118, C120
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 Ru3, C51
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C72, C73
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Uiso/Uaniso restraints and constraints
C111 \\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Ru3 \\sim C46 \\sim C48 \\sim C47 \\sim C52 \\sim C51 \\sim C50 \\sim C49 \\sim
C53 \\sim C54 \\sim C55: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C46 \\sim C52: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C40 \\sim C43 \\sim C44 \\sim C45: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim
C109 \\sim C110: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C101 \\sim C102 \\sim C103 \\sim C107: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
C121 \\sim C122 \\sim C127 \\sim C126 \\sim C125 \\sim C124 \\sim C123 \\sim
C128 \\sim C129 \\sim C130: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C59 \\sim C60 \\sim C61: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O28 \\sim O29 \\sim O30 \\sim N10: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C36 \\sim C37 \\sim C38 \\sim C42: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118 \\sim
C119 \\sim C120: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O31 \\sim O32 \\sim O33 \\sim N11: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O25 \\sim O26 \\sim O27 \\sim N9: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O19 \\sim O20 \\sim O21 \\sim N7: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O22 \\sim O23 \\sim O24 \\sim N8: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O7 \\sim O8 \\sim O9 \\sim N3: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O4 \\sim O5 \\sim O6 \\sim N2: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O34 \\sim O35 \\sim O36 \\sim N12: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O18) \\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(O17) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(N4) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(O12) \\sim Ueq, Uanis(O11)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N6) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
7.a Ternary CH refined with riding coordinates:
 C16(H16), C17(H17), C19(H19), C20(H20), C43(H43), C53(H53), C63(H63),
 C67(H67), C108(H108), C118(H118), C128(H128)
7.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B), C21(H21A,H21B), C28(H28A,H28B), C35(H35A,H35B),
 C72(H72A,H72B), C79(H79A,H79B), C86(H86A,H86B), C93(H93A,H93B), C100(H10A,H10B)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13),
 C23(H23), C24(H24), C26(H26), C27(H27), C30(H30), C31(H31), C33(H33), C34(H34),
  C41(H41), C42(H42), C38(H38), C39(H39), C48(H48), C52(H52), C51(H51),
 C49(H49), C59(H59), C61(H61), C62(H62), C58(H58), C68(H68), C70(H70), C71(H71),
  C74(H74), C75(H75), C77(H77), C78(H78), C85(H85), C84(H84), C82(H82),
 C81(H81), C88(H88), C89(H89), C91(H91), C92(H92), C99(H99), C98(H98), C96(H96),
  C95(H95), C103(H103), C104(H104), C106(H106), C107(H107), C113(H113),
 C114(H114), C116(H116), C117(H117), C127(H127), C126(H126), C124(H124),
 C123(H123)
7.d Fitted hexagon refined as free rotating group:
 C8(C9,C10,C11,C12,C13), C40(C41,C42,C37,C38,C39), C48(C47,C52,C51,C50,C49),
 C59(C60,C61,C62,C57,C58), C80(C85,C84,C83,C82,C81), C94(C99,C98,C97,C96,C95),
 C102(C103,C104,C105,C106,C107), C112(C113,C114,C115,C116,C117), C122(C127,C126,
 C125,C124,C123)
7.e Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C101(H10C,H10D,H10E), C109(H10F,H10G,H10H),
 C110(H11A,H11B,H11C), C111(H11D,H11E,H11F), C119(H11G,H11H,H11I), C120(H12A,
 H12B,H12C), C121(H12D,H12E,H12F), C129(H12G,H12H,H12I), C130(H13A,H13B,H13C)
;
_shelx_res_checksum              41112
_shelx_hkl_checksum              52249
_shelx_fab_checksum              19966
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'