Unusual formation of (E)-11-(amino­methyl­ene)-8,9,10,11-tetra­hydro­pyrido[2′,3′:4,5]pyrimido[1,2-a]azepin-5(7H)-one and its crystal structure

Khodjaniyazov, Kh.U.; Makhmudov, U.S.; Turgunov, K.K.; Elmuradov, B.Z.

doi:10.1107/S2056989017013093

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ISSN: 2056-9890

Volume 73| Part 10| October 2017| Pages 1497-1500

https://doi.org/10.1107/S2056989017013093

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Unusual formation of (E)-11-(aminomethylene)-8,9,10,11-tetrahydropyrido[2′,3′:4,5]pyrimido[1,2-a]azepin-5(7H)-one and its crystal structure

Khamid U. Khodjaniyazov,^a Utkir S. Makhmudov,^a Kambarali K. Turgunov ^a ^* and Burkhon Z. Elmuradov ^a

^aS.Yunusov Institute of the Chemistry of Plant Substances Academy of Sciences of, Uzbekistan Mirzo Ulugbek Str., 77, Tashkent 100170, Uzbekistan
^*Correspondence e-mail: kk_turgunov@rambler.ru

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 29 August 2017; accepted 13 September 2017; online 19 September 2017)

Selective C-formylation of 8,9,10,11-tetrahydropyrido[2′,3′:4,5]pyrimido[1,2-a]-azepin-5(7H)-one has been studied for the first time. It was revealed that formylation proceeds by the formation of an intermediate salt, which due to the re-amination process on treatment with aqueous ammonia transformed into the corresponding (E)-11-(aminomethylene)-8,9,10,11-tetrahydropyrido[2′,3′:4,5]-pyrimido[1,2-a]azepin-5(7H)-one, C₁₃H₁₄N₄O, as an E-isomer. Formylation was carried out by Vilsmeier–Haack reagent and the structure of the synthesized compound was confirmed by X-ray structural analysis, spectroscopic and LC–MS methods. In the molecule, the seven-membered pentamethylene ring adopts a twist-boat conformation.

Keywords: fused pyrimidines; formylation; Vilsmeier–Haack reagent; X-ray structure analysis; crystal structure.

CCDC reference: 1530092

1. Chemical context

Pyrimidine-containing heterocyclic compounds are widely distributed in nature (Lagoja, 2005 ) and among synthetic compounds (Joshi et al., 2016 ; Roopan & Sompalle, 2016 ). These compounds are of theoretical and practical interest, having plural reactivity and with many prospective biologically active compounds among the synthesized derivatives.

In previous reports we have described several syntheses, viz. the reaction of 2,3-trimethylenepyrido[2,3-d]pyrimidin-4-one with aromatic aldehydes (Khodjaniyazov, 2015a ,b ; Khodjaniyazov & Ashurov, 2016 ), selective reduction with sodium borohydride (Khodjaniyazov et al., 2016b ), and the formation of (E)-9-(N,N-dimethylaminomethylidene)-8,9-dihydropyrido[2,3-d]pyrrolo[1,2-a]pyrimidin-5(7H)-one (Khodjaniyazov et al., 2016a ). In this current report we present the results of reaction of 8,9,10,11-tetrahydropyrido[2′,3′:4,5]pyrimido[1,2-a]azepin-5(7H)-one (1) with the Vilsmeier–Haack reagent, decomposition by water and subsequent treatment with aqueous ammonia. We carried out the interaction of 1 with a formylating agent and, at the end of the reaction, the unusual final product (E)-11-(aminomethylene)-8,9,10,11-tetrahydropyrido[2′,3′:4,5]pyrimido-[1,2-a]azepin-5(7H)-one (3) was isolated after treatment (re-amination) of 11-dimethylaminomethylidene derivative (2) with aqueous ammonia. The reaction proceeds as shown in Fig. 1. The reaction product was different from that obtained in the case of formylation of 2,3-trimethylenepyrido[2,3-d]pyrimidin-4-one [pyrido[2,3-d]pyrrolo[1,2-a]pyrimidin-5(7H)-one; Khodjaniyazov et al., 2016a]. This fact was explained by re-amination of the initially formed dimethylaminomethylidene derivative 2 under action of aqueous ammonia to give (E)-11-(aminomethylene)-8,9,10,11-tetrahydropyrido[2′,3′:4,5]pyrimido[1,2-a]azepin-5(7H)-one (3) as the final product

Figure 1
Reaction scheme.

2. Structural commentary

The title compound crystallizes in the centrosymmetric monoclinic P2₁/c (No. 14) space group. The asymmetric unit contains one crystallographically independent molecule. A displacement ellipsoid plot showing the atom-numbering scheme is presented in Fig. 2. In the molecule, the seven-membered pentamethylene ring exhibits a twist-boat conformation and has an approximate twofold symmetry with a C₂ axis passing through atom C12 and midpoint of the C2—C9 bond. The amino group is E-oriented and hybridization of the N atom in this group lies between sp³ and sp². The C—N bond makes an angle of 155° with the bisector of the H—N—H angle. The equivalent angle in methylamine with a pyramidal sp³-hybridized N atom is ∼123° (Klingebiel et al., 2002 ) and it is nearly 180° in formamide with a planar sp²-hybridized N atom (Gajda & Katrusiak, 2011 ). The pyrimidine ring is twisted slightly, which may be because of the influence of the twisted seven-membered azepane ring. The N1—C8A—N4A—C4 torsion angle of is 8.7 (4)°.

Figure 2
The molecular structure of compound 3, with the atom labelling and 50% probability displacement ellipsoids.

3. Supramolecular features

In the crystal, hydrogen bonds with 16 ring and three chain motifs are generated by N—H⋯N and N—H⋯O contacts (Table 1). The amino group is located close to the nitrogen atoms N1 and N8 of an inversion-related molecule, forming hydrogen bonds with R₁²(4) and R₂²(12) graph-set motifs (Fig. 3). This amino group also forms a hydrogen bond with the C=O oxygen atom of a molecule translated along the a axis, which links the molecules into R₄⁴(16) rings. Hydrogen-bonded chains are formed along [100] by alternating R₂²(12) and R₄⁴(16) rings (Fig. 4). These chains are stabilized by intermolecular π-π-stacking interactions observed between the pyridine and pyrimidine rings [centroid–centroid distance = 3.669 (2) Å; symmetry operation 1 − x, 1 − y, 1 − z].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N15—H1⋯O1ⁱ	0.85 (3)	2.21 (3)	3.017 (3)	159 (3)
N15—H2⋯N1ⁱⁱ	0.85 (5)	2.31 (5)	3.146 (3)	168 (4)
N15—H2⋯N8ⁱⁱ	0.85 (5)	2.79 (5)	3.401 (4)	131 (4)
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+1, -z+1.

Figure 3
Hydrogen bonding in the title compound showing the R₁²(4) and R₂²(12) graph-set motifs.

Figure 4
Hydrogen-bonded chain formation in 3.

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, last update November 2016; Groom et al., 2016 ) for the 4-azaquinazoline moiety gave eight hits. Only one of these is a related structure, a tricyclic 4-azaquinazolin-4-one with a substituent on the third ring (VAMBET; Khodjaniyazov & Ashurov, 2016).

5. Synthesis and crystallization

Materials and methods. The results of electro spray ionization mass spectrometry (ESI–MS) were recorded using a 6420 TripleQuadLC/MC (Agilent Technologies, US) LC–MS spectrometer. The measurements were carried out in positive-ion mode. ¹H NMR spectra were recorded in CD₃OD on a Varian 400-MR spectrometer operating accordingly at 400 MHz. Hexamethyldisiloxcane (HMDSO) was used as internal standard and the chemical shift of ¹H was recorded in ppm. Melting points were measured on a Boetius and MEL–TEMP apparatus manufactured by Branstead international (USA) and are uncorrected. IR spectra were recorded on an IR Fourier System 2000 (Perkin–Elmer) as KBr pellets.

The reaction process was monitored by TLC on Silufol UV-254 plates using a CHCl₃/CH₃OH (12:1) solvent system and the developed plates were visualized under a UV lamp. Solvents were purified by standard procedures. Organic solutions were dried over anhydrous Na₂SO₄ or with dried CaCl₂.

Synthesis of (E)-11-(aminomethylene)-8,9,10,11-tetrahydropyrido[2′,3′:4,5]-pyrimido[1,2-a]azepin-5(7H)-one (3). A round-bottom flask with freshly distilled DMF (3 ml, 39 mmol) was cooled by an ice–water bath and POCl₃ (1 ml, 10.7 mmol) was added dropwise. The mixture was stirred (30 min), then 8,9,10,11-tetrahydropyrido[2′,3′:4,5]pyrimido[1,2-a]azepin-5(7H)-one (1) (0.51 g, 2.4 mmol) was added into the reaction mixture. The reaction mixture was heated in a water bath for 1.5 h at 343 K and left for another day. Water (4 ml) was poured into the flask. TLC monitoring showed that the initial compound had fully transformed. The reaction mixture was treated by aqueous ammonia solution up to pH 9. The obtained solution was extracted by chloroform (30 mL) three times. The chloroform part was dried over Na₂SO₄ and the solvent was removed. Yield 0.34 g (60%), m.p. 458–460 K, R_f 0.63. Single crystals of 3 were grown from acetone solution by slow evaporation of the solvent at room temperature.

UV spectrum (ethanol, λ_max, nm) neutral medium: 279.58, 348.97; acidic medium (HCl): 280.24, 362.37, 420.80; neutralization (HCl+NaOH): 279.12, 318.11, 362.29; basic medium (NaOH): 275.83, 347.71. IR spectrum (KBr, ν, cm⁻¹): 3382 (NH₂), 3325, 3203, 3064, 2924, 2869, 2824, 1642, 1613 (NH), 1591, 1562, 1523, 1470, 1433, 1389, 1353, 1319, 1267, 1249, 1227, 1184, 1126, 1107, 1077, 1045, 976, 934, 864, 825, 783, 735, 688, 663, 601, 548, 420. LC–MS (+ESI): 243 [M+H]⁺, 216.1, 201.1, 174, 160.9, 148.0, 121.0, 93.0, 79.0, 55.1, 39.1. ¹H NMR spectrum [400 MHz, CD₃OD, δ, ppm, J (Hz]): 1.77 (2H, m, γ-CH₂), 1.92 (2H, m, δ-CH₂), 2.385 (2H, m, β-CH₂), 4.195 (2H, t, J = 6.1, ∊-CH₂), 7.454 (1H, br s, =CH), 7.28 (1H, dd, J = 4.6, 7.9, H-6), 8.45 (1H, dd, J = 7.9, 2.1, H-5), 8.735 (1H, dd, J = 4.6, 2.1, H-7).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H-bound N atoms were freely refined. C-bound H atoms were refined as riding with C—H = 0.93 or 0.97 Å and U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₄N₄O
M_r	242.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.7260 (7), 15.236 (3), 8.6642 (7)
β (°)	98.046 (8)
V (Å³)	1140.6 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.76
Crystal size (mm)	0.40 × 0.35 × 0.15

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Ruby
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 $[Oxford Diffraction. (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ )
T_min, T_max	0.965, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7589, 2328, 1478
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.141, 1.04
No. of reflections	2328
No. of parameters	171
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20
Computer programs: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction. (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS7 and XP in SHELXTL (Sheldrick, 2008 ) and SHELXL2014/7 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1530092

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989017013093/xu5905sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017013093/xu5905Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS7 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015).

(E)-11-(Aminomethylene)-8,9,10,11-tetrahydropyrido[2',3':4,5]pyrimido[1,2-a]azepin-5(7H)-one top

Crystal data top

C₁₃H₁₄N₄O	D_x = 1.411 Mg m⁻³
M_r = 242.28	Melting point: 458(2) K
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 8.7260 (7) Å	Cell parameters from 911 reflections
b = 15.236 (3) Å	θ = 5.9–75.7°
c = 8.6642 (7) Å	µ = 0.76 mm⁻¹
β = 98.046 (8)°	T = 293 K
V = 1140.6 (3) Å³	Plate, colourless
Z = 4	0.40 × 0.35 × 0.15 mm
F(000) = 512

Data collection top

Oxford Diffraction Xcalibur, Ruby diffractometer	2328 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1478 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 10.2576 pixels mm^-1	θ_max = 76.7°, θ_min = 5.1°
ω scans	h = −9→10
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2007)	k = −19→18
T_min = 0.965, T_max = 1.000	l = −10→8
7589 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.0554P)² + 0.003P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2328 reflections	Δρ_max = 0.18 e Å⁻³
171 parameters	Δρ_min = −0.20 e Å⁻³

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

	x	y	z	U_iso*/U_eq
O1	0.6098 (2)	0.35990 (15)	0.1710 (2)	0.0621 (5)
N3	0.3638 (2)	0.39263 (13)	0.2102 (2)	0.0449 (4)
N1	0.2921 (2)	0.40925 (14)	0.4621 (2)	0.0472 (5)
N8	0.4731 (3)	0.39670 (16)	0.6821 (2)	0.0569 (5)
N15	−0.1422 (3)	0.49351 (19)	0.2758 (3)	0.0606 (6)
C2	0.2547 (3)	0.40679 (15)	0.3099 (3)	0.0438 (5)
C9	0.0935 (3)	0.41797 (17)	0.2412 (3)	0.0478 (5)
C4A	0.5549 (3)	0.36809 (16)	0.4323 (3)	0.0468 (5)
C8A	0.4417 (3)	0.39271 (15)	0.5243 (3)	0.0459 (5)
C4	0.5167 (3)	0.37221 (16)	0.2626 (3)	0.0476 (5)
C14	0.0100 (3)	0.47631 (17)	0.3123 (3)	0.0491 (5)
H14A	0.0630	0.5078	0.3950	0.059*
C13	0.3195 (3)	0.40613 (17)	0.0415 (3)	0.0502 (6)
H13A	0.4110	0.4200	−0.0056	0.060*
H13B	0.2492	0.4556	0.0247	0.060*
C5	0.7016 (3)	0.34430 (18)	0.5046 (3)	0.0557 (6)
H5A	0.7782	0.3280	0.4457	0.067*
C12	0.2420 (3)	0.32550 (18)	−0.0367 (3)	0.0560 (6)
H12A	0.1995	0.3400	−0.1432	0.067*
H12B	0.3189	0.2798	−0.0403	0.067*
C6	0.7310 (3)	0.34538 (19)	0.6636 (3)	0.0576 (6)
H6A	0.8268	0.3281	0.7154	0.069*
C10	0.0156 (3)	0.3637 (2)	0.1043 (3)	0.0607 (7)
H10A	−0.0772	0.3374	0.1341	0.073*
H10B	−0.0163	0.4030	0.0177	0.073*
C7	0.6134 (3)	0.3731 (2)	0.7466 (3)	0.0603 (6)
H7A	0.6354	0.3750	0.8547	0.072*
C11	0.1136 (3)	0.2911 (2)	0.0480 (3)	0.0617 (7)
H11A	0.1589	0.2566	0.1368	0.074*
H11B	0.0474	0.2527	−0.0214	0.074*
H1	−0.201 (4)	0.456 (2)	0.224 (4)	0.112 (16)*
H2	−0.181 (6)	0.527 (3)	0.338 (5)	0.16 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0464 (10)	0.0880 (14)	0.0538 (10)	0.0053 (9)	0.0141 (8)	−0.0095 (9)
N3	0.0398 (10)	0.0537 (11)	0.0415 (10)	−0.0006 (8)	0.0065 (8)	−0.0030 (8)
N1	0.0420 (10)	0.0574 (12)	0.0430 (10)	0.0022 (9)	0.0082 (8)	−0.0032 (8)
N8	0.0562 (13)	0.0707 (14)	0.0428 (11)	0.0026 (10)	0.0039 (9)	−0.0027 (9)
N15	0.0465 (13)	0.0786 (17)	0.0566 (13)	0.0100 (11)	0.0072 (10)	0.0016 (11)
C2	0.0416 (12)	0.0462 (12)	0.0440 (12)	−0.0003 (9)	0.0070 (9)	−0.0030 (9)
C9	0.0400 (12)	0.0593 (14)	0.0443 (12)	0.0014 (10)	0.0071 (9)	−0.0003 (10)
C4A	0.0424 (12)	0.0492 (13)	0.0484 (12)	−0.0002 (10)	0.0047 (10)	−0.0026 (9)
C8A	0.0430 (12)	0.0494 (13)	0.0450 (12)	0.0015 (9)	0.0049 (9)	−0.0019 (9)
C4	0.0404 (12)	0.0500 (12)	0.0533 (13)	0.0002 (10)	0.0097 (10)	−0.0076 (10)
C14	0.0393 (12)	0.0630 (15)	0.0446 (12)	0.0021 (11)	0.0042 (9)	0.0033 (10)
C13	0.0478 (13)	0.0601 (15)	0.0436 (12)	0.0002 (11)	0.0088 (10)	0.0018 (10)
C5	0.0450 (14)	0.0610 (16)	0.0611 (15)	0.0061 (11)	0.0074 (11)	−0.0003 (11)
C12	0.0616 (16)	0.0598 (16)	0.0457 (13)	0.0034 (12)	0.0044 (11)	−0.0082 (10)
C6	0.0467 (13)	0.0625 (16)	0.0600 (15)	0.0042 (11)	−0.0053 (11)	0.0051 (12)
C10	0.0461 (14)	0.0748 (18)	0.0598 (16)	−0.0004 (13)	0.0023 (11)	−0.0098 (13)
C7	0.0628 (16)	0.0693 (17)	0.0455 (13)	−0.0001 (13)	−0.0036 (11)	0.0008 (11)
C11	0.0616 (17)	0.0634 (17)	0.0589 (16)	−0.0091 (13)	0.0046 (12)	−0.0110 (12)

Geometric parameters (Å, º) top

O1—C4	1.227 (3)	C14—H14A	0.9300
N3—C4	1.383 (3)	C13—C12	1.516 (4)
N3—C2	1.389 (3)	C13—H13A	0.9700
N3—C13	1.473 (3)	C13—H13B	0.9700
N1—C2	1.314 (3)	C5—C6	1.365 (4)
N1—C8A	1.364 (3)	C5—H5A	0.9300
N8—C7	1.323 (4)	C12—C11	1.516 (4)
N8—C8A	1.357 (3)	C12—H12A	0.9700
N15—C14	1.347 (3)	C12—H12B	0.9700
N15—H1	0.852 (19)	C6—C7	1.398 (4)
N15—H2	0.849 (19)	C6—H6A	0.9300
C2—C9	1.458 (3)	C10—C11	1.519 (4)
C9—C14	1.352 (3)	C10—H10A	0.9700
C9—C10	1.525 (4)	C10—H10B	0.9700
C4A—C5	1.392 (3)	C7—H7A	0.9300
C4A—C8A	1.405 (3)	C11—H11A	0.9700
C4A—C4	1.463 (3)	C11—H11B	0.9700

C4—N3—C2	122.98 (19)	C12—C13—H13B	109.3
C4—N3—C13	117.70 (18)	H13A—C13—H13B	107.9
C2—N3—C13	119.16 (19)	C6—C5—C4A	118.8 (2)
C2—N1—C8A	118.76 (19)	C6—C5—H5A	120.6
C7—N8—C8A	117.3 (2)	C4A—C5—H5A	120.6
C14—N15—H1	120 (3)	C11—C12—C13	112.1 (2)
C14—N15—H2	116 (4)	C11—C12—H12A	109.2
H1—N15—H2	118 (4)	C13—C12—H12A	109.2
N1—C2—N3	122.2 (2)	C11—C12—H12B	109.2
N1—C2—C9	119.8 (2)	C13—C12—H12B	109.2
N3—C2—C9	118.0 (2)	H12A—C12—H12B	107.9
C14—C9—C2	116.2 (2)	C5—C6—C7	118.4 (2)
C14—C9—C10	120.1 (2)	C5—C6—H6A	120.8
C2—C9—C10	123.6 (2)	C7—C6—H6A	120.8
C5—C4A—C8A	119.3 (2)	C11—C10—C9	115.8 (2)
C5—C4A—C4	121.9 (2)	C11—C10—H10A	108.3
C8A—C4A—C4	118.7 (2)	C9—C10—H10A	108.3
N8—C8A—N1	115.9 (2)	C11—C10—H10B	108.3
N8—C8A—C4A	121.6 (2)	C9—C10—H10B	108.3
N1—C8A—C4A	122.3 (2)	H10A—C10—H10B	107.4
O1—C4—N3	121.1 (2)	N8—C7—C6	124.6 (2)
O1—C4—C4A	124.5 (2)	N8—C7—H7A	117.7
N3—C4—C4A	114.40 (19)	C6—C7—H7A	117.7
N15—C14—C9	126.7 (2)	C12—C11—C10	113.0 (2)
N15—C14—H14A	116.6	C12—C11—H11A	109.0
C9—C14—H14A	116.6	C10—C11—H11A	109.0
N3—C13—C12	111.7 (2)	C12—C11—H11B	109.0
N3—C13—H13A	109.3	C10—C11—H11B	109.0
C12—C13—H13A	109.3	H11A—C11—H11B	107.8
N3—C13—H13B	109.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N15—H1···O1ⁱ	0.85 (3)	2.21 (3)	3.017 (3)	159 (3)
N15—H2···N1ⁱⁱ	0.85 (5)	2.31 (5)	3.146 (3)	168 (4)
N15—H2···N8ⁱⁱ	0.85 (5)	2.79 (5)	3.401 (4)	131 (4)

Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1.

Funding information

The work was supported by fundamental grant FA-F7-T207 `Theoretical aspects of formation of the asymmetric centers in biologically active heterocyclic molecules' from the Academy of Sciences of the Republic of Uzbekistan.

References

Gajda, R. & Katrusiak, A. (2011). Cryst. Growth Des. 11, 4768–4774. Web of Science CSD CrossRef CAS
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals
Joshi, G., Nayyar, H., Marin Alex, J. S., Vishwakarma, G. S., Mittal, S. & Kumar, R. (2016). Curr. Top. Med. Chem. 16, 3175–3210. CrossRef CAS PubMed
Khodjaniyazov, Kh. U. (2015a). J. Adv. Chem. 11, 3873–3875. CAS
Khodjaniyazov, Kh. U. (2015b). Uzb. Chem. J. 22-25.
Khodjaniyazov, Kh. U. & Ashurov, J. M. (2016). Acta Cryst. E72, 452–455. CSD CrossRef IUCr Journals
Khodjaniyazov, Kh. U., Makhmudov, U. S. & Kutlimuratov, N. M. (2016a). J. Basic Appl. Res. 2, 382–385.
Khodjaniyazov, Kh. U., Mamadrakhimov, A. A., Tadjimukhamedov, Kh. S. & Levkovich, M. G. (2016b). J. Basic Appl. Res. 2, 82–85.
Klingebiel, U., Neugebauer, P., Müller, I., Noltemeyer, M. & Usón, I. (2002). Eur. J. Inorg. Chem. pp. 717–722. CSD CrossRef
Lagoja, I. M. (2005). Chem. Biodivers. 2, 1-50. Web of Science CrossRef PubMed CAS
Oxford Diffraction. (2007). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.
Roopan, S. M. & Sompalle, R. (2016). Syn. Commun. 46, 645-672. CAS
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals

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