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ISSN: 2056-9890

5,5-Di­chloro-6-hy­dr­oxy­di­hydro­pyrimidine-2,4(1H,3H)-dione: mol­ecular and crystal structure, Hirshfeld surface analysis and the new route for synthesis with Mg(ReO4)2 as a new catalyst

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aPeoples' Friendship University of Russia, 6 Miklukho-Maklaya St, 117198, Moscow, Russian Federation, bA. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospekt bldg 4, 119071 Moscow, Russian Federation, and cMedical University REAVIZ, Moscow branch, Krasnobogatyrskaya 2, 107564 Moscow, Russian Federation
*Correspondence e-mail: tony.novickoff@yandex.ru

Edited by O. Blacque, University of Zürich, Switzerland (Received 5 August 2020; accepted 27 August 2020; online 4 September 2020)

The mol­ecular and crystal structures of the title compound, C4H4Cl2N2O3, were investigated by single-crystal X-ray diffraction and a Hirshfeld surface analysis. The title compound was synthesized by a new type of reaction using Mg(ReO4)2 as a new catalyst and a possible mechanism for this reaction is proposed. The six-membered ring adopts a half-chair conformation. In the crystal, hydrogen bonds connect the mol­ecules into double layers, which are connected to each other by halogen bonds. The Hirshfeld surface analysis revealed that the most important contributions for the crystal packing are from O⋯H/H⋯O (35.8%), Cl⋯Cl (19.6%), Cl⋯H/H⋯Cl (17.0%), H⋯H (8.3%), C⋯O/O⋯C (4.3%), Cl⋯O/O⋯Cl (4.2%) and O⋯O (4.1%) contacts.

1. Chemical context

Nitro­gen heterocycles and pyrimidines are examples of the most important biologically active compounds and find a wide use in modern medicine (Pałasz et al., 2015[Pałasz, A. & Ciez, D. (2015). Eur. J. Med. Chem. 97, 582-611.]; Takeshita et al., 2006[Takeshita, J., Byun, J., Nhan, T. Q., Pritchard, D. K., Pennathur, S., Schwartz, S. M., Chait, A. & Heinecke, J. W. (2006). J. Biol. Chem. 281, 3096-3104.]; Henderson et al., 2003[Henderson, J. P., Byun, J., Takeshita, J. & Heinecke, J. W. (2003). J. Biol. Chem. 278, 23522-23528.]). Uracil is widespread in nature as a pyrimidine derivative, and is found as a part of nucleic acids. Uracil derivatives are used for therapeutic purposes (Smith et al., 2004[Smith, N. F., Figg, W. D. & Sparreboom, A. (2004). Drug Dev. Res. 62, 233-253.]; Kasradze et al., 2012[Kasradze, V. G., Ignatyeva, I. B., Khusnutdinov, R. A., Suponitskii, K. Yu., Antipin, M. Yu. & Yunusov, M. S. (2012). Chem. Heterocycl. Compd, 48, 1018-1027.]) . Halogen derivatives of uracil serve as convenient inter­mediates for the preparation of compounds with various functional groups (Wamhoff et al., 1992[Wamhoff, H., Dzenis, J. & Hirota, K. (1992). Adv. Heterocycl. Chem. 55, 129-259.]). Halogen–halogen bonding has recently attracted attention as it expands the possibilities of understanding the new properties of compounds containing halogens and their applications (Szell et al., 2017[Szell, P. M. J., Gabriel, S. A., Gill, R. D. D., Wan, S. Y. H., Gabidullin, B. & Bryce, D. L. (2017). Acta Cryst. C73, 157-167.]). Pyrimidine derivatives are used as inter­mediates for the production of various complex organic mol­ecules for the treatment of cancer and AIDS (Fawcett et al., 1996[Fawcett, J., Henderson, W., Kemmitt, R. D. W., Russell, D. R. & Upreti, A. (1996). J. Chem. Soc. Dalton Trans. pp. 1897-1903.]). Several pyrimidine derivatives belong to the class of central nervous system depressants (Soayed et al., 2015[Soayed, A. A., Refaat, H. M. & Sinha, L. (2015). J. Saudi Chem. Soc. 19, 217-226.]).

[Scheme 1]

5,5-Di­chloro-6-hy­droxy­dihydro­pyrimidine-2,4(1H,3H)-di­one (1) was earlier synthesized by two reaction schemes starting with uracil: (1) by addition of Cl2 in H2O (Johnson et al., 1943[Johnson, T. B. (1943). J. Am. Chem. Soc. 65, 1220-1222.]) or (2) by addition of Na2S2O8 and NaCl in acetic acid (Itahara et al., 1986[Itahara, T., Ebihara, R., Fujii, Y. & Tada, M. (1986). Chem. Lett. 15, 1319-1322.]). We have found a new reaction for the synthesis of 1 by the reaction of uracil with hydro­chloric acid and water in the presence of Mg(ReO4)2 as a catalyst. The reaction scheme is shown in Fig. 1[link].

[Figure 1]
Figure 1
Synthesis scheme of 1.

2. Structural commentary

The title compound crystallizes in the space group C2/c with eight mol­ecules in the unit cell. The asymmetric unit is illustrated in Fig. 2[link]. A similar compound with a methyl group instead of an H atom at C5 (ZEQYIF; Kasradze et al., 2012[Kasradze, V. G., Ignatyeva, I. B., Khusnutdinov, R. A., Suponitskii, K. Yu., Antipin, M. Yu. & Yunusov, M. S. (2012). Chem. Heterocycl. Compd, 48, 1018-1027.]; ZEQYIF01; Sharutin, 2016[Sharutin, V. (2016). Private Communication (refcode ZEQYIF01). CCDC, Cambridge, England.]) crystallizes in the space group P[\overline{1}]. The six-membered ring adopts a half-chair conformation, as in ZEQYIF (Kasradze et al., 2012[Kasradze, V. G., Ignatyeva, I. B., Khusnutdinov, R. A., Suponitskii, K. Yu., Antipin, M. Yu. & Yunusov, M. S. (2012). Chem. Heterocycl. Compd, 48, 1018-1027.]). The largest angle at nitro­gen atom, C6—N1—C2, is 126.69 (13)°. The angle involving the two chlorine atoms, Cl1—C5—Cl2, is 109.29 (8)°. The two C—N bonds at the N1 atom are similar in length while those at N3 differ because of the N3—C2 sp2-conjugation, the latter bond being only 1.344 (2) Å (Table 1[link]). The six atoms N3, C2, O2, N1, C6 and O1 are almost planar (r.m.s. deviation of fitted atoms = 0.0462 Å) while the two other ring atoms of the ring C4 and C5 are displaced from this plane by −0.275 (2) and 0.411 (3) Å, respectively, forming the above mentioned half-chair.

Table 1
Selected geometric parameters (Å, °)

N1—C6 1.3658 (19) N3—C4 1.447 (2)
N1—C2 1.375 (2) C4—C5 1.531 (2)
N3—C2 1.344 (2) C5—C6 1.536 (2)
       
C6—N1—C2 126.69 (13) Cl1—C5—Cl2 109.29 (8)
[Figure 2]
Figure 2
Mol­ecular structure of the title compound, including atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supra­molecular features

The hydrogen-bond system is shown in Fig. 3[link]. In the structure, there are two bifurcated hydrogen bonds. O3—H3 forms a bifurcated hydrogen bond with the O1i and O2ii atoms [symmetry codes: (i) x, y + 1, z; (ii) x, −y + 2, z + [{1\over 2}]] of different mol­ecules. The C4—H4A⋯O1i hydrogen bond also involves O1i with a H4A⋯O1i distance of 3.058 (2) Å (Table 2[link]). In the similar compound ZEQYIF (Kasradze et al., 2012[Kasradze, V. G., Ignatyeva, I. B., Khusnutdinov, R. A., Suponitskii, K. Yu., Antipin, M. Yu. & Yunusov, M. S. (2012). Chem. Heterocycl. Compd, 48, 1018-1027.]), the OH group participates as proton donor in a very strong hydrogen bond with the O atom of one of the CO groups of a neighbouring mol­ecule. In our crystal structure, such strong hydrogen bonds are absent. N3—H3A forms a bifurcated hydrogen bond weaker than O3—H3 with atoms O2iv and O3v [symmetry codes: (iv) −x, −y + 2, −z + 1; (v) x, −y + 2, z − [{1\over 2}]] of different mol­ecules. The strongest hydrogen bond is N1—H1A⋯O2iii [symmetry code: (iii) −x, −y + 1, −z + 1] with an N1⋯O2iii distance of 2.793 (2) Å. The hydrogen bonds connect the mol­ecules into double layers parallel to the (100) plane, as shown in Fig. 4[link]. Halogen bonds Cl1⋯Cl1vi [3.3670 (9) Å] and Cl2⋯Cl2vii [3.3568 (8) Å; symmetry codes: (vi) [{1\over 2}] − x, [{3\over 2}] − y, 2 − z; (vii) [{1\over 2}] − x, [{3\over 2}] − y, 1 − z] connect the layers, forming a three-dimensional framework.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H3⋯O1i 0.81 (2) 2.41 (2) 3.045 (2) 136 (2)
O3—H3⋯O2ii 0.81 (2) 2.16 (2) 2.8076 (18) 138 (2)
N1—H1A⋯O2iii 0.89 (2) 1.91 (2) 2.7932 (17) 178 (2)
N3—H3A⋯O2iv 0.79 (2) 2.46 (2) 3.0978 (19) 138 (2)
N3—H3A⋯O3v 0.79 (2) 2.60 (2) 3.147 (2) 128 (2)
C4—H4A⋯O1i 1.00 2.45 3.058 (2) 119
Symmetry codes: (i) x, y+1, z; (ii) [x, -y+2, z+{\script{1\over 2}}]; (iii) -x, -y+1, -z+1; (iv) -x, -y+2, -z+1; (v) [x, -y+2, z-{\script{1\over 2}}].
[Figure 3]
Figure 3
View showing the hydrogen bonds in 1. [Symmetry codes: (i) x, y + 1, z; (ii) x, −y + 2, z + [{1\over 2}]; (iii) −x, −y + 1, −z + 1; (iv) −x, −y + 2, −z + 1; (v) x, −y + 2, z − [{1\over 2}].]
[Figure 4]
Figure 4
Crystal packing of 1 showing the double layers with halogen bonds between them.

4. Hirshfeld surface analysis

The Crystal Explorer 17.5 (Turner et al., 2017[Turner, M. J., Mckinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17.5. The University of Western Australia.]) program was used to analyse the inter­actions within the crystal. The donor–acceptor groups are visualized using a standard (high) surface resolution and dnorm surfaces are mapped over a fixed colour scale of −0.640 (red) to 0.986 (blue) a.u., as illustrated in Fig. 5[link]. Red spots on the surface of the dnorm plot indicate inter­molecular contacts involving the hydrogen and halogen bonds. The brightest red spots correspond to the strongest hydrogen bonds, N1—H1A⋯O2 and O3—H3⋯O2 (Table 2[link]). There are no ππ inter­actions in the mol­ecule, as can be seen from Fig. 5[link]b by the absence of characteristic triangles. The fingerprint plots (Fig. 6[link]) show that the O⋯H/H⋯O contacts (35.8%) make the largest contribution to the overall packing of the crystal, which is due to the fact that hydrogen bonds of the O—H⋯O and N—H⋯O types are predominantly formed in the crystal. Then, the Cl⋯Cl (19.6%) and Cl⋯H/H⋯Cl (17.0%) contacts make approximately the same contribution. H⋯H (8.3%) contacts make an insignificant contribution, similarly for the C⋯O/O⋯C (4.3%), Cl⋯O/O⋯Cl (4.2%) and O⋯O (4.1%) contacts, which make approximately the same contribution. Other contacts make weaker contributions to the packaging and are not shown in Fig. 6[link].

[Figure 5]
Figure 5
Hirshfeld surface mapper over (a) dnorm and (b) shape-index to visualize the inter­actions in the title compound.
[Figure 6]
Figure 6
(a) A full two-dimensional fingerprint plot for the title compound, together with those delineated into (b) O⋯H/H⋯O, (c) Cl⋯Cl, (d) Cl⋯H/H⋯Cl, (e) H⋯H, (f) C⋯O/O⋯C, (g) Cl⋯O/O⋯Cl and (h) O⋯O contacts.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.41, update of November 2019; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) for different possible substituents at C4 and C5 atoms gave only a few results. A similar compound was found with a methyl group instead of an H atom at C5 (ZEQYIF; Kasradze et al., 2012[Kasradze, V. G., Ignatyeva, I. B., Khusnutdinov, R. A., Suponitskii, K. Yu., Antipin, M. Yu. & Yunusov, M. S. (2012). Chem. Heterocycl. Compd, 48, 1018-1027.]; ZEQYIF01; Sharutin, 2016[Sharutin, V. (2016). Private Communication (refcode ZEQYIF01). CCDC, Cambridge, England.]). In cis-thymine glycol (THYGLY10; Flippen, 1973[Flippen, J. L. (1973). Acta Cryst. B29, 1756-1762.]), one of the chlorine atoms is replaced by an OH group, and the second chlorine atom is replaced by a methyl group. FUFDIT (Flippen-Anderson, 1987[Flippen-Anderson, J. L. (1987). Acta Cryst. C43, 2228-2230.]) is the same as cis-thymine glycol, except that the H atom in the hydroxyl group is replaced by OH group and water of crystallization is present.

6. Synthesis and crystallization

The title compound was synthesized by adding 5 mg of uracil (Sigma Aldrich) to 1 ml of 1 mol l−1 hydro­chloric acid aqueous solution in the presence of magnesium perrhenate. This solution was heated in a water bath (at 348 K) until the components were completely dissolved. Crystallization occurred with isothermal evaporation of the resulting solution at room temperature for several weeks, giving colourless needle-shaped crystals, composition according to chemical analysis (obs./calc.): C, 24.12/24.14; H, 2.04/2.03; Cl, 35.64/35.63; N, 14.07/14.08; O, 24.13/24.12. Crystals suitable for a X-ray structural analysis were extracted manually from this batch.

We suggest a possible mechanism of the observed reaction. Typically, ReO4 does not react with HCl while TcO4 is actively reduced (German et al., 2002[German, K. E. & Kryutchkov, S. V. (2002). Russ. J. Inorg. Chem. 47(4), 578-583.]). We found that in the presence of Mg2+, the ReO4 being distorted according to (Khrustalev, 2000[Khrustalev, V. N. (2000). Synthesis and X-ray single crystal investigation of the 3d group of the Periodic Table perrhenates, pp. 62-65. PhD Thesis. Moscow. (In Russian.)]; Ravi et al., 2018[Ravi, A., Oshchepkov, A. S., German, K. E., Kirakosyan, G. A., Safonov, A. V., Khrustalev, V. N. & Kataev, E. A. (2018). Chem. Commun. 54, 4826-4829.]) attacks the HCl, forming Cl2 that is readily reacted with water to form HOCl. In the air and in low acidic HCl·H2O solution, the Re is then oxidized back to ReVII. Cl2 is thus formed by the action of hydro­chloric acid on the rhenium salt as a result of a redox reaction. The process of hypohalogenation is then likely to occur. Since the reaction takes place in an aqueous medium, the formation of hypohalogenic acid is possible by the reaction Cl2 + H2O = HOCl + HCl. Hypohalogenation is usually carried out with an aqueous solution of halogen. The addition to positions 5 and 6 is electrophilic, in accordance with the electron-density distribution. The partially positively charged halogen atom is directed towards carbon C5, which has a higher partial negative charge compared to the C6 atom, towards which the hydroxyl is directed. Then, at position C5, hydrogen is possibly replaced by Cl2 by electrophilic (more likely in an aqueous medium) and possibly through radical substitution.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The C-bound hydrogen atom was placed at a calculated position (C—H = 1.00 Å) and refined using a riding-atom model [Uiso(H) = 1.2Ueq(C)]. O- and N-bound H atoms were refined isotropically [Uiso(H) = 1.2Ueq(O, N)].

Table 3
Experimental details

Crystal data
Chemical formula C4H4Cl2N2O3
Mr 198.99
Crystal system, space group Monoclinic, C2/c
Temperature (K) 100
a, b, c (Å) 19.9042 (10), 6.6243 (4), 10.5636 (7)
β (°) 90.819 (4)
V3) 1392.68 (14)
Z 8
Radiation type Mo Kα
μ (mm−1) 0.89
Crystal size (mm) 0.50 × 0.10 × 0.02
 
Data collection
Diffractometer Bruker Kappa APEXII area-detector diffractometer
Absorption correction Multi-scan (SADABS; Bruker, 2008[Bruker (2008). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.802, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections 12430, 3046, 2128
Rint 0.045
(sin θ/λ)max−1) 0.807
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.103, 1.02
No. of reflections 3046
No. of parameters 109
No. of restraints 3
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.91, −0.55
Computer programs: APEX2 and SAINT-Plus (Bruker, 2012[Bruker (2012). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and SHELXL2018 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

Supporting information


Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT-Plus (Bruker, 2012); data reduction: SAINT-Plus (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015).

5,5-Dichloro-6-hydroxydihydropyrimidine-2,4(1H,3H)-dione top
Crystal data top
C4H4Cl2N2O3F(000) = 800
Mr = 198.99Dx = 1.898 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 19.9042 (10) ÅCell parameters from 3314 reflections
b = 6.6243 (4) Åθ = 3.8–34.7°
c = 10.5636 (7) ŵ = 0.89 mm1
β = 90.819 (4)°T = 100 K
V = 1392.68 (14) Å3Needle, colourless
Z = 80.50 × 0.10 × 0.02 mm
Data collection top
Bruker Kappa APEXII area-detector
diffractometer
2128 reflections with I > 2σ(I)
φ and ω scansRint = 0.045
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
θmax = 35.0°, θmin = 4.1°
Tmin = 0.802, Tmax = 0.983h = 3231
12430 measured reflectionsk = 910
3046 independent reflectionsl = 1716
Refinement top
Refinement on F23 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0468P)2 + 0.922P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3046 reflectionsΔρmax = 0.91 e Å3
109 parametersΔρmin = 0.55 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.18354 (2)0.69299 (6)0.90632 (4)0.02208 (10)
Cl20.22188 (2)0.68819 (7)0.64394 (4)0.02409 (11)
O10.11148 (7)0.36996 (19)0.76917 (14)0.0270 (3)
O20.01449 (6)0.75547 (19)0.46558 (12)0.0218 (3)
O30.07140 (7)0.9344 (2)0.82106 (14)0.0296 (3)
H30.0619 (12)1.052 (3)0.828 (2)0.036*
N10.05958 (6)0.57272 (19)0.62634 (13)0.0142 (2)
H1A0.0352 (10)0.469 (3)0.598 (2)0.017*
N30.08836 (7)0.9086 (2)0.60091 (15)0.0209 (3)
H3A0.0803 (11)1.010 (4)0.564 (2)0.025*
C20.05203 (8)0.7500 (2)0.55987 (15)0.0160 (3)
C40.11860 (8)0.9140 (2)0.72628 (16)0.0177 (3)
H4A0.1521641.0260600.7319820.021*
C50.15341 (7)0.7110 (2)0.74935 (15)0.0135 (3)
C60.10627 (7)0.5334 (2)0.71907 (15)0.0148 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02396 (18)0.0258 (2)0.01618 (18)0.00256 (15)0.01093 (14)0.00345 (15)
Cl20.01459 (16)0.0329 (2)0.0248 (2)0.00212 (15)0.00148 (14)0.00355 (17)
O10.0290 (6)0.0180 (6)0.0334 (8)0.0055 (5)0.0147 (5)0.0107 (5)
O20.0269 (6)0.0176 (5)0.0204 (6)0.0034 (4)0.0153 (5)0.0025 (5)
O30.0226 (6)0.0338 (7)0.0323 (8)0.0093 (5)0.0071 (5)0.0185 (6)
N10.0149 (5)0.0114 (5)0.0160 (6)0.0017 (4)0.0059 (4)0.0003 (5)
N30.0280 (7)0.0099 (6)0.0242 (8)0.0025 (5)0.0163 (6)0.0042 (5)
C20.0174 (6)0.0133 (6)0.0169 (7)0.0003 (5)0.0075 (5)0.0008 (5)
C40.0195 (7)0.0133 (6)0.0200 (7)0.0019 (5)0.0104 (6)0.0028 (6)
C50.0122 (5)0.0149 (6)0.0132 (6)0.0001 (5)0.0038 (5)0.0013 (5)
C60.0147 (6)0.0143 (6)0.0152 (7)0.0011 (5)0.0048 (5)0.0025 (5)
Geometric parameters (Å, º) top
Cl1—C51.7592 (15)N1—H1A0.89 (2)
Cl2—C51.7787 (16)N3—C21.344 (2)
O1—C61.2086 (19)N3—C41.447 (2)
O2—C21.2371 (18)N3—H3A0.79 (2)
O3—C41.389 (2)C4—C51.531 (2)
O3—H30.805 (16)C4—H4A1.0000
N1—C61.3658 (19)C5—C61.536 (2)
N1—C21.375 (2)
C4—O3—H3109.1 (19)O3—C4—H4A110.0
C6—N1—C2126.69 (13)N3—C4—H4A110.0
C6—N1—H1A117.2 (13)C5—C4—H4A110.0
C2—N1—H1A115.5 (13)C4—C5—C6111.48 (12)
C2—N3—C4121.97 (14)C4—C5—Cl1110.91 (11)
C2—N3—H3A113.8 (17)C6—C5—Cl1110.09 (10)
C4—N3—H3A120.2 (17)C4—C5—Cl2108.90 (11)
O2—C2—N3123.56 (15)C6—C5—Cl2106.02 (11)
O2—C2—N1119.77 (14)Cl1—C5—Cl2109.29 (8)
N3—C2—N1116.65 (13)O1—C6—N1122.56 (14)
O3—C4—N3112.65 (13)O1—C6—C5123.13 (13)
O3—C4—C5106.26 (14)N1—C6—C5114.24 (13)
N3—C4—C5107.77 (13)
C4—N3—C2—O2164.69 (16)O3—C4—C5—Cl2172.67 (10)
C4—N3—C2—N117.2 (2)N3—C4—C5—Cl266.35 (14)
C6—N1—C2—O2169.06 (16)C2—N1—C6—O1176.62 (17)
C6—N1—C2—N39.1 (3)C2—N1—C6—C50.6 (2)
C2—N3—C4—O370.5 (2)C4—C5—C6—O1152.65 (17)
C2—N3—C4—C546.4 (2)Cl1—C5—C6—O129.1 (2)
O3—C4—C5—C670.70 (16)Cl2—C5—C6—O188.98 (18)
N3—C4—C5—C650.28 (18)C4—C5—C6—N130.10 (19)
O3—C4—C5—Cl152.36 (14)Cl1—C5—C6—N1153.63 (12)
N3—C4—C5—Cl1173.35 (11)Cl2—C5—C6—N188.27 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O1i0.81 (2)2.41 (2)3.045 (2)136 (2)
O3—H3···O2ii0.81 (2)2.16 (2)2.8076 (18)138 (2)
N1—H1A···O2iii0.89 (2)1.91 (2)2.7932 (17)178 (2)
N3—H3A···O2iv0.79 (2)2.46 (2)3.0978 (19)138 (2)
N3—H3A···O3v0.79 (2)2.60 (2)3.147 (2)128 (2)
C4—H4A···O1i1.002.453.058 (2)119
Symmetry codes: (i) x, y+1, z; (ii) x, y+2, z+1/2; (iii) x, y+1, z+1; (iv) x, y+2, z+1; (v) x, y+2, z1/2.
 

Acknowledgements

The X-ray diffraction experiment was carried out at the Centre of Shared Use of Physical Methods of Investigation of IPCE RAS.

Funding information

Funding for this research was provided by: Ministry of Science and Higher Education of the Russian Federation (subject No. AAAA-A18-118040590105-4).

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