Unexpected 20-membered macrocycles obtained by the condensation of α,α-dihalo-β-oxoaldehydes with diaminofurazan
Guseinov, Firudin I.; Ovsyannikov, Viacheslav O.; Shuvalova, Elena V.; Kustov, Leonid M.; Kobrakov, Konstantin I.; Samigullina, Aida I.; Mahmudov, Kamran T.; New Journal of Chemistry 48 (2024) 12869–12872; doi:10.1039/D4NJ01789G

data_7063300
_publ_section_title
;
 Unexpected 20-membered macrocycles obtained by the condensation of
 \a,\a-dihalo-\b-oxoaldehydes with diaminofurazan
;
_journal_issue                   29
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              12869
_journal_page_last               12872
_journal_paper_doi               10.1039/D4NJ01789G
_journal_volume                  48
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety
'2(C44 H28 Cl12 N16 O8), 5.868(C2 H6 O S), 2.132(C3 H7 N O), C2 H3 N'
_chemical_formula_sum            'C108.13 H109.13 Cl24 N35.13 O24 S5.87'
_chemical_formula_weight         3323.80
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-02-06
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2024-03-06 deposited with the CCDC.	2024-07-01 downloaded from the CCDC.
;
_cell_angle_alpha                78.320(2)
_cell_angle_beta                 88.543(2)
_cell_angle_gamma                81.663(2)
_cell_formula_units_Z            1
_cell_length_a                   9.7467(2)
_cell_length_b                   17.9670(4)
_cell_length_c                   21.3451(4)
_cell_measurement_reflns_used    32205
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.5850
_cell_measurement_theta_min      2.5260
_cell_volume                     3621.82(13)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.92a 64-bit (release 05-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL n/a (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_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    -74.00  27.00   0.50    3.00    --  -46.46  85.00 171.00  202
  2  \w    -21.00  74.00   0.50    3.00    --   46.46 -85.00  52.00  190
  3  \w    -21.00  74.00   0.50    3.00    --   46.46 -85.00  52.00  190
  4  \w   -119.00 -19.00   0.50   11.00    --  -91.75  85.00 171.00  200
  5  \w   -164.00 -79.00   0.50   11.00    --  -91.75 -85.00  52.00  170
  6  \w    101.00 178.00   0.50   11.00    --  113.25  85.00 171.00  154
  7  \w    -86.00 -13.00   0.50    3.00    --  -46.46 125.00-120.00  146
  8  \w    -27.00  29.00   0.50    3.00    --  -46.46  19.00 -60.00  112
  9  \w   -101.00 -60.00   0.50    3.00    --  -46.46 -38.00 -60.00   82
 10  \w   -116.00 -31.00   0.50    3.00    --  -46.46 -57.00  30.00  170
 11  \w    -20.00  11.00   0.50    3.00    --  -46.46  19.00  90.00   62
 12  \w    -29.00  -3.00   0.50    3.00    --   46.46 -19.00 -90.00   52
 13  \w    -27.00  18.00   0.50    3.00    --   46.46 -19.00 150.00   90
 14  \w     54.00  93.00   0.50    3.00    --   46.46-125.00-120.00   78
 15  \w    -27.00  42.00   0.50    3.00    --   46.46 -38.00  60.00  138
 16  \w    -51.00 -21.00   0.50   11.00    --  -91.75  45.00  30.00   60
 17  \w    -45.00 -20.00   0.50   11.00    --  -91.75  45.00 -30.00   50
 18  \w     48.00 106.00   0.50   11.00    --  113.25 -95.00-150.00  116
 19  \w     41.00  71.00   0.50   11.00    --  113.25 -61.00 -60.00   60
 20  \w     44.00  69.00   0.50   11.00    --  113.25 -61.00  60.00   50
 21  \w     80.00 108.00   0.50   11.00    --  113.25-106.00-179.19   56
 22  \w     42.00  67.00   0.50   11.00    --  113.25 -61.00-120.00   50
 23  \w     61.00 108.00   0.50   11.00    --  113.25-106.00  30.98   94
 24  \w    101.00 174.00   0.50   11.00    --  113.25  30.00  90.00  146
 25  \w    100.00 158.00   0.50   11.00    --  113.25  30.00-150.00  116
 26  \w     74.00 104.00   0.50   11.00    --  113.25 -95.00-180.00   60
 27  \w     49.00 103.00   0.50   11.00    --  113.25 -95.00-120.00  108
 28  \w     75.00 106.00   0.50   11.00    --  113.25 -95.00  30.00   62
 29  \w    112.00 154.00   0.50   11.00    --  113.25  61.00  30.00   84
 30  \w     96.00 178.00   0.50   11.00    --  113.25  15.00 -60.00  164
 31  \w     43.00 105.00   0.50   11.00    --  113.25 -95.00 -60.00  124
 32  \w     67.00 107.00   0.50   11.00    --  113.25-125.00  30.00   80
 33  \w    148.00 173.00   0.50   11.00    --  113.25  61.00-150.00   50
 34  \w    115.00 140.00   0.50   11.00    --  113.25 -84.00 138.09   50
 35  \w     52.00 106.00   0.50   11.00    --  113.25 -95.00  90.00  108
 36  \w     43.00  68.00   0.50   11.00    --  113.25 -77.00-120.00   50
 37  \w     53.00 107.00   0.50   11.00    --  113.25-103.00 136.69  108
 38  \w     43.00  69.00   0.50   11.00    --  113.25 -95.00-180.00   52
 39  \w     71.00 111.00   0.50   11.00    --  113.25-125.00 -30.00   80
 40  \w    104.00 177.00   0.50   11.00    --  113.25  30.00   0.00  146
 41  \w     78.00 111.00   0.50   11.00    --  113.25-125.00   0.00   66
 42  \w     41.00  71.00   0.50   11.00    --  113.25 -61.00   0.00   60
 43  \w     42.00  70.00   0.50   11.00    --  113.25 -61.00 150.00   56
 44  \w     48.00  83.00   0.50   11.00    --  113.25 -95.00   0.00   70
 45  \w     41.00  71.00   0.50   11.00    --  113.25 -61.00  30.00   60
 46  \w     48.00  74.00   0.50   11.00    --  113.25-125.00   0.00   52
 47  \w     42.00 103.00   0.50   11.00    --  113.25 -95.00 -90.00  122
 48  \w    106.00 131.00   0.50   11.00    --  113.25  61.00  60.00   50
 49  \w    135.00 172.00   0.50   11.00    --  113.25  61.00  60.00   74
 50  \w    103.00 177.00   0.50   11.00    --  113.25  30.00-120.00  148
 51  \w     44.00 111.00   0.50   11.00    --  113.25-125.00 150.00  134
 52  \w    100.00 178.00   0.50   11.00    --  113.25  45.00 -60.00  156
 53  \w     78.00 104.00   0.50   11.00    --  113.25 -95.00  60.00   52
 54  \w     59.00 111.00   0.50   11.00    --  113.25-125.00-150.00  104
 55  \w     43.00 110.00   0.50   11.00    --  113.25-125.00  90.00  134
 56  \w     95.00 152.00   0.50   11.00    --  113.25 125.00 120.00  114
 57  \w    101.00 150.00   0.50   11.00    --  113.25  45.00 150.00   98
 58  \w     45.00 111.00   0.50   11.00    --  113.25-125.00  60.00  132
 59  \w    129.00 155.00   0.50   11.00    --  113.25  45.00  90.00   52
 60  \w    106.00 131.00   0.50   11.00    --  113.25  61.00-150.00   50
 61  \w    117.00 142.00   0.50   11.00    --  113.25  15.00  60.00   50
 62  \w     56.00  82.00   0.50   11.00    --  113.25 -84.00 138.09   52
 63  \w     86.00 111.00   0.50   11.00    --  113.25-125.00-180.00   50
 64  \w     53.00  80.00   0.50   11.00    --  113.25-125.00-180.00   54
 65  \w     61.00  87.00   0.50   11.00    --  113.25 -77.00 -30.00   52
 66  \w     41.00  76.00   0.50   11.00    --  113.25 -77.00 150.00   70
 67  \w     45.00  93.00   0.50   11.00    --  113.25 -95.00 -30.00   96
 68  \w     80.00 106.00   0.50   11.00    --  113.25 -95.00 150.00   52
 69  \w    131.00 177.00   0.50   11.00    --  113.25  30.00 -30.00   92
 70  \w    100.00 176.00   0.50   11.00    --  113.25  45.00 120.00  152
 71  \w     41.00  67.00   0.50   11.00    --  113.25 -61.00-150.00   52
 72  \w     87.00 113.00   0.50   11.00    --  113.25 -88.00 165.96   52
 73  \w     73.00  99.00   0.50   11.00    --  113.25 -85.00  52.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1242525000
_diffrn_orient_matrix_UB_12      -0.0495925000
_diffrn_orient_matrix_UB_13      -0.0243509000
_diffrn_orient_matrix_UB_21      -0.0065303000
_diffrn_orient_matrix_UB_22      -0.0630836000
_diffrn_orient_matrix_UB_23      0.0603421000
_diffrn_orient_matrix_UB_31      -0.1001922000
_diffrn_orient_matrix_UB_32      -0.0372416000
_diffrn_orient_matrix_UB_33      -0.0346071000
_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  0.0605
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            76433
_diffrn_reflns_point_group_measured_fraction_full 0.755
_diffrn_reflns_point_group_measured_fraction_max 0.724
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.979
_diffrn_reflns_theta_min         2.537
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.580
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.438
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1697.7
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.775
_refine_diff_density_min         -1.032
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Flack x determined using 5913 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.074(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1822
_refine_ls_number_reflns         22939
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0592
_refine_ls_R_factor_gt           0.0540
_refine_ls_shift/su_max          0.012
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0842P)^2^+2.6550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1396
_refine_ls_wR_factor_ref         0.1428
_reflns_Friedel_coverage         0.477
_reflns_Friedel_fraction_full    0.511
_reflns_Friedel_fraction_max     0.468
_reflns_number_gt                20912
_reflns_number_total             22939
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj01789g2.cif
_cod_data_source_block           G-26
_cod_depositor_comments
'Adding full bibliography for 7063299--7063301.cif.'
_cod_database_code               7063300
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         C110H126Cl24N34S7O24
_chemical_oxdiff_usercomment     G-26
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.433
_platon_squeeze_void_probe_radius 1.20
_reflns_odcompleteness_completeness 99.32
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_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 C(H,H,H,H,H,H) groups
2. Restrained distances
 S79-C80 \\sim C80A-S79A
 with sigma of 0.02
 S79-O79 \\sim O79-S79A
 with sigma of 0.02
 S79A-C81 \\sim C81-S79
 with sigma of 0.02
 C52A-C51A \\sim C51A-C52C
 with sigma of 0.02
 C52A-C53A \\sim C52C-C53C
 with sigma of 0.02
 C53A-C51A \\sim C51A-C53C
 with sigma of 0.04
 C56A-C51A \\sim C51A-C56C
 with sigma of 0.02
 C55A-C51A \\sim C51A-C55C
 with sigma of 0.04
 C55A-C56A \\sim C55C-C56C
 with sigma of 0.02
 C54A-Cl9 \\sim C54C-Cl25
 with sigma of 0.02
 C53A-C54A \\sim C53C-C54C
 with sigma of 0.02
 C54A-C52A \\sim C52C-C54C
 with sigma of 0.04
 C54A-C56A \\sim C56C-C54C
 with sigma of 0.04
 C54A-C55A \\sim C54C-C55C
 with sigma of 0.02
 C63A-C59A \\sim C59A-C63C
 with sigma of 0.04
 C63A-C64A \\sim C64C-C63C
 with sigma of 0.02
 C64A-C59A \\sim C59A-C64C
 with sigma of 0.02
 C64A-C60A \\sim C60A-C64C
 with sigma of 0.04
 C62A-Cl12 \\sim C62C-Cl26
 with sigma of 0.02
 C63A-C62A \\sim C63C-C62C
 with sigma of 0.02
 C62A-C64A \\sim C62C-C64C
 with sigma of 0.04
 C62A-C61A \\sim C62C-C61C
 with sigma of 0.02
 C61C-C59A \\sim C59A-C61A
 with sigma of 0.02
 C61A-C63A \\sim C61C-C63C
 with sigma of 0.02
 C62A-C60A \\sim C60A-C62C
 with sigma of 0.04
 C61C-C60A \\sim C60A-C61A
 with sigma of 0.02
3. Restrained planarity
 Cl25, C50A, C51A, C52C, C53C, C54C, C55C, C56C
 with sigma of 0.01
 Cl12, C58A, C59A, C60A, C61A, C62A, C63A, C64A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(S79A) = Uanis(S79)
Uanis(C80) = Uanis(C80A)
Uanis(C90) = Uanis(C90A)
Uanis(C91) = Uanis(C91A)
Uanis(O89A) = Uanis(O92)
Uanis(O95) = Uanis(O95A)
Uanis(C97) = Uanis(C98A) = Uanis(C97A) = Uanis(C96)
Uanis(C52A) = Uanis(C52C)
Uanis(Cl9) = Uanis(Cl25)
Uanis(C53C) = Uanis(C53A)
Uanis(C56C) = Uanis(C56A)
Uanis(C55A) = Uanis(C55C)
Uanis(C54A) = Uanis(C54C)
Uanis(Cl12) = Uanis(Cl26)
Uanis(C63A) = Uanis(C63C)
Uanis(C64A) = Uanis(C64C)
Uanis(C62A) = Uanis(C62C) = Uanis(C61C) = Uanis(C61A)
5. Others
 Sof(S89A)=Sof(O89A)=Sof(C90A)=Sof(H90D)=Sof(H90E)=Sof(H90F)=Sof(C91A)=
 Sof(H91D)=Sof(H91E)=Sof(H91F)=1-FVAR(1)
 Sof(O92)=Sof(N89)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=Sof(C91)=Sof(H91A)=
 Sof(H91B)=Sof(H91C)=Sof(C92)=Sof(H92)=FVAR(1)
 Sof(S79A)=Sof(C80A)=Sof(H80D)=Sof(H80E)=Sof(H80F)=Sof(H81D)=Sof(H81E)=
 Sof(H81F)=1-FVAR(2)
 Sof(S79)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=Sof(H81A)=Sof(H81B)=Sof(H81C)=
 FVAR(2)
 Sof(O95A)=Sof(N96A)=Sof(C95A)=Sof(H95A)=Sof(C97A)=Sof(H97A)=Sof(H97B)=
 Sof(H97C)=Sof(C98A)=Sof(H98A)=Sof(H98B)=Sof(H98C)=1-FVAR(3)
 Sof(S95)=Sof(O95)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=Sof(C97)=Sof(H97D)=
 Sof(H97E)=Sof(H97F)=FVAR(3)
 Sof(Cl25)=Sof(C52C)=Sof(H52C)=Sof(C53C)=Sof(H53C)=Sof(C54C)=Sof(C55C)=
 Sof(H55C)=Sof(C56C)=Sof(H56C)=1-FVAR(4)
 Sof(Cl9)=Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(C55A)=
 Sof(H55A)=Sof(C56A)=Sof(H56A)=FVAR(4)
 Sof(Cl26)=Sof(H60B)=Sof(C61C)=Sof(H61C)=Sof(C62C)=Sof(C63C)=Sof(H63C)=
 Sof(C64C)=Sof(H64C)=1-FVAR(5)
 Sof(Cl12)=Sof(H60A)=Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(C63A)=Sof(H63A)=
 Sof(C64A)=Sof(H64A)=FVAR(5)
6.a Free rotating group:
 S89A(O89A,C90A,C91A), O92(N89,C90,C91,C92), S95(O95,C96,C97), O95A(N96A,C95A,
 C97A,C98A)
6.b Ternary CH refined with riding coordinates:
 C7A(H7A), C15A(H15A), C23A(H23A), C31A(H31A), C7B(H7B), C15B(H15B),
 C23B(H23B), C31B(H31B)
6.c Me refined with riding coordinates:
 C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C74(H74A,H74B,H74C), C75(H75A,H75B,
 H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C80(H80A,H80B,H80C),
 C80A(H80D,H80E,H80F), C81(H81A,H81B,H81C), C81(H81D,H81E,H81F), C83(H83A,H83B,
 H83C), C84(H84A,H84B,H84C), C90A(H90D,H90E,H90F), C91A(H91D,H91E,H91F),
 C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C96(H96A,H96B,H96C), C97(H97D,H97E,
 H97F), C97A(H97A,H97B,H97C), C98A(H98A,H98B,H98C), C86(H86A,H86B,H86C),
 C87(H87A,H87B,H87C)
6.d Aromatic/amide H refined with riding coordinates:
 N6A(H6A), N8A(H8A), N14A(H14A), N16A(H16A), N22A(H22A), N24A(H24A),
 N30A(H30A), N32A(H32A), C36A(H36A), C37A(H37A), C39A(H39A), C40A(H40A),
 C44A(H44A), C45A(H45A), C47A(H47A), C48A(H48A), C52A(H52A), C52C(H52C),
 C53A(H53A), C53C(H53C), C55A(H55A), C55C(H55C), C56A(H56A), C56C(H56C),
 C60A(H60A), C60A(H60B), C61A(H61A), C61C(H61C), C63A(H63A), C63C(H63C),
 C64A(H64A), C64C(H64C), N6B(H6B), N8B(H8B), N14B(H14B), N16B(H16B), N22B(H22B),
  N24B(H24B), N30B(H30B), N32B(H32B), C36B(H36B), C37B(H37B), C39B(H39B),
 C40B(H40B), C44B(H44B), C45B(H45B), C47B(H47B), C48B(H48B), C52B(H52B),
 C53B(H53B), C55B(H55B), C56B(H56B), C60B(H60C), C61B(H61B), C63B(H63B),
 C64B(H64B), C92(H92), C95A(H95A), C88(H88)
6.e Idealised Me refined as rotating group:
 C94(H94A,H94B,H94C)
;
_shelx_res_checksum              74925
_shelx_hkl_checksum              59220
_shelx_fab_checksum              97086
_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 1.974
_oxdiff_exptl_absorpt_empirical_full_min 0.576