Redetermination at 113 K of 2,2-tetra­methyl­ene-1,2-dihydro­quinazolin-4(3H)-one

The title compound {systematic name: spiro­[cyclo­pentane-1,2′(1′H)-quinazolin]-4′(3′H)-one]}, C₁₂H₁₄N₂O, has been reported previously [Klemm, Weakley, Gilbertson & Song (1998). J. Heterocycl Chem. 35, 1269–1273]. Its structure has been redetermined at 113 K with greater precision for all data. The mol­ecule is built up from two fused six-membered rings and one five-membered ring linked through a spiro C atom. The pyrimidine ring has an envelope conformation and the cyclopentane ring adopts a distorted boat form. There are inter­molecular N—H...O hydrogen bonds, which form a two-dimensional sheet parallel to the (001) plane.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.104
• Data-to-parameter ratio = 16.9

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S1. Comment

When we used 2-aminobenzonitrile and cyclopentanone in presence of zinc chloride to synthesize tacrine (Summers et al., 1986) derivative, the unexpected spiro compound (I) (Scheme 1), was obtained. Its structure has been already reported (Klemm et al., 1998), however, as we were investigating the molecular and supramolecular architecture of related compounds, its structural redetermination at lower temperature (113 K) has been undertaken

The molecular structure of (I) is built up with two fused six membered ring and a five membered ring linked through a spiro C atom (Fig. 1). The pyrimidine ring has an envelope conformation with puckering parameters Q=0.3821 (11) Å, Θ= 115.21 (16)° and ϕ= 108.70 (19)° (Cremer & Pople, 1975). The five-membered ring displays an enveloppe conformation at C12 with puckering parameters Q(2)= O.3925 (15)Å and ϕ(2)= 319.8 (2)\%. The geometry of the fused rings compares well with the related 3-phenyl-1,2-dihydroquinazolin-4(3H)-one derivative (Shi et al., 2004).

The crystal structure of (I) is stabilized by the interplay of N—H···O interactions. The two N—H groups form N—H···O hydrogen bonds with the ketone O atom of symmetry related molecules building a R₂²(8) graph set motif (Etter et al., 1990; Bernstein et al., 1995). Those motifs formed with N—H···O hydrogen bonds link to each other building a two dimensionnal network parallel to the (0 0 1) plane (Fig. 2, Table 1).

Related literature

For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); Etter et al. (1990); Shi et al. (2004); Summers et al. (1986).

S2. Experimental

2,2-Tetramethylene-1,2-dihydroquinazolin-4(3H)-one (I) was prepared from the reflux of 2-aminobenzonitrile (1 mmol) with cyclopentanone (1 mmol) in presence of zinc chloride (1.2 mmol) in 10 ml DMF for 1.5 h. Then the reaction mixture was cooled and quenched with water and the precipitate was separated by filtration. The filtration residue was dispersed into water and titrated to pH 12–13 by 20% sodium hydroxide. After filtration, the product was obtained in 70% yield by column chromatography (200–300 mesh silica gel, ethyl acetate–petroleum with 1:2).

The single-crystal of (I) was cultured from a solution of ethanol by slow evaporation at room temperature.

Spectra data: IR (KBr, cm^-1): 3289, 3166, 2934, 1638, 1613, 1429; ¹H NMR (DMSO-d₆) δ_H: 1.75–2.08 (8H, m, C₄H₈), 6.07 (1H, s, NH), 6.73 (2H, dd, J=7.8, 8.0 Hz, ArH), 7.19 (1H, s, NH), 7.24–7.26 (1H, m, J=7.2 Hz, ArH), 7.73 (1H, d, J=8.0 Hz, ArH); ¹³C NMR (DMSO-d₆) δ_C: 21.97 (2 C), 38.88 (2 C), 77.05, 114.32, 114.57, 116.53, 127.23, 132.99, 147.49, 163.42; MS (ESI): m/z (%) =203.1 (100) [M+H]⁺; C₁₂H₁₄N₂O: calcd. C 71.26, H 6.98, N 13.85; found C 71.38, H 6.71, N 13.49.

S3. Refinement

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene) with U_iso(H) = 1.2U_eq(C or N). H atoms of NH group were located in difference Fourier maps and included in the subsequent refinement using restraints (N—H= 0.85 (1) Å) with U_iso(H) = 1.2U_eq(N).

Computing details

Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of (I), with the atom-labelling scheme. Displacement elipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing showing one sheet of molecules connected by N—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bondings have been omitted for clarity.

spiro[cyclopentane-1,2'(1'H)-quinazolin]-4'(3'H)-one]

Crystal data

C12H14N2O	F(000) = 864
Mr = 202.25	Dx = 1.319 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5598 reflections
a = 10.3872 (12) Å	θ = 2.6–27.9°
b = 12.0252 (13) Å	µ = 0.09 mm^−1
c = 16.3027 (19) Å	T = 113 K
V = 2036.3 (4) Å^3	Prism, colorless
Z = 8	0.26 × 0.24 × 0.16 mm

Data collection

Rigaku Saturn diffractometer	2403 independent reflections
Radiation source: rotating anode	2200 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.033
Detector resolution: 7.31 pixels mm^-1	θmax = 27.9°, θmin = 2.9°
ω scans	h = −13→13
Absorption correction: multi-scan (Jacobson, 1998)	k = −15→15
Tmin = 0.972, Tmax = 0.984	l = −21→21
23533 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.9123P] where P = (Fo^2 + 2Fc^2)/3
2403 reflections	(Δ/σ)max = 0.001
142 parameters	Δρmax = 0.31 e Å^−3
2 restraints	Δρmin = −0.23 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.08554 (8)	0.58043 (6)	0.58072 (5)	0.01704 (19)
N1	0.14762 (9)	0.42225 (8)	0.51639 (6)	0.0162 (2)
H1	0.0821 (11)	0.4272 (12)	0.4846 (8)	0.019*
N2	0.30566 (10)	0.30494 (8)	0.57191 (6)	0.0176 (2)
H2	0.3437 (13)	0.2417 (9)	0.5745 (9)	0.021*
C1	0.27524 (10)	0.48724 (9)	0.62879 (6)	0.0149 (2)
C2	0.34067 (10)	0.38442 (9)	0.62795 (7)	0.0155 (2)
C3	0.43548 (11)	0.36400 (10)	0.68791 (7)	0.0189 (2)
H3	0.4778	0.2959	0.6891	0.023*
C4	0.46564 (11)	0.44475 (10)	0.74485 (7)	0.0208 (3)
H4	0.5295	0.4308	0.7835	0.025*
C5	0.40171 (12)	0.54737 (10)	0.74554 (7)	0.0210 (3)
H5	0.4232	0.6013	0.7840	0.025*
C6	0.30602 (11)	0.56750 (9)	0.68820 (7)	0.0186 (2)
H6	0.2618	0.6347	0.6891	0.022*
C7	0.16430 (10)	0.50191 (9)	0.57324 (7)	0.0144 (2)
C8	0.24515 (11)	0.33881 (9)	0.49553 (6)	0.0148 (2)
C9	0.18435 (11)	0.23692 (10)	0.45265 (7)	0.0182 (2)
H9A	0.1703	0.1774	0.4918	0.022*
H9B	0.1023	0.2568	0.4283	0.022*
C10	0.27944 (13)	0.20002 (11)	0.38614 (9)	0.0300 (3)
H10A	0.3038	0.1229	0.3942	0.036*
H10B	0.2410	0.2075	0.3322	0.036*
C11	0.39717 (12)	0.27571 (10)	0.39391 (8)	0.0229 (3)
H11A	0.4620	0.2424	0.4290	0.027*
H11B	0.4348	0.2906	0.3406	0.027*
C12	0.34353 (11)	0.38216 (10)	0.43211 (7)	0.0195 (2)
H12A	0.3019	0.4282	0.3911	0.023*
H12B	0.4111	0.4248	0.4585	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0156 (4)	0.0139 (4)	0.0217 (4)	0.0012 (3)	−0.0010 (3)	−0.0011 (3)
N1	0.0137 (4)	0.0154 (4)	0.0194 (5)	0.0023 (3)	−0.0038 (4)	−0.0026 (4)
N2	0.0213 (5)	0.0138 (5)	0.0178 (5)	0.0050 (4)	−0.0044 (4)	−0.0006 (4)
C1	0.0145 (5)	0.0152 (5)	0.0149 (5)	−0.0015 (4)	0.0004 (4)	0.0010 (4)
C2	0.0144 (5)	0.0165 (5)	0.0155 (5)	−0.0010 (4)	0.0016 (4)	0.0010 (4)
C3	0.0180 (5)	0.0210 (5)	0.0178 (5)	0.0034 (4)	0.0003 (4)	0.0027 (4)
C4	0.0179 (5)	0.0287 (6)	0.0157 (5)	−0.0010 (5)	−0.0031 (4)	0.0020 (5)
C5	0.0231 (6)	0.0220 (6)	0.0180 (5)	−0.0051 (5)	−0.0032 (4)	−0.0020 (4)
C6	0.0204 (6)	0.0161 (5)	0.0194 (6)	−0.0017 (4)	−0.0002 (4)	−0.0007 (4)
C7	0.0140 (5)	0.0132 (5)	0.0159 (5)	−0.0015 (4)	0.0018 (4)	0.0015 (4)
C8	0.0141 (5)	0.0134 (5)	0.0168 (5)	0.0015 (4)	−0.0010 (4)	−0.0008 (4)
C9	0.0164 (5)	0.0171 (5)	0.0212 (5)	−0.0009 (4)	−0.0007 (4)	−0.0035 (4)
C10	0.0310 (7)	0.0266 (7)	0.0324 (7)	−0.0065 (5)	0.0113 (6)	−0.0128 (5)
C11	0.0196 (6)	0.0256 (6)	0.0235 (6)	0.0013 (5)	0.0037 (5)	−0.0038 (5)
C12	0.0199 (6)	0.0187 (6)	0.0198 (5)	−0.0028 (4)	0.0021 (4)	0.0002 (4)

Geometric parameters (Å, º)

O1—C7	1.2553 (13)	C5—H5	0.9300
N1—C7	1.3442 (14)	C6—H6	0.9300
N1—C8	1.4659 (14)	C8—C12	1.5443 (15)
N1—H1	0.857 (9)	C8—C9	1.5456 (15)
N2—C2	1.3712 (15)	C9—C10	1.5323 (17)
N2—C8	1.4531 (14)	C9—H9A	0.9700
N2—H2	0.857 (9)	C9—H9B	0.9700
C1—C6	1.4041 (15)	C10—C11	1.5297 (17)
C1—C2	1.4110 (15)	C10—H10A	0.9700
C1—C7	1.4762 (15)	C10—H10B	0.9700
C2—C3	1.4091 (16)	C11—C12	1.5287 (17)
C3—C4	1.3794 (16)	C11—H11A	0.9700
C3—H3	0.9300	C11—H11B	0.9700
C4—C5	1.4014 (17)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700
C5—C6	1.3857 (16)
C7—N1—C8	123.96 (9)	N1—C8—C12	112.43 (9)
C7—N1—H1	118.0 (9)	N2—C8—C9	110.01 (9)
C8—N1—H1	117.1 (10)	N1—C8—C9	111.42 (9)
C2—N2—C8	119.36 (9)	C12—C8—C9	103.60 (9)
C2—N2—H2	117.6 (10)	C10—C9—C8	106.63 (9)
C8—N2—H2	119.3 (10)	C10—C9—H9A	110.4
C6—C1—C2	119.95 (10)	C8—C9—H9A	110.4
C6—C1—C7	121.25 (10)	C10—C9—H9B	110.4
C2—C1—C7	118.35 (10)	C8—C9—H9B	110.4
N2—C2—C3	121.74 (10)	H9A—C9—H9B	108.6
N2—C2—C1	119.31 (10)	C11—C10—C9	106.53 (10)
C3—C2—C1	118.85 (10)	C11—C10—H10A	110.4
C4—C3—C2	120.19 (11)	C9—C10—H10A	110.4
C4—C3—H3	119.9	C11—C10—H10B	110.4
C2—C3—H3	119.9	C9—C10—H10B	110.4
C3—C4—C5	121.17 (11)	H10A—C10—H10B	108.6
C3—C4—H4	119.4	C12—C11—C10	103.92 (10)
C5—C4—H4	119.4	C12—C11—H11A	111.0
C6—C5—C4	119.23 (11)	C10—C11—H11A	111.0
C6—C5—H5	120.4	C12—C11—H11B	111.0
C4—C5—H5	120.4	C10—C11—H11B	111.0
C5—C6—C1	120.57 (11)	H11A—C11—H11B	109.0
C5—C6—H6	119.7	C11—C12—C8	103.37 (9)
C1—C6—H6	119.7	C11—C12—H12A	111.1
O1—C7—N1	121.26 (10)	C8—C12—H12A	111.1
O1—C7—C1	122.62 (10)	C11—C12—H12B	111.1
N1—C7—C1	116.01 (9)	C8—C12—H12B	111.1
N2—C8—N1	106.98 (9)	H12A—C12—H12B	109.1
N2—C8—C12	112.46 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86 (1)	2.04 (1)	2.8936 (12)	171 (1)
N2—H2···O1^ii	0.86 (1)	2.08 (1)	2.9303 (13)	173 (1)

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