Elucidation of naphthalene diimide metallomacrocycles and catenanes by solvent dependent excimer and exciplex emission
Boer, Stephanie A.; Cox, Rosalind P.; Beards, Michael; Wang, Huixin; Donald, William; Bell, Toby D. M.; Turner, David Roger; Chemical Communications  (2018) –; doi:10.1039/C8CC09191A

data_7122683
_publ_section_title
;
 Elucidation of naphthalene diimide metallomacrocycles and catenanes by
 solvent dependent excimer and exciplex emission
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C8CC09191A
_journal_year                    2018
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C76 H67 Cd2 N8 O18, 2(H2 O), 0.5(C3 H7 N O)'
_chemical_formula_sum            'C77.5 H74.5 Cd2 N8.5 O20.5'
_chemical_formula_weight         1677.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_symmetry_space_group_name_Hall  'C 2y'
_symmetry_space_group_name_H-M   'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-03-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2018-03-10 deposited with the CCDC.
2018-12-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.1577(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.9956(5)
_cell_length_b                   14.8843(2)
_cell_length_c                   18.7743(2)
_cell_measurement_reflns_used    24779
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      66.8940
_cell_measurement_theta_min      3.7980
_cell_volume                     7475.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3389
_diffrn_detector_type            Ruby
_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    105.00 131.00   1.00    4.00    --   92.50  77.00  30.00   26
  2  \w    127.00 163.00   1.00    4.00    --   92.50  77.00   0.00   36
  3  \w    128.00 164.00   1.00    4.00    --   92.50 125.00  60.00   36
  4  \w    130.00 166.00   1.00    4.00    --   92.50  77.00  90.00   36
  5  \w    121.00 164.00   1.00    4.00    --   92.50  77.00  60.00   43
  6  \w    101.00 127.00   1.00    4.00    --   92.50  77.00 -60.00   26
  7  \w    101.00 136.00   1.00    4.00    --   92.50  61.00 -90.00   35
  8  \w    137.00 168.00   1.00    4.00    --   92.50  77.00-120.00   31
  9  \w    135.00 166.00   1.00    4.00    --   92.50  77.00-180.00   31
 10  \w    105.00 131.00   1.00    4.00    --   92.50  77.00-150.00   26
 11  \w    101.00 149.00   1.00    4.00    --   92.50  61.00-120.00   48
 12  \w     99.00 129.00   1.00    4.00    --   92.50  77.00-120.00   30
 13  \w     91.00 118.00   1.00    4.00    --   92.50  77.00 -30.00   27
 14  \w    100.00 152.00   1.00    4.00    --   92.50  61.00 -30.00   52
 15  \w     93.00 118.00   1.00    1.00    --   41.37  77.00  90.00   25
 16  \w    100.00 167.00   1.00    4.00    --   92.50  77.00 120.00   67
 17  \w     99.00 159.00   1.00    4.00    --   92.50  61.00 150.00   60
 18  \w     86.00 117.00   1.00    4.00    --   92.50 125.00  60.00   31
 19  \w     63.00 132.00   1.00    4.00    --   92.50  61.00 120.00   69
 20  \w     64.00  93.00   1.00    4.00    --   92.50  61.00 150.00   29
 21  \w     60.00 140.00   1.00    4.00    --   92.50  77.00 150.00   80
 22  \w     65.00 151.00   1.00    4.00    --   92.50  61.00  30.00   86
 23  \w     79.00 106.00   1.00    1.00    --   41.37  77.00 -90.00   27
 24  \w     68.00 157.00   1.00    4.00    --   92.50  61.00 -60.00   89
 25  \w     67.00 103.00   1.00    4.00    --   92.50 -45.00  60.00   36
 26  \w     90.00 130.00   1.00    4.00    --   92.50 -93.00  75.34   40
 27  \w     65.00 121.00   1.00    4.00    --   92.50 -61.00 120.00   56
 28  \w     48.00 125.00   1.00    4.00    --   92.50 -93.00  -4.54   77
 29  \w     97.00 122.00   1.00    4.00    --   92.50 -93.00 -83.20   25
 30  \w     58.00  98.00   1.00    4.00    --   92.50 -45.00-180.00   40
 31  \w     42.00 122.00   1.00    4.00    --   92.50 -93.00-146.43   80
 32  \w     41.00  84.00   1.00    4.00    --   92.50 -95.00 -30.00   43
 33  \w     35.00 129.00   1.00    1.00    --   41.37-178.00  30.00   94
 34  \w     25.00  54.00   1.00    4.00    --   92.50 -45.00  60.00   29
 35  \w     28.00  53.00   1.00    4.00    --   92.50 -61.00 120.00   25
 36  \w     23.00 108.00   1.00    4.00    --   92.50 -61.00  60.00   85
 37  \w     18.00 109.00   1.00    1.00    --   41.37  38.00 -30.00   91
 38  \w     60.00  87.00   1.00    4.00    --   92.50  77.00  30.00   27
 39  \w     66.00 157.00   1.00    4.00    --   92.50  61.00  60.00   91
 40  \w     66.00  96.00   1.00    4.00    --   92.50  61.00 -30.00   30
 41  \w     64.00 165.00   1.00    4.00    --   92.50  61.00   0.00  101
 42  \w     60.00  97.00   1.00    4.00    --   92.50  77.00  90.00   37
 43  \w     63.00 128.00   1.00    4.00    --   92.50  61.00  90.00   65
 44  \w     60.00  86.00   1.00    4.00    --   92.50  77.00 -30.00   26
 45  \w     60.00  86.00   1.00    4.00    --   92.50  77.00 -60.00   26
 46  \w     60.00 106.00   1.00    4.00    --   92.50  77.00 -90.00   46
 47  \w     60.00 112.00   1.00    4.00    --   92.50  77.00-180.00   52
 48  \w     60.00  86.00   1.00    4.00    --   92.50  77.00-150.00   26
 49  \w     64.00  95.00   1.00    4.00    --   92.50  61.00-120.00   31
 50  \w     63.00  95.00   1.00    4.00    --   92.50  61.00 -90.00   32
 51  \w     60.00  95.00   1.00    4.00    --   92.50  77.00-120.00   35
 52  \w     63.00 154.00   1.00    4.00    --   92.50  64.00-147.04   91
 53  \w     64.00 144.00   1.00    4.00    --   92.50  62.00-176.32   80
 54  \w     60.00 109.00   1.00    4.00    --   92.50  77.00   0.00   49
 55  \w     60.00 111.00   1.00    4.00    --   92.50  77.00  60.00   51
 56  \w     60.00  86.00   1.00    4.00    --   92.50  77.00 120.00   26
 57  \w      9.00  80.00   1.00    1.00    --   41.37  77.00  90.00   71
 58  \w     17.00 100.00   1.00    4.00    --   92.50 -30.00  90.00   83
 59  \w     24.00  73.00   1.00    4.00    --   92.50 -95.00  30.00   49
 60  \w     17.00 109.00   1.00    4.00    --   92.50 -77.00  30.00   92
 61  \w     14.00  44.00   1.00    4.00    --   92.50 -93.00  -4.54   30
 62  \w     14.00  63.00   1.00    4.00    --   92.50 -93.00 -83.20   49
 63  \w     19.00  48.00   1.00    4.00    --   92.50 -45.00-180.00   29
 64  \w      5.00 119.00   1.00    1.00    --   41.37  19.00-120.00  114
 65  \w     12.00  60.00   1.00    1.00    --   41.37  77.00-180.00   48
 66  \w      9.00  35.00   1.00    1.00    --   41.37  77.00 -90.00   26
 67  \w    -62.00  -9.00   1.00    1.00    --  -41.37 -77.00  30.00   53
 68  \w    -61.00  -9.00   1.00    1.00    --  -41.37 -77.00 -30.00   52
 69  \w    -43.00  -9.00   1.00    1.00    --  -41.37 -77.00-120.00   34
 70  \w   -107.00 -13.00   1.00    1.00    --  -41.37 -57.00  60.00   94
 71  \w   -113.00 -80.00   1.00    1.00    --  -41.37 -77.00  30.00   33
 72  \w   -126.00 -57.00   1.00    1.00    --  -41.37-178.00  30.00   69
 73  \w     13.00  64.00   1.00    4.00    --   92.50 -93.00  75.34   51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0003620000
_diffrn_orient_matrix_UB_12      -0.0468281000
_diffrn_orient_matrix_UB_13      -0.0733782000
_diffrn_orient_matrix_UB_21      -0.0546467000
_diffrn_orient_matrix_UB_22      0.0295384000
_diffrn_orient_matrix_UB_23      -0.0352963000
_diffrn_orient_matrix_UB_31      0.0181605000
_diffrn_orient_matrix_UB_32      0.0874196000
_diffrn_orient_matrix_UB_33      -0.0273715000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0597
_diffrn_reflns_av_unetI/netI     0.0361
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            89995
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.925
_diffrn_reflns_theta_max         66.925
_diffrn_reflns_theta_min         3.901
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.229
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58433
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.491
_exptl_crystal_description       block
_exptl_crystal_F_000             3436
_exptl_crystal_size_max          0.217
_exptl_crystal_size_mid          0.193
_exptl_crystal_size_min          0.032
_refine_diff_density_max         1.211
_refine_diff_density_min         -1.086
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Flack x determined using 4915 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
_platon_squeeze_void_probe_radius                  1.20
_platon_squeeze_details                           SQUEEZE showed solvent accessible voids of 166 \%A3 containing 52 electrons per asymmetric unit, which is accounted for by the solvent not modelled in the crystal structure, 1 DMF and 2 water molecules, which are present in the microanalysis and TGA.

;
_refine_ls_abs_structure_Flack   0.026(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.905
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1042
_refine_ls_number_reflns         13273
_refine_ls_number_restraints     111
_refine_ls_restrained_S_all      0.907
_refine_ls_R_factor_all          0.0586
_refine_ls_R_factor_gt           0.0514
_refine_ls_shift/su_max          0.016
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0788P)^2^+59.9857P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1380
_refine_ls_wR_factor_ref         0.1441
_reflns_Friedel_coverage         0.914
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                11774
_reflns_number_total             13273
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc09191a2.cif
_cod_data_source_block           1
_cod_original_formula_sum        'C77.50 H74.50 Cd2 N8.50 O20.50'
_cod_database_code               7122683
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C50 H50 Cd2 N4 O8'
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. 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, All O(H,H) groups
2. Restrained distances
 O20-H20A = O20-H20B
 0.82 with sigma of 0.02
 O17-H17A = O17-H17B
 0.82 with sigma of 0.001
 O19-C77
 1.15 with sigma of 0.02
 N9-C77
 1.32 with sigma of 0.001
 O18A-H18A = O18A-H18B
 0.82 with sigma of 0.02
 O18B-H18C = O18B-H18D
 0.82 with sigma of 0.02
 N9-C78 = N9-C79
 1.44 with sigma of 0.02
 C6-C4 = C24-C23 = C25-C23 = C23-C22
 1.5 with sigma of 0.005
 H20A-H20B
 1.34 with sigma of 0.04
 H17A-H17B
 1.34 with sigma of 0.04
 H17A-O20_$2
 2 with sigma of 0.04
 O14_$2-H17B
 2 with sigma of 0.04
 C25-C24 = C22-C24
 2.5 with sigma of 0.001
 H18A-H18B
 1.34 with sigma of 0.04
 H18C-H18D
 1.34 with sigma of 0.04
 H18C-Cd2
 2.7 with sigma of 0.04
 O18A-O18B
 1 with sigma of 0.04
 H21B_$3-H65
 2.2 with sigma of 0.08
 C5-C6
 2.5 with sigma of 0.04
 Cd1-H17A \\sim Cd1-H17B
 with sigma of 0.02
 Cd2-H18A \\sim Cd2-H18B
 with sigma of 0.02
 Cd2-H18C \\sim Cd2-H18D
 with sigma of 0.02
3. Rigid bond restraints
 C78, C77, N9, O19, C79
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3, C4, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C77) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C6) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O18B) \\sim Ueq, Uanis(O18A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 C21, C22, C24, C23, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C48, C49, C51, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O18B)=Sof(H18C)=Sof(H18D)=1-FVAR(1)
 Sof(O18A)=Sof(H18A)=Sof(H18B)=FVAR(1)
 Fixed Sof: C78(0.5) H78A(0.5) H78B(0.5) H78C(0.5) C77(0.5) H77(0.5) N9(0.5)
 O19(0.5) C79(0.5) H79A(0.5) H79B(0.5) H79C(0.5)
7.a Free rotating group:
 O21(H21A,H21B)
7.b Ternary CH refined with riding coordinates:
 C21(H21), C47(H47), C30(H30), C2(H2), C28(H28), C49(H49), C23(H23), C4(H4)
7.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C29(H29A,H29B), C48(H48A,H48B)
7.d Me refined with riding coordinates:
 C32(H32A,H32B,H32C), C51(H51A,H51B,H51C), C25(H25A,H25B,H25C), C50(H50A,H50B,
 H50C), C78(H78A,H78B,H78C)
7.e Aromatic/amide H refined with riding coordinates:
 C62(H62), C67(H67), C55(H55), C76(H76), C54(H54), C74(H74), C64(H64),
 C63(H63), C75(H75), C66(H66), C70(H70), C42(H42), C22(H22), C53(H53), C65(H65),
  C17(H17), C16(H16), C43(H43), C37(H37), C11(H11), C71(H71), C59(H59),
 C58(H58), C36(H36), C10(H10), C77(H77)
7.f Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C5(H5A,H5B,H5C), C31(H31A,H31B,H31C), C6(H6A,H6B,H6C),
 C79(H79A,H79B,H79C)
;
_shelx_res_checksum              73911
_shelx_fab_checksum              78765
_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 1.528
_oxdiff_exptl_absorpt_empirical_full_min 0.785