(E)-6-(Furan-2-yl­methyl­idene)-6,7,8,9-tetra­hydro­pyrido[2,1-b]quinazoline-11-thione

Tojiboev, A.; Nasrullaev, A.; Turgunov, K.; Elmuradov, B.; Tashkhodjaev, B.

doi:10.1107/S2414314620003569

organic compounds

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ISSN: 2414-3146

Volume 5| Part 3| March 2020|

https://doi.org/10.1107/S2414314620003569

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(E)-6-(Furan-2-ylmethylidene)-6,7,8,9-tetrahydropyrido[2,1-b]quinazoline-11-thione

Akmal Tojiboev,^a ^* Azizbek Nasrullaev,^b Kambarali Turgunov,^b,^c Burkhan Elmuradov ^b and Bakhodir Tashkhodjaev ^b

^aInstitute of Ion-Plasma and Laser Technologies, Academy of Sciences of Uzbekistan, Durmon Yuli Str. 33, 100125 Tashkent, Uzbekistan, ^bS. Yunusov Institute of Chemistry of Plant Substances, Academy of Sciences of Uzbekistan, Mirzo Ulugbek Str. 77, 100170 Tashkent, Uzbekistan, and ^cTurin Polytechnic University in Tashkent, Kichik Khalka Yuli Str. 17, Tashkent 100095, Uzbekistan
^*Correspondence e-mail: a_tojiboev@yahoo.com

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 5 February 2020; accepted 9 March 2020; online 13 March 2020)

A quinazolinthione, C₁₇H₁₄N₂OS, was synthesized by the condensation reaction of 6,7,8,9-tetrahydro-11H-pyrido[2,1-b]quinazolin-11-thione with furfural. The molecule crystallizes in the monoclinic system (Cc space group) and has an E configuration with respect to the exocyclic C=C bond. In the crystal, molecules are linked through C—H⋯π(furan) interactions, forming zigzag chains propagating along the [001] direction.

Keywords: crystal structure; quinazolinthione; E-configuration.

CCDC reference: 1989156

Structure description

Quinazoline derivatives are biologically active heterocyclic compounds (Shakhidoyatov, 1988 ; Elmuradov & Shakhidoyatov, 2006 ), used as drugs, such as cardiovascular agents (Volzhina & Yakhontov, 1982 ), herbicides (Chupp, 1974 ; Dayan, 2019 ), fungicides (Vicentini et al., 2002 ; Sun et al., 2011 ), etc. Among them, quinazoline and its homologues exhibit plural reactivity while maintaining several functional groups. The study of their reaction properties is of theoretical interest (Shakhidoyatov & Elmuradov, 2014 ). Alkylation and condensation reactions have been previously studied to produce tricyclic derivatives of quinazolinthione (Nasrullayev et al., 2012 ; Nasrullaev et al., 2015 , 2016 , 2017 ). In the present work, we report the crystal structure of a new quinazolinthione derivative.

The title compound (Fig. 1), consist of 6,7,8,9-tetrahydropyrido[2,1-b]quinazoline and furan-2-ylmethylene groups linked through the C6=C12 double bond [1.348 (5) Å]. The molecule adopts an E configuration relative to this bond. The quinazoline moiety is almost planar with anr.m.s. deviation of 0.0234 Å. Atoms C7 and C8 deviate from the plane through atoms C6, C5A, N10, C9 (r.m.s. deviation of 0.0053 Å) of the six-membered tetramethylene ring by 0.418 (8) and 0.912 (9) Å, respectively. These values are similar to those found for related compounds, for example 6,7,8,9-tetrahydro-11H-pyrido[2,1-b]quinazolin-11-thione and 6,7,8,9,10,12-hexahydroazepino[2,1-b]quinazolin-12-thione (Nasrullayev et al., 2016).

Figure 1
The molecular structure of title compound with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, molecules are linked by C—H⋯π(furan) interactions between molecules related by the c glide plane of space group Cc, forming zigzag chains propagating along the [001] direction (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the furan ring (O/C2–C16).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯Cgⁱ	0.97	2.76	3.596 (5)	145
Symmetry code: (i) $[x, -y+1, z+{\script{1\over 2}}]$ .

Figure 2
Chain of molecules of the title compound linked by C—H⋯π interactions. For clarity, H atoms not involved in these interactions have been omitted, and only atom H8B has been included.

Synthesis and crystallization

6,7,8,9-Tetrahydro-11H-pyrido[2,1-b]quinazolin-11-thione (1 mmol) was dissolved in 2–3 ml of glacial acetic acid and furfural (1 mmol) was added. The reaction mixture was refluxed for 5.5 h and cooled. Distilled water (10 ml) was added to the reaction mixture and the precipitate that formed was filtered off, washed with distilled water and dried. After recrystallization from cyclohexane solution, the title compound was recovered in good yield (68%), m.p. 170°C, R_f = 0.88. ¹H NMR, δ, p.p.m., J (Hz): 8.28 (1H, d, J = 8.2, H-1), 7.5 (1H, t, J = 8.2, H-2), 7.39 (1H, d, J = 1.7, H-5′), 7.30 (1H, t, J = 1.7, =CH), 7.23–7.29 (2H, m, H-3,4), 6.68 (1H, d, J = 3.4, H-3′), 6.3 (1H, dd, J = 3.4, J = 1.7, H-4′), 4.36 (2H, t, J = 5.5, δ-CH₂), 2.78 (2H, dt, J = 6.8, J = 1.7, β-CH₂), 1.85 (2H, m, γ-CH₂). IR spectrum: ν, cm⁻¹: 1569 (C=N), 1469 (C—N), 1272 (C=S). Light-orange prismatic single crystals suitable for X-ray diffraction analysis were obtained by were grown from acetone by slow evaporation of the solvent.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₄N₂OS
M_r	294.36
Crystal system, space group	Monoclinic, Cc
Temperature (K)	295
a, b, c (Å)	9.4340 (19), 17.134 (4), 8.8260 (18)
β (°)	105.01 (4)
V (Å³)	1378.0 (6)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.08
Crystal size (mm)	0.50 × 0.20 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Ruby
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO, Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.371, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2724, 1969, 1717
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.123, 1.04
No. of reflections	1969
No. of parameters	190
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25
Absolute structure	Flack x determined using 451 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.12 (3)
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO, Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1989156

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620003569/bh4051sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620003569/bh4051Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620003569/bh4051Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

(E)-6-(Furan-2-ylmethylidene)-6,7,8,9-tetrahydropyrido[2,1-b]quinazoline-11-thione top

Crystal data top

C₁₇H₁₄N₂OS	D_x = 1.419 Mg m⁻³
M_r = 294.36	Melting point: 443 K
Monoclinic, Cc	Cu Kα radiation, λ = 1.54184 Å
a = 9.4340 (19) Å	Cell parameters from 1371 reflections
b = 17.134 (4) Å	θ = 5.2–75.6°
c = 8.8260 (18) Å	µ = 2.08 mm⁻¹
β = 105.01 (4)°	T = 295 K
V = 1378.0 (6) Å³	Prism, light-orange
Z = 4	0.50 × 0.20 × 0.20 mm
F(000) = 616

Data collection top

Oxford Diffraction Xcalibur, Ruby diffractometer	1969 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1717 reflections with I > 2σ(I)
Detector resolution: 10.2576 pixels mm^-1	R_int = 0.028
ω scans	θ_max = 75.7°, θ_min = 5.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −11→11
T_min = 0.371, T_max = 1.000	k = −21→20
2724 measured reflections	l = −10→8

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.0857P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.123	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.22 e Å⁻³
1969 reflections	Δρ_min = −0.25 e Å⁻³
190 parameters	Absolute structure: Flack x determined using 451 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: 0.12 (3)

Special details top

Refinement. All C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(carrier C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S	0.84058 (15)	0.72703 (6)	0.43163 (16)	0.0570 (4)
O	0.3377 (3)	0.35652 (18)	0.0790 (4)	0.0470 (7)
N5	0.7682 (4)	0.46996 (18)	0.4826 (4)	0.0375 (7)
C5A	0.6819 (4)	0.5126 (2)	0.3748 (4)	0.0335 (8)
N10	0.6960 (4)	0.59229 (18)	0.3632 (4)	0.0361 (7)
C11	0.8105 (4)	0.6337 (2)	0.4601 (5)	0.0371 (9)
C11A	0.9040 (4)	0.5873 (2)	0.5853 (5)	0.0348 (8)
C1	1.0187 (5)	0.6216 (2)	0.7004 (6)	0.0458 (10)
H1A	1.0354	0.6750	0.6982	0.055*
C2	1.1058 (5)	0.5765 (3)	0.8156 (6)	0.0523 (11)
H2A	1.1800	0.5998	0.8926	0.063*
C3	1.0842 (5)	0.4955 (3)	0.8188 (6)	0.0474 (10)
H3A	1.1453	0.4652	0.8963	0.057*
C4	0.9728 (4)	0.4610 (2)	0.7072 (5)	0.0417 (9)
H4A	0.9585	0.4073	0.7095	0.050*
C4A	0.8803 (4)	0.5065 (2)	0.5895 (5)	0.0352 (8)
C6	0.5610 (4)	0.4721 (2)	0.2591 (5)	0.0347 (8)
C7	0.4301 (5)	0.5176 (2)	0.1681 (5)	0.0429 (10)
H7A	0.3412	0.4939	0.1828	0.051*
H7B	0.4261	0.5153	0.0573	0.051*
C8	0.4371 (5)	0.6018 (2)	0.2199 (6)	0.0478 (11)
H8A	0.3663	0.6321	0.1432	0.057*
H8B	0.4115	0.6053	0.3193	0.057*
C9	0.5873 (5)	0.6349 (2)	0.2377 (6)	0.0493 (11)
H9A	0.6143	0.6303	0.1392	0.059*
H9B	0.5876	0.6898	0.2643	0.059*
C12	0.5812 (4)	0.3956 (2)	0.2360 (5)	0.0376 (9)
H12A	0.6717	0.3757	0.2907	0.045*
C13	0.4845 (5)	0.3402 (2)	0.1402 (5)	0.0391 (9)
C14	0.5114 (6)	0.2665 (2)	0.0973 (6)	0.0481 (11)
H14A	0.6018	0.2413	0.1226	0.058*
C15	0.3780 (6)	0.2352 (3)	0.0079 (6)	0.0539 (12)
H15A	0.3628	0.1856	−0.0360	0.065*
C16	0.2774 (6)	0.2914 (3)	−0.0014 (6)	0.0536 (12)
H16A	0.1791	0.2867	−0.0556	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0620 (7)	0.0336 (5)	0.0682 (8)	−0.0066 (5)	0.0039 (6)	0.0005 (5)
O	0.0388 (14)	0.0429 (16)	0.0531 (19)	−0.0076 (12)	0.0006 (14)	−0.0058 (14)
N5	0.0360 (15)	0.0295 (15)	0.0408 (19)	−0.0022 (13)	−0.0013 (14)	0.0014 (13)
C5A	0.0355 (18)	0.0289 (17)	0.033 (2)	0.0003 (15)	0.0039 (16)	0.0005 (15)
N10	0.0420 (17)	0.0263 (15)	0.0349 (18)	0.0003 (13)	0.0007 (15)	−0.0001 (13)
C11	0.038 (2)	0.0310 (17)	0.041 (2)	0.0002 (15)	0.0078 (17)	−0.0006 (15)
C11A	0.0349 (17)	0.0320 (17)	0.036 (2)	−0.0028 (15)	0.0058 (17)	−0.0019 (15)
C1	0.044 (2)	0.040 (2)	0.048 (3)	−0.0052 (17)	0.002 (2)	−0.0046 (18)
C2	0.041 (2)	0.060 (3)	0.048 (3)	−0.011 (2)	−0.004 (2)	−0.009 (2)
C3	0.038 (2)	0.056 (3)	0.043 (2)	0.0028 (18)	0.0003 (19)	0.005 (2)
C4	0.038 (2)	0.0384 (19)	0.044 (3)	−0.0003 (16)	0.0030 (19)	0.0025 (17)
C4A	0.0320 (17)	0.0336 (17)	0.037 (2)	−0.0013 (14)	0.0040 (17)	0.0006 (15)
C6	0.0319 (17)	0.0336 (18)	0.035 (2)	−0.0034 (15)	0.0017 (16)	−0.0014 (14)
C7	0.0366 (19)	0.041 (2)	0.044 (2)	−0.0005 (16)	−0.0024 (18)	−0.0082 (17)
C8	0.047 (2)	0.037 (2)	0.051 (3)	0.0117 (17)	−0.003 (2)	−0.0025 (18)
C9	0.057 (3)	0.035 (2)	0.046 (3)	0.0042 (19)	−0.005 (2)	0.0103 (18)
C12	0.0372 (18)	0.0307 (18)	0.040 (2)	−0.0014 (15)	0.0001 (17)	0.0028 (16)
C13	0.042 (2)	0.037 (2)	0.035 (2)	−0.0020 (16)	0.0048 (18)	−0.0004 (16)
C14	0.054 (2)	0.033 (2)	0.051 (3)	−0.0027 (18)	0.003 (2)	−0.0029 (18)
C15	0.067 (3)	0.035 (2)	0.054 (3)	−0.014 (2)	0.004 (2)	−0.0083 (19)
C16	0.050 (2)	0.053 (3)	0.051 (3)	−0.019 (2)	0.001 (2)	−0.010 (2)

Geometric parameters (Å, º) top

S—C11	1.655 (4)	C4—H4A	0.9300
O—C16	1.365 (5)	C6—C12	1.348 (5)
O—C13	1.378 (5)	C6—C7	1.504 (5)
N5—C5A	1.304 (5)	C7—C8	1.510 (5)
N5—C4A	1.373 (5)	C7—H7A	0.9700
C5A—N10	1.379 (4)	C7—H7B	0.9700
C5A—C6	1.491 (5)	C8—C9	1.497 (7)
N10—C11	1.387 (5)	C8—H8A	0.9700
N10—C9	1.491 (5)	C8—H8B	0.9700
C11—C11A	1.458 (6)	C9—H9A	0.9700
C11A—C4A	1.405 (5)	C9—H9B	0.9700
C11A—C1	1.406 (6)	C12—C13	1.431 (6)
C1—C2	1.368 (7)	C12—H12A	0.9300
C1—H1A	0.9300	C13—C14	1.361 (6)
C2—C3	1.404 (7)	C14—C15	1.407 (7)
C2—H2A	0.9300	C14—H14A	0.9300
C3—C4	1.374 (6)	C15—C16	1.340 (7)
C3—H3A	0.9300	C15—H15A	0.9300
C4—C4A	1.407 (5)	C16—H16A	0.9300

C16—O—C13	106.2 (4)	C6—C7—H7A	109.3
C5A—N5—C4A	118.1 (3)	C8—C7—H7A	109.3
N5—C5A—N10	123.7 (3)	C6—C7—H7B	109.3
N5—C5A—C6	117.5 (3)	C8—C7—H7B	109.3
N10—C5A—C6	118.8 (3)	H7A—C7—H7B	108.0
C5A—N10—C11	122.4 (3)	C9—C8—C7	111.1 (4)
C5A—N10—C9	118.7 (3)	C9—C8—H8A	109.4
C11—N10—C9	118.9 (3)	C7—C8—H8A	109.4
N10—C11—C11A	114.2 (3)	C9—C8—H8B	109.4
N10—C11—S	122.5 (3)	C7—C8—H8B	109.4
C11A—C11—S	123.2 (3)	H8A—C8—H8B	108.0
C4A—C11A—C1	119.3 (4)	N10—C9—C8	110.0 (4)
C4A—C11A—C11	119.2 (3)	N10—C9—H9A	109.7
C1—C11A—C11	121.4 (4)	C8—C9—H9A	109.7
C2—C1—C11A	120.2 (4)	N10—C9—H9B	109.7
C2—C1—H1A	119.9	C8—C9—H9B	109.7
C11A—C1—H1A	119.9	H9A—C9—H9B	108.2
C1—C2—C3	120.7 (4)	C6—C12—C13	129.8 (4)
C1—C2—H2A	119.7	C6—C12—H12A	115.1
C3—C2—H2A	119.7	C13—C12—H12A	115.1
C4—C3—C2	120.0 (4)	C14—C13—O	108.7 (4)
C4—C3—H3A	120.0	C14—C13—C12	130.0 (4)
C2—C3—H3A	120.0	O—C13—C12	121.3 (4)
C3—C4—C4A	120.2 (4)	C13—C14—C15	107.8 (4)
C3—C4—H4A	119.9	C13—C14—H14A	126.1
C4A—C4—H4A	119.9	C15—C14—H14A	126.1
N5—C4A—C11A	122.1 (3)	C16—C15—C14	106.1 (4)
N5—C4A—C4	118.3 (3)	C16—C15—H15A	127.0
C11A—C4A—C4	119.6 (4)	C14—C15—H15A	127.0
C12—C6—C5A	116.3 (3)	C15—C16—O	111.2 (4)
C12—C6—C7	123.5 (3)	C15—C16—H16A	124.4
C5A—C6—C7	120.1 (3)	O—C16—H16A	124.4
C6—C7—C8	111.6 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the furan ring (O/C2–C16).

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cgⁱ	0.97	2.76	3.596 (5)	145

Symmetry code: (i) x, −y+1, z+1/2.

Acknowledgements

The authors acknowledge the Institute of Bioorganic Chemistry of Academy of Sciences of Uzbekistan for the use of the Oxford Diffraction Xcalibur Ruby diffractometer.

Funding information

These investigations were supported by research projects VA-FA-F-7–006 of the Academy of Sciences of the Republic of Uzbekistan.

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