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_7063301
_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_formula_moiety         'C44 H27 Br8 Cl4 N16 O8, 2(C3 H7 N O)'
_chemical_formula_sum            'C50 H41 Br8 Cl4 N18 O10'
_chemical_formula_weight         1835.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-02-08
_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                90
_cell_angle_beta                 112.866(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.1145(6)
_cell_length_b                   23.3689(5)
_cell_length_c                   19.3970(5)
_cell_measurement_reflns_used    11444
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2160
_cell_measurement_theta_min      2.6500
_cell_volume                     7565.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.104a 64-bit (release 22-12-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.104a (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  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_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 0.997
_diffrn_measured_fraction_theta_max 0.959
_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    -44.00  32.00   0.50    8.00    --  -44.12  39.00 146.00  152
  2  \w    -44.00  32.00   0.50    8.00    --  -44.12  39.00 146.00  152
  3  \w   -120.00 -25.00   0.50    8.00    --  -44.12 -39.00  -7.00  190
  4  \w     25.00 120.00   0.50    8.00    --   44.12  39.00 146.00  190
  5  \w   -172.00 -76.00   0.50   20.00    --  -96.00 -39.00  -7.00  192
  6  \w     98.00 178.00   0.50   20.00    --  117.50  39.00 146.00  160
  7  \w    -86.00 -13.00   0.50    8.00    --  -44.12 125.00 -90.00  146
  8  \w    -86.00 -13.00   0.50    8.00    --  -44.12 125.00 -90.00  146
  9  \w     25.00 120.00   0.50    8.00    --   44.12  39.00 146.00  190
 10  \w    -31.00  44.00   0.50    8.00    --   44.12 -39.00  -7.00  150
 11  \w     34.00  94.00   0.50    8.00    --   44.12-125.00  90.00  120
 12  \w     34.00  94.00   0.50    8.00    --   44.12-125.00-150.00  120
 13  \w    -71.00 -22.00   0.50   20.00    --  -96.00  61.00 -30.00   98
 14  \w    -51.00 -21.00   0.50   20.00    --  -96.00  45.00-150.00   60
 15  \w    -51.00 -21.00   0.50   20.00    --  -96.00  45.00 -60.00   60
 16  \w    -51.00 -21.00   0.50   20.00    --  -96.00  45.00 120.00   60
 17  \w    -51.00 -21.00   0.50   20.00    --  -96.00  45.00 150.00   60
 18  \w     98.00 178.00   0.50   20.00    --  117.50  45.00-120.00  160
 19  \w     45.00 105.00   0.50   20.00    --  117.50 -95.00 -90.00  120
 20  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00 -90.00   52
 21  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00 -60.00   52
 22  \w     98.00 178.00   0.50   20.00    --  117.50  45.00  30.00  160
 23  \w     98.00 178.00   0.50   20.00    --  117.50  45.00  30.00  160
 24  \w     45.00 105.00   0.50   20.00    --  117.50 -95.00 -90.00  120
 25  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00 120.00   52
 26  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00 150.00   52
 27  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00  30.00   52
 28  \w     45.00 105.00   0.50   20.00    --  117.50 -77.00 150.00  120
 29  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00 -30.00   52
 30  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00  60.00   52
 31  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00-150.00   52
 32  \w     86.00 155.00   0.50   20.00    --  117.50  15.00 -30.00  138
 33  \w    128.00 155.00   0.50   20.00    --  117.50  15.00 -30.00   54
 34  \w     99.00 126.00   0.50   20.00    --  117.50  61.00-150.00   54
 35  \w    140.00 178.00   0.50   20.00    --  117.50  61.00-150.00   76
 36  \w     58.00 105.00   0.50   20.00    --  117.50 -77.00-150.00   94
 37  \w     59.00  87.00   0.50   20.00    --  117.50 -95.00 120.00   56
 38  \w     45.00  70.00   0.50   20.00    --  117.50 -61.00  90.00   50
 39  \w    152.00 177.00   0.50   20.00    --  117.50  45.00   0.00   50
 40  \w    109.00 143.00   0.50   20.00    --  117.50  45.00   0.00   68
 41  \w     45.00 103.00   0.50   20.00    --  117.50 -77.00 -30.00  116
 42  \w     51.00  99.00   0.50   20.00    --  117.50 -77.00 -90.00   96
 43  \w     45.00  70.00   0.50   20.00    --  117.50 -61.00-120.00   50
 44  \w     45.00  71.00   0.50   20.00    --  117.50 -61.00   0.00   52
 45  \w     63.00  89.00   0.50   20.00    --  117.50 -77.00-120.00   52
 46  \w     46.00 104.00   0.50   20.00    --  117.50 -95.00  60.00  116
;
_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      -0.0150505000
_diffrn_orient_matrix_UB_12      0.0115218000
_diffrn_orient_matrix_UB_13      0.0716520000
_diffrn_orient_matrix_UB_21      -0.0789601000
_diffrn_orient_matrix_UB_22      0.0307003000
_diffrn_orient_matrix_UB_23      -0.0466930000
_diffrn_orient_matrix_UB_31      -0.0453973000
_diffrn_orient_matrix_UB_32      -0.0571863000
_diffrn_orient_matrix_UB_33      -0.0106095000
_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  0.0830
_diffrn_reflns_av_unetI/netI     0.0586
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            87376
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         82.005
_diffrn_reflns_theta_min         2.647
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.875
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.535
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.104a (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    1.611
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3580
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.385
_refine_diff_density_min         -1.561
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     852
_refine_ls_number_reflns         16093
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.1219
_refine_ls_R_factor_gt           0.0776
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1338P)^2^+5.5487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2208
_refine_ls_wR_factor_ref         0.2498
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9627
_reflns_number_total             16093
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj01789g2.cif
_cod_data_source_block           G-31
_cod_depositor_comments
'Adding full bibliography for 7063299--7063301.cif.'
_cod_database_code               7063301
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Br8Cl4C63N16O8
_chemical_oxdiff_usercomment     G-31
_shelx_estimated_absorpt_t_max   0.875
_shelx_estimated_absorpt_t_min   0.446
_platon_squeeze_void_probe_radius 1.20
_reflns_odcompleteness_completeness 99.20
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl1-C38 \\sim C38A-Cl1A
 with sigma of 0.02
 C38-C39 \\sim C38A-C39A
 with sigma of 0.02
 O73A-C73A \\sim O73-C73
 with sigma of 0.02
 C73A-N73A \\sim C73-N73
 with sigma of 0.02
 C58A-C57A \\sim C58-C57
 with sigma of 0.02
 O58A-C57A \\sim O58-C57
 with sigma of 0.04
 C58A-O58A \\sim C58-O58
 with sigma of 0.02
 C60-C61 \\sim C60A-C61A
 with sigma of 0.02
 C61A-C62A \\sim C61-C62
 with sigma of 0.02
 C62-C63 \\sim C62A-C63A
 with sigma of 0.02
 C64-C63 \\sim C63A-C64A
 with sigma of 0.02
 C62-C64 \\sim C62A-C64A
 with sigma of 0.04
 C62-C60 \\sim C60A-C62A
 with sigma of 0.04
 C59-C60 \\sim C60A-C59A
 with sigma of 0.02
 C64-C59 \\sim C59A-C64A
 with sigma of 0.02
 C59-C61 \\sim C61A-C59A
 with sigma of 0.04
 C59-C63 \\sim C59A-C63A
 with sigma of 0.04
 C58-C59 \\sim C58A-C59A
 with sigma of 0.02
 C58-C60 \\sim C58A-C60A
 with sigma of 0.04
 C58A-C64A \\sim C58-C64
 with sigma of 0.04
 O58A-C59A \\sim O58-C59
 with sigma of 0.04
 N73A-C74A \\sim N73-C74
 with sigma of 0.02
 N73-C75 \\sim N73A-C75A
 with sigma of 0.02
 C74-C75 \\sim C75A-C74A
 with sigma of 0.04
 C37-C36 \\sim C36A-C37A
 with sigma of 0.02
 C36-C35 \\sim C35A-C36A
 with sigma of 0.02
 C35-C34 \\sim C34-C35A
 with sigma of 0.02
 C40-C39 \\sim C39A-C40A
 with sigma of 0.02
 C35-C40 \\sim C40A-C35A
 with sigma of 0.02
 C62-Cl4 \\sim Cl4A-C62A
 with sigma of 0.02
 C61-Cl4 \\sim C61A-Cl4A
 with sigma of 0.04
 Cl4A-C63A \\sim Cl4-C63
 with sigma of 0.04
3. Restrained planarity
 Cl1A, C34, C35A, C36A, C37A, C38A, C39A, C40A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C59 \\sim C59A \\sim C60 \\sim C60A \\sim C61 \\sim C61A \\sim C62 \\sim C62A
\\sim C63 \\sim C63A \\sim C64 \\sim C64A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C58) \\sim Ueq, Uanis(C58A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O58) \\sim Ueq, Uanis(O58A) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(Cl4) \\sim Ueq, Uanis(Cl4A) \\sim Ueq: with sigma of 0.008 and sigma for
terminal atoms of 0.016
Uanis(C38) = Uanis(C38A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(C37) = Uanis(C37A)
Uanis(C39) = Uanis(C39A)
Uanis(Br8A) = Uanis(Br8)
Uanis(Br7) = Uanis(Br7A)
Uanis(C57) = Uanis(C57A)
Uanis(O73A) = Uanis(O73)
Uanis(N73A) = Uanis(N73)
Uanis(C73A) = Uanis(C73)
Uanis(C58) = Uanis(C58A)
Uanis(O58) = Uanis(O58A)
Uanis(C60) = Uanis(C60A)
Uanis(C61A) = Uanis(C61)
Uanis(C62) = Uanis(C62A)
Uanis(C63) = Uanis(C63A)
Uanis(C64) = Uanis(C64A)
Uanis(C74) = Uanis(C74A) = Uanis(C75) = Uanis(C75A)
Uanis(C36) = Uanis(C36A) = Uanis(C35) = Uanis(C35A) = Uanis(C40) = Uanis(C40A)
Uanis(Cl4) = Uanis(Cl4A)
5. Others
 Sof(Cl1A)=Sof(C35A)=Sof(C36A)=Sof(H36A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=
 Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40A)=1-FVAR(1)
 Sof(Cl1)=Sof(C35)=Sof(C36)=Sof(H36)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(C39)=
 Sof(H39)=Sof(C40)=Sof(H40)=FVAR(1)
 Sof(Br7A)=Sof(Br8A)=Sof(Cl4A)=Sof(O58A)=Sof(C57A)=Sof(C58A)=Sof(C59A)=
 Sof(C64A)=Sof(H64A)=Sof(C63A)=Sof(H63A)=Sof(C62A)=Sof(C61A)=Sof(H61A)=
 Sof(C60A)=Sof(H60A)=1-FVAR(2)
 Sof(Br7)=Sof(Br8)=Sof(Cl4)=Sof(O58)=Sof(C57)=Sof(C58)=Sof(C59)=Sof(C64)=
 Sof(H64)=Sof(C63)=Sof(H63)=Sof(C62)=Sof(C61)=Sof(H61)=Sof(C60)=Sof(H60)=FVAR(2)
 Sof(O73A)=Sof(N73A)=Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(H74D)=Sof(H74E)=
 Sof(H74F)=Sof(C75A)=Sof(H75D)=Sof(H75E)=Sof(H75F)=1-FVAR(3)
 Sof(O73)=Sof(N73)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C15(H15), C23(H23)
6.b Me refined with riding coordinates:
 C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C74A(H74D,H74E,H74F), C75A(H75D,
 H75E,H75F)
6.c Aromatic/amide H refined with riding coordinates:
 N6(H6), N8(H8), N14(H14), N16(H16), N22(H22), N24(H24), N30(H30), N32(H32),
 C36(H36), C36A(H36A), C37(H37), C37A(H37A), C39(H39), C39A(H39A), C40(H40),
 C40A(H40A), C44(H44), C45(H45), C47(H47), C48(H48), C52(H52), C53(H53),
 C55(H55), C56(H56), C64(H64), C63(H63), C61(H61), C60(H60), C64A(H64A),
 C63A(H63A), C61A(H61A), C60A(H60A), C70(H70), C73(H73), C73A(H73A)
6.d Fitted hexagon refined as free rotating group:
 C59(C64,C63,C62,C61,C60), C59A(C64A,C63A,C62A,C61A,C60A)
6.e Idealised Me refined as rotating group:
 C71(H71A,H71B,H71C), C72(H72A,H72B,H72C)
;
_shelx_res_checksum              38344
_shelx_hkl_checksum              46372
_shelx_fab_checksum              60748
_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 3.173
_oxdiff_exptl_absorpt_empirical_full_min 0.488