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_7063299
_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
'C48 H40 Br8 N16 O12, 3.117(C3 H7 N O), 0.883(C2 H6 O S) '
_chemical_formula_sum            'C59.12 H67.12 Br8 N19.12 O16 S0.88'
_chemical_formula_weight         1969.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-02-07
_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                 109.326(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8694(4)
_cell_length_b                   29.3492(6)
_cell_length_c                   19.4086(5)
_cell_measurement_reflns_used    27196
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.1900
_cell_measurement_theta_min      2.7800
_cell_volume                     7455.2(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)'
_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 0.995
_diffrn_measured_fraction_theta_max 0.971
_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    -75.00  24.00   0.50    3.00    --  -42.41  86.00  -0.00  198
  2  \w    -75.00  24.00   0.50    3.00    --  -42.41  86.00  -0.00  198
  3  \w      4.00  64.00   0.50    3.00    --   42.41 -86.00-118.00  120
  4  \w   -100.00 -74.00   0.50   22.00    --  -96.00  86.00  -0.00   52
  5  \w     57.00 122.00   0.50   22.00    --  117.50 -86.00-118.00  130
  6  \w    101.00 178.00   0.50   22.00    --  117.50  86.00  -0.00  154
  7  \w    -16.00  38.00   0.50    3.00    --  -42.41  19.00  90.00  108
  8  \w    -27.00  34.00   0.50    3.00    --  -42.41  38.00 120.00  122
  9  \w     35.00  94.00   0.50    3.00    --   42.41-125.00  90.00  118
 10  \w     49.00  75.00   0.50    3.00    --   42.41-125.00 120.00   52
 11  \w   -104.00 -67.00   0.50   22.00    --  -96.00 -77.00 -60.00   74
 12  \w   -149.00-123.00   0.50   22.00    --  -96.00 -77.00 -60.00   52
 13  \w    -50.00 -21.00   0.50   22.00    --  -96.00  45.00-150.00   58
 14  \w   -155.00-110.00   0.50   22.00    --  -96.00 -86.00-118.00   90
 15  \w     54.00 104.00   0.50   22.00    --  117.50 -77.00 120.00  100
 16  \w     48.00  77.00   0.50   22.00    --  117.50-125.00 120.00   58
 17  \w     46.00 104.00   0.50   22.00    --  117.50-125.00  90.00  116
 18  \w     81.00 111.00   0.50   22.00    --  117.50-125.00 120.00   60
 19  \w     65.00 103.00   0.50   22.00    --  117.50 -95.00  90.00   76
 20  \w     92.00 178.00   0.50   22.00    --  117.50  77.00 -90.00  172
 21  \w     44.00  97.00   0.50   22.00    --  117.50 -77.00  60.00  106
 22  \w     44.00  69.00   0.50   22.00    --  117.50 -61.00  90.00   50
 23  \w     46.00  93.00   0.50   22.00    --  117.50 -77.00 -90.00   94
 24  \w     44.00  69.00   0.50   22.00    --  117.50 -61.00 150.00   50
 25  \w     44.00  88.00   0.50   22.00    --  117.50 -77.00 150.00   88
 26  \w     94.00 128.00   0.50   22.00    --  117.50  77.00  30.00   68
 27  \w    140.00 175.00   0.50   22.00    --  117.50  77.00  30.00   70
 28  \w     45.00 103.00   0.50   22.00    --  117.50 -77.00 -60.00  116
 29  \w     50.00  84.00   0.50   22.00    --  117.50 -77.00   0.00   68
 30  \w    103.00 129.00   0.50   22.00    --  117.50  45.00 -90.00   52
 31  \w    135.00 161.00   0.50   22.00    --  117.50  45.00 -90.00   52
 32  \w     55.00 108.00   0.50   22.00    --  117.50-125.00-120.00  106
 33  \w     98.00 160.00   0.50   22.00    --  117.50  61.00 -30.00  124
 34  \w     95.00 121.00   0.50   22.00    --  117.50 125.00   0.00   52
 35  \w     45.00  70.00   0.50   22.00    --  117.50 -61.00 -30.00   50
;
_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      0.0513918000
_diffrn_orient_matrix_UB_12      0.0239404000
_diffrn_orient_matrix_UB_13      -0.0493663000
_diffrn_orient_matrix_UB_21      0.0744117000
_diffrn_orient_matrix_UB_22      -0.0403713000
_diffrn_orient_matrix_UB_23      0.0098667000
_diffrn_orient_matrix_UB_31      -0.0754312000
_diffrn_orient_matrix_UB_32      -0.0235162000
_diffrn_orient_matrix_UB_33      -0.0673216000
_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  0.0615
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            60350
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.331
_diffrn_reflns_theta_min         2.844
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.026
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.682
_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    1.754
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             3911
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.594
_refine_diff_density_min         -1.937
_refine_diff_density_rms         0.180
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.150
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     952
_refine_ls_number_reflns         15830
_refine_ls_number_restraints     47
_refine_ls_restrained_S_all      1.149
_refine_ls_R_factor_all          0.1258
_refine_ls_R_factor_gt           0.1193
_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^)+(0.0268P)^2^+171.4857P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2430
_refine_ls_wR_factor_ref         0.2458
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14317
_reflns_number_total             15830
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj01789g2.cif
_cod_data_source_block           G-29
_cod_depositor_comments
'Adding full bibliography for 7063299--7063301.cif.'
_cod_database_code               7063299
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H20N8O12Br
_chemical_oxdiff_usercomment     G-29
_shelx_estimated_absorpt_t_max   0.840
_shelx_estimated_absorpt_t_min   0.314
_reflns_odcompleteness_completeness 98.90
_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
 C46-C47 \\sim C46A-C47A
 with sigma of 0.02
 C47-C48 \\sim C47A-C48A
 with sigma of 0.02
 C48-C49 \\sim C48A-C49A
 with sigma of 0.02
 C49-C47 \\sim C47A-C49A
 with sigma of 0.04
 C45-C46 \\sim C45A-C46A
 with sigma of 0.02
 C47A-C45A \\sim C45-C47
 with sigma of 0.04
 C47-O50 \\sim C47A-O50A
 with sigma of 0.02
 O50-C50 \\sim O50A-C50A
 with sigma of 0.02
 N73-C75 \\sim N73A-C75A
 with sigma of 0.02
 O73A-N73A \\sim O73-N73
 with sigma of 0.04
 N73-C74 \\sim N73A-C74A
 with sigma of 0.02
 O73A-C73A \\sim O73-C73
 with sigma of 0.02
 C73A-C75A \\sim C73-C75
 with sigma of 0.04
 C73A-C74A \\sim C73-C74
 with sigma of 0.04
 C73A-N73A \\sim C73-N73
 with sigma of 0.02
3. Restrained planarity
 C75A, C74A, N73A, C73A, O73A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq: with sigma of 0.03 and sigma for
terminal atoms of 0.06
Uanis(C73) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C80) \\sim Ueq, Uanis(C80A) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C47) = Uanis(C46)
Uanis(C48) = Uanis(C48A) = Uanis(C47A) = Uanis(C47) = Uanis(C46A) = Uanis(C46)
Uanis(C50) = Uanis(C50A)
Uanis(C19) = Uanis(C20)
Uanis(C49) = Uanis(C49A) = Uanis(C45A) = Uanis(C45)
Uanis(O50) = Uanis(O50A)
Uanis(C75A) = Uanis(C75)
Uanis(O73A) = Uanis(O73)
Uanis(N73A) = Uanis(N73)
Uanis(C74A) = Uanis(C74) = Uanis(C73A) = Uanis(C73)
Uanis(O76) = Uanis(O76A)
Uanis(C77A) = Uanis(C77)
Uanis(C78) = Uanis(C78A)
Uanis(C80) = Uanis(C80A)
Uanis(C81) = Uanis(C81A)
Uanis(C79A) = Uanis(S79)
Uanis(O79) = Uanis(O79A)
5. Others
 Sof(S76A)=Sof(O76A)=Sof(C77A)=Sof(H77D)=Sof(H77E)=Sof(H77F)=Sof(C78A)=
 Sof(H78D)=Sof(H78E)=Sof(H78F)=1-FVAR(1)
 Sof(O76)=Sof(N76)=Sof(C76)=Sof(H76)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=FVAR(1)
 Sof(O79A)=Sof(N79A)=Sof(C79A)=Sof(H79A)=Sof(C80A)=Sof(H80A)=Sof(H80B)=
 Sof(H80C)=Sof(C81A)=Sof(H81A)=Sof(H81B)=Sof(H81C)=1-FVAR(2)
 Sof(S79)=Sof(O79)=Sof(C80)=Sof(H80D)=Sof(H80E)=Sof(H80F)=Sof(C81)=Sof(H81D)=
 Sof(H81E)=Sof(H81F)=FVAR(2)
 Sof(O50A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(C48A)=
 Sof(H48A)=Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(H50D)=Sof(H50E)=Sof(H50F)=1-FVAR(3)
 Sof(O50)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=Sof(C47)=Sof(C48)=Sof(H48)=
 Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=FVAR(3)
 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(4)
 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(4)
6.a Free rotating group:
 S76A(O76A,C77A,C78A), S79(O79,C80,C81), O76(N76,C76,C77,C78), O79A(N79A,C79A,
 C80A,C81A)
6.b Ternary CH refined with riding coordinates:
 C7(H7), C15(H15), C23(H23), C31(H31)
6.c Me refined with riding coordinates:
 C77A(H77D,H77E,H77F), C78A(H78D,H78E,H78F), C80(H80D,H80E,H80F), C81(H81D,
 H81E,H81F), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C74(H74A,H74B,H74C),
 C74A(H74D,H74E,H74F), C75(H75A,H75B,H75C), C75A(H75D,H75E,H75F), C77(H77A,H77B,
 H77C), C78(H78A,H78B,H78C), C80A(H80A,H80B,H80C), C81A(H81A,H81B,H81C)
6.d 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), C37(H37), C39(H39), C40(H40), C45(H45), C45A(H45A), C46(H46),
 C46A(H46A), C48(H48), C48A(H48A), C49(H49), C49A(H49A), C54(H54), C55(H55),
 C57(H57), C58(H58), C63(H63), C64(H64), C66(H66), C67(H67), C70(H70), C73(H73),
  C73A(H73A), C76(H76), C79A(H79A)
6.e Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C50(H50A,H50B,H50C), C50A(H50D,H50E,H50F), C59(H59A,H59B,
 H59C), C68(H68A,H68B,H68C)
;
_shelx_res_checksum              80782
_shelx_hkl_checksum              2005
_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 1.493
_oxdiff_exptl_absorpt_empirical_full_min 0.637