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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1776.
Published online 2009 July 4. doi:  10.1107/S160053680902460X
PMCID: PMC2977403

6,7,8,9,10,11-Hexahydro-13H-azocino[2,1-b]quinazolin-13-one

Abstract

The title compound, C14H16N2O, is a synthetic analogue of quinazolone alkaloids with pyrrilo, pyrido and azopino rings. The quinazolinic part of the mol­ecule is generally planar within 0.037 (3) Å; the eight-membered ring exhibits an inter­mediate conformation between the chair and boat forms as it is typical for cyclo­octene rings. An ethyl­ene group of the azopino ring is disordered over two positions with a refined occupancy ratio of 0.910 (7):0.090 (7). In the crystal, the H atoms of the aromatic rings form weak C—H(...)O and C—H(...)N hydrogen bonds. One C—H(...)O hydrogen bond leads to the formation of a one-dimensional chain. Another C—H(...)O and a C—H(...)N bond link these chains, generating a three-dimensional network.

Related literature

For the synthesis of the title compound, see: Shakhidoyatov et al. (1976 [triangle]). For its physiological activity, see: Shakhidoyatov (1988 [triangle]). For crystal structures of pyrido-quinazolone and azopino-quinazolone, see: Tashkhodzhaev et al. (1995 [triangle]). For spectroscopic data and the chemical structures of pyrido-quinazoline and -quinazolone alkaloids, see: Turgunov et al. (1995 [triangle]). For cyclo­octene ring conformations, see: Barnes et al. (1992 [triangle]). For weak hydrogen bonds in alkaloids, see: Rajnikant et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1776-scheme1.jpg

Experimental

Crystal data

  • C14H16N2O
  • M r = 228.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1776-efi1.jpg
  • a = 9.5490 (19) Å
  • b = 10.584 (2) Å
  • c = 11.693 (2) Å
  • V = 1181.8 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 300 K
  • 0.60 × 0.42 × 0.35 mm

Data collection

  • Stoe Stadi-4 four-circle diffractometer
  • Absorption correction: none
  • 1229 measured reflections
  • 1208 independent reflections
  • 1061 reflections with I > 2σ(I)
  • 3 standard reflections frequency: 60 min intensity decay: 3.9%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.079
  • S = 1.17
  • 1208 reflections
  • 174 parameters
  • H-atom parameters constrained
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.11 e Å−3

Data collection: STADI4 (Stoe & Cie, 1997 [triangle]); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1997 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP (Bruker, 1998 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902460X/zl2205sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902460X/zl2205Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Academy of Sciences of the Republic of Uzbekistan for supporting this study (grant MP-34).

supplementary crystallographic information

Comment

Tricyclic quinazolin-4-ones with polymethylenic fragments and their analogues are widely spread in plants and possess various physiological activities (Shakhidoyatov, 1988). With this in mind the title compound was synthesized (Shakhidoyatov et al., 1976) and its crystal structure has been investigated by single crystal X-ray diffraction.

Figure 1 shows an ortep style plot of the molecular structure of the title compound. An ethylene group of the molecule is disordered over two positions (C3, C3', C4, C4'). Refinement of the structure yielded an occupancy ratio of the disordered atoms (i.e. two conformers) of 0.910 (7):0.090 (7).

The quinazoline part of the molecule is a generally flat within a standard deviation of ±0.037 Å. The electronic system of the N7—C14—N15—C12 fragment of the pyrymidinic ring is delocalized as reflected by the bond lengths. The length of the formal double bond N7═C14 and the single bond C14—N15 in the structure of the title compound are 1.297 (3) and 1.383 (3) Å, respectively, which is in agreement with the range observed in crystals of pyrrilo, pyrido, and azopino quinazolones (Turgunov et al., 1995; Tashkhodzhaev et al., 1995). The length of the C═O bond (1.227 (3) Å) is also compareable to those observed in above mentioned analogues. The eight-membered ring has taken on an intermediate form between a chair and boat conformation typical for cycloectene rings (Barnes et al., 1992).

In the crystal structure of the title compound weak intermolecular C-H···X hydrogen bonds are observed as it is often the case in alkaloids (Rajnikant et al., 2005). The hydrogen bond C8–H8A···O1i leads to the formation of a one dimensional chain. Another C–H···O and a C–H···N bond (C10–H10A···O1iii and a C9–H9A···N7ii) link these chains to generate a three-dimensional network (Fig. 2 and 3; for numerical values and symmetry operators see Table 1).

Experimental

The title compound was synthesized on the basis of a well–known method (Shakhidoyatov, et al., 1976). Powder of title compound was dissolved in hot aqueous ethanol and from the solution yellow prismatic crystals were obtained during slow evaporation in a thermostat at a temperature of 313 K.

Refinement

In the absence of anomalous scatteres and using molybdenum radiation Friedel pairs were merged prior to refinement. The C3 and C4 atoms of the molecule are disordered over two positions (C3, C3', C4, C4'). Refinement of the structure by using a free variable for the occupancy led to a ratio for the disordered atoms of 0.910 (7):0.090 (7). The bond lengths of the disordfered hexamethylenic fragment were restrained to be the same within a standard deviation of 0.02 Å.

The H atoms bonded to C atoms were placed geometrically (with C—H distances of 0.97 Å for CH2 and 0.93 Å for Car) and included in the refinement with a riding motion approximation with Uiso = 1.2Ueq(C) [Uiso = 1.5Ueq(C) for methyl H atoms].

Figures

Fig. 1.
The molecular structure of the title compound, with 50% probability displacement ellipsoids (bonds of the minor disordered moiety are represented by dashed lines).
Fig. 2.
The H-bonding networks in the crystal of the title compound. Minor moiety disordered atoms are omitted for clarity.
Fig. 3.
Schematic showing the weak hydrogen bonds (dashed lines).

Crystal data

C14H16N2ODx = 1.283 Mg m3
Mr = 228.29Melting point: 391(3) K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 12 reflections
a = 9.5490 (19) Åθ = 10–15°
b = 10.584 (2) ŵ = 0.08 mm1
c = 11.693 (2) ÅT = 300 K
V = 1181.8 (4) Å3Prizmatic, yellow
Z = 40.60 × 0.42 × 0.35 mm
F(000) = 488

Data collection

Stoe Stadi-4 four-circle diffractometerRint = 0.0000
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.6°
graphiteh = 0→11
ω/2θ scansk = 0→12
1229 measured reflectionsl = 0→13
1208 independent reflections3 standard reflections every 60 min
1061 reflections with I > 2σ(I) intensity decay: 3.9%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.079w = 1/[σ2(Fo2) + (0.0252P)2 + 0.261P] where P = (Fo2 + 2Fc2)/3
S = 1.17(Δ/σ)max < 0.001
1208 reflectionsΔρmax = 0.14 e Å3
174 parametersΔρmin = −0.10 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.040 (3)

Special details

Experimental. Scan width (omega) = 1.56 - 1.68, scan ratio 2theta:omega = 1.00 I(Net) and sigma(I) calculated according to Blessing, (1987).
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/UeqOcc. (<1)
O10.48619 (19)0.50852 (16)0.48326 (16)0.0541 (5)
C10.4342 (3)0.7278 (3)0.3757 (2)0.0501 (7)
H1A0.35550.67030.38230.060*
H1B0.41670.78250.31070.060*
C20.4418 (3)0.8074 (3)0.4824 (3)0.0626 (8)
H2A0.43890.75190.54830.075*
H2B0.35930.86080.48550.075*
C30.5710 (4)0.8909 (3)0.4918 (3)0.0625 (11)0.910 (7)
H3A0.65290.83730.49900.075*0.910 (7)
H3B0.56390.94090.56110.075*0.910 (7)
C40.5920 (5)0.9800 (3)0.3902 (4)0.0672 (12)0.910 (7)
H4A0.50240.99300.35300.081*0.910 (7)
H4B0.62341.06120.41880.081*0.910 (7)
C3'0.492 (4)0.938 (3)0.437 (4)0.076 (16)0.090 (7)
H3C0.45130.95510.36290.091*0.090 (7)
H3D0.46261.00460.48950.091*0.090 (7)
C4'0.654 (3)0.934 (5)0.429 (3)0.057 (11)0.090 (7)
H4C0.69351.00780.46660.068*0.090 (7)
H4D0.68920.85930.46670.068*0.090 (7)
C50.6969 (3)0.9334 (3)0.3012 (3)0.0659 (9)
H5A0.78160.90850.34110.079*
H5B0.72091.00420.25230.079*
C60.6522 (3)0.8230 (3)0.2240 (2)0.0556 (8)
H6A0.55590.83660.20070.067*
H6B0.70950.82470.15550.067*
N70.7692 (2)0.62498 (19)0.24573 (17)0.0431 (5)
C80.8961 (3)0.4294 (3)0.2602 (2)0.0504 (7)
H8A0.95450.45580.20120.061*
C90.9186 (3)0.3150 (3)0.3122 (3)0.0563 (8)
H9A0.99230.26420.28800.068*
C100.8327 (3)0.2743 (3)0.4005 (3)0.0562 (8)
H10A0.85050.19740.43610.067*
C110.7218 (3)0.3469 (2)0.4355 (2)0.0485 (7)
H11A0.66380.31920.49430.058*
C120.5754 (3)0.5395 (2)0.4132 (2)0.0377 (6)
C130.6967 (2)0.4634 (2)0.38186 (19)0.0366 (6)
C140.6629 (3)0.6936 (2)0.2763 (2)0.0400 (6)
N150.5625 (2)0.65339 (18)0.35342 (16)0.0385 (5)
C160.7848 (2)0.5065 (2)0.2960 (2)0.0379 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0525 (11)0.0515 (11)0.0582 (11)−0.0064 (10)0.0185 (10)0.0010 (10)
C10.0372 (13)0.0490 (15)0.0642 (17)0.0079 (12)0.0023 (13)−0.0053 (14)
C20.0607 (18)0.0529 (16)0.0743 (19)0.0055 (16)0.0161 (17)−0.0140 (16)
C30.063 (2)0.058 (2)0.067 (2)0.006 (2)−0.007 (2)−0.0217 (19)
C40.069 (3)0.0387 (19)0.094 (3)0.002 (2)−0.002 (3)−0.007 (2)
C3'0.11 (4)0.035 (18)0.08 (3)0.01 (2)0.05 (3)−0.010 (19)
C4'0.04 (2)0.08 (3)0.04 (2)0.00 (2)−0.016 (17)0.022 (19)
C50.0635 (19)0.0414 (15)0.093 (2)0.0014 (15)0.0113 (18)0.0164 (17)
C60.0584 (17)0.0541 (17)0.0543 (16)0.0136 (15)0.0060 (14)0.0176 (14)
N70.0404 (11)0.0434 (12)0.0456 (12)0.0009 (10)0.0059 (10)0.0035 (10)
C80.0415 (15)0.0526 (16)0.0572 (17)0.0040 (13)0.0082 (14)−0.0044 (15)
C90.0487 (16)0.0490 (16)0.0713 (19)0.0148 (15)−0.0032 (15)−0.0076 (15)
C100.0618 (17)0.0392 (14)0.0674 (18)0.0080 (14)−0.0075 (17)0.0010 (15)
C110.0537 (16)0.0396 (14)0.0523 (16)−0.0029 (14)−0.0010 (13)0.0034 (12)
C120.0398 (13)0.0368 (13)0.0365 (12)−0.0059 (11)0.0001 (13)−0.0044 (11)
C130.0368 (13)0.0353 (12)0.0377 (13)−0.0032 (11)−0.0011 (11)−0.0058 (10)
C140.0418 (14)0.0417 (14)0.0366 (13)0.0020 (12)−0.0008 (12)0.0004 (12)
N150.0362 (11)0.0390 (11)0.0401 (10)0.0020 (10)0.0014 (10)−0.0052 (9)
C160.0382 (14)0.0363 (12)0.0392 (12)−0.0005 (12)−0.0027 (11)−0.0030 (11)

Geometric parameters (Å, °)

O1—C121.227 (3)C5—C61.537 (4)
C1—N151.480 (3)C5—H5A0.9700
C1—C21.507 (4)C5—H5B0.9700
C1—H1A0.9700C6—C141.503 (4)
C1—H1B0.9700C6—H6A0.9700
C2—C31.521 (4)C6—H6B0.9700
C2—C3'1.56 (3)N7—C141.298 (3)
C2—H2A0.9700N7—C161.393 (3)
C2—H2B0.9700C8—C91.371 (4)
C3—C41.530 (6)C8—C161.404 (3)
C3—H3A0.9700C8—H8A0.9300
C3—H3B0.9700C9—C101.387 (4)
C4—C51.526 (5)C9—H9A0.9300
C4—H4A0.9700C10—C111.371 (4)
C4—H4B0.9700C10—H10A0.9300
C3'—C4'1.55 (3)C11—C131.404 (3)
C3'—H3C0.9700C11—H11A0.9300
C3'—H3D0.9700C12—N151.398 (3)
C4'—C51.55 (3)C12—C131.458 (3)
C4'—H4C0.9700C13—C161.387 (3)
C4'—H4D0.9700C14—N151.383 (3)
N15—C1—C2113.8 (2)C4—C5—H5A107.9
N15—C1—H1A108.8C6—C5—H5A107.9
C2—C1—H1A108.8C4'—C5—H5A76.1
N15—C1—H1B108.8C4—C5—H5B107.9
C2—C1—H1B108.8C6—C5—H5B107.9
H1A—C1—H1B107.7C4'—C5—H5B128.7
C1—C2—C3115.1 (2)H5A—C5—H5B107.2
C1—C2—C3'103.5 (16)C14—C6—C5115.8 (2)
C1—C2—H2A108.5C14—C6—H6A108.3
C3—C2—H2A108.5C5—C6—H6A108.3
C3'—C2—H2A144.7C14—C6—H6B108.3
C1—C2—H2B108.5C5—C6—H6B108.3
C3—C2—H2B108.5H6A—C6—H6B107.4
C3'—C2—H2B75.1C14—N7—C16118.1 (2)
H2A—C2—H2B107.5C9—C8—C16119.9 (3)
C2—C3—C4114.1 (4)C9—C8—H8A120.0
C2—C3—H3A108.7C16—C8—H8A120.0
C4—C3—H3A108.7C8—C9—C10120.8 (3)
C2—C3—H3B108.7C8—C9—H9A119.6
C4—C3—H3B108.7C10—C9—H9A119.6
H3A—C3—H3B107.6C11—C10—C9120.3 (3)
C5—C4—C3114.6 (4)C11—C10—H10A119.8
C5—C4—H4A108.6C9—C10—H10A119.8
C3—C4—H4A108.6C10—C11—C13119.4 (3)
C5—C4—H4B108.6C10—C11—H11A120.3
C3—C4—H4B108.6C13—C11—H11A120.3
H4A—C4—H4B107.6O1—C12—N15120.2 (2)
C4'—C3'—C2108 (4)O1—C12—C13124.9 (2)
C4'—C3'—H3C110.2N15—C12—C13114.9 (2)
C2—C3'—H3C110.2C16—C13—C11120.6 (2)
C4'—C3'—H3D110.2C16—C13—C12118.8 (2)
C2—C3'—H3D110.2C11—C13—C12120.6 (2)
H3C—C3'—H3D108.5N7—C14—N15123.3 (2)
C5—C4'—C3'109 (3)N7—C14—C6116.8 (2)
C5—C4'—H4C109.9N15—C14—C6119.9 (2)
C3'—C4'—H4C109.9C14—N15—C12122.0 (2)
C5—C4'—H4D109.9C14—N15—C1121.7 (2)
C3'—C4'—H4D109.9C12—N15—C1116.3 (2)
H4C—C4'—H4D108.3C13—C16—N7122.4 (2)
C4—C5—C6117.7 (3)C13—C16—C8119.0 (2)
C6—C5—C4'119.9 (16)N7—C16—C8118.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8A···O1i0.932.643.490 (3)153
C9—H9A···N7ii0.932.743.660 (3)170
C10—H10A···O1iii0.932.713.599 (3)162

Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) −x+2, y−1/2, −z+1/2; (iii) x+1/2, −y+1/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2205).

References

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  • Bruker (1998). XP Bruker AXS Ins., Madison, Wisconsin, USA.
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  • Rajnikant, Dinesh & Kamni (2005). Bull. Mater. Sci.28, 187–198.
  • Shakhidoyatov, Kh. M. (1988). Quinazolin-4-one and their biological activity, edited by M. S. Yunusov, S. R. Tulyaganov & M. M. Yunusov, p. 103. Tashkent: Fan.
  • Shakhidoyatov, Kh. M., Irisbaev, A., Yun, L. M., Oripov, E. & Kadirov, Ch. Sh. (1976). Khim. Geterotsikl. Soedin.11, 1286–1291.
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  • Stoe & Cie (1997). STADI4 and X-RED Stoe & Cie, Darmstadt, Germany.
  • Tashkhodzhaev, B., Turgunov, K. K., D’yakonov, A. L., Belova, G. A. & Shakhidoyatov, Kh. M. (1995). Chem. Nat. Compd, 31, 342–348.
  • Turgunov, K. K., Tashkhodzhaev, B., Molchanov, L. V. & Aripov, Kh. N. (1995). Chem. Nat. Compd, 31, 714–718.

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