8-Chloro-5,5-dimethyl-5,6-dihydro­tetra­zolo[1,5-c]quinazoline

In the title compound, C₁₀H₁₀ClN₅, the tetra­zole ring and the phenyl ring make a dihedral angle of 7.7 (2)°. The hexa­hydro­pyrimidine ring adopts a screw-boat conformation. In the crystal, inter­molecular bifurcated N—H...(N,N) hydrogen bonds link the mol­ecules into [001] chains.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.053
• wR factor = 0.137
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          3

Alert level G
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ..           1
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

A number of tetrazole derivatives were reported as to be antifungal agents (Upadhayaya et al., 2004), antiviral agents (Poonian et al., 1976), angiotensin II AT¹ receptor antagonists (Ismail et al., 2006), antibacterial agents (Mulwad & Kewat, 2008) and anti-ulcer agents (Uchida et al., 1989). On the basis of these considerations, our particular attention was directed to synthesize some tetrazole derivatives.

The title compound is a three fused-ring structure (Fig. 1). The tetrazole ring and the phenyl ring make dihedral angle of 7.7 (2)°. The hexahydropyrimidine ring adopts a screw-boat conformation, with puckering amplitude Q = 0.308 (3) Å, θ = 61.8 (6)°, φ = 270.4 (7)° (Boeyens, 1978). In the crystal structure, intermolecular bifurcated N5—H1N5···N1 and N5—H1N5···N2 hydrogen bonds link the molecules into chains along c axis (Fig. 2, Table 1).

Related literature

For applications of tetrazole derivatives, see: Upadhayaya et al. (2004); Poonian et al. (1976); Ismail et al. (2006); Mulwad & Kewat (2008); Uchida et al. (1989). For ring conformations, see: Boeyens (1978). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

S2. Experimental

To a solution of 2-amino-4-chlorobenzonitrile (4.2 mmol) in N,N-dimethylformamide was added ammonium chloride (3 eq) and sodium azide (3 eq). The resulting reaction mixture was refluxed for 12 h. The completion of reaction was checked by TLC (100% EA). The reaction mixture was poured into ice-water after cooling to RT and acidified to give tetrazoles as a white mass. The resulting compound was then condensed with acetone to get the title compound: colourless plates were obtained by crystallization from acetone under slow evaporation (Mp. 501 K).

S3. Refinement

The N-bound hydrogen atom was located from difference Fourier map and refined freely. The rest of hydrogen atoms were positioned geometrically [C–H = 0.93 or 0.96 Å] and refined using a riding model [U_iso(H) = 1.2 or 1.5U_eq]. A rotating-group model were applied for methyl groups.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title compound with 50% probability ellipsoids for non-H atoms.
	Fig. 2. The crystal packing of title compound, viewed down b axis, showing the molecules are linked into chains along c axis. Intermolecular hydrogen bonds are shown as dashed lines.

8-Chloro-5,5-dimethyl-5,6-dihydrotetrazolo[1,5-c]quinazoline

Crystal data

C10H10ClN5	F(000) = 488
Mr = 235.68	Dx = 1.491 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1888 reflections
a = 6.8324 (16) Å	θ = 3.0–29.9°
b = 21.532 (5) Å	µ = 0.34 mm^−1
c = 9.4337 (16) Å	T = 100 K
β = 130.823 (11)°	Plate, colourless
V = 1050.2 (4) Å^3	0.16 × 0.11 × 0.05 mm
Z = 4

Data collection

Bruker APEXII DUO CCD diffractometer	2412 independent reflections
Radiation source: fine-focus sealed tube	1777 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
φ and ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.948, Tmax = 0.982	k = −27→27
9660 measured reflections	l = −12→12

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0361P)^2 + 1.9098P] where P = (Fo^2 + 2Fc^2)/3
2412 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
Cl1	0.68351 (15)	0.62515 (4)	0.46138 (11)	0.0285 (2)
N1	0.0252 (5)	0.85800 (13)	−0.2050 (3)	0.0225 (6)
N2	0.0079 (5)	0.92121 (14)	−0.2261 (3)	0.0276 (6)
N3	0.1672 (5)	0.94937 (13)	−0.0661 (3)	0.0248 (6)
N4	0.2938 (4)	0.90385 (12)	0.0634 (3)	0.0192 (5)
N5	0.6368 (5)	0.85848 (12)	0.3484 (3)	0.0210 (6)
C1	0.2056 (5)	0.84885 (14)	−0.0218 (4)	0.0190 (6)
C2	0.3106 (5)	0.79248 (14)	0.0880 (4)	0.0185 (6)
C3	0.2129 (6)	0.73316 (15)	0.0145 (4)	0.0216 (7)
H3A	0.0704	0.7285	−0.1122	0.026*
C4	0.3259 (6)	0.68153 (15)	0.1280 (4)	0.0234 (7)
H4A	0.2613	0.6420	0.0797	0.028*
C5	0.5397 (6)	0.69013 (15)	0.3174 (4)	0.0213 (6)
C6	0.6402 (6)	0.74777 (15)	0.3947 (4)	0.0209 (6)
H6A	0.7816	0.7518	0.5218	0.025*
C7	0.5276 (5)	0.80012 (14)	0.2800 (4)	0.0176 (6)
C8	0.4845 (5)	0.91539 (14)	0.2689 (4)	0.0189 (6)
C9	0.6573 (6)	0.96910 (15)	0.3100 (4)	0.0271 (7)
H9A	0.7358	0.9608	0.2569	0.041*
H9B	0.7896	0.9742	0.4431	0.041*
H9C	0.5561	1.0064	0.2561	0.041*
C10	0.3352 (6)	0.92761 (16)	0.3348 (4)	0.0254 (7)
H10A	0.2294	0.8923	0.3065	0.038*
H10B	0.2275	0.9635	0.2718	0.038*
H10C	0.4549	0.9347	0.4675	0.038*
H1N5	0.751 (8)	0.8595 (18)	0.467 (6)	0.039 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0280 (4)	0.0248 (4)	0.0334 (4)	0.0052 (3)	0.0204 (3)	0.0085 (4)
N1	0.0187 (12)	0.0307 (16)	0.0131 (12)	0.0000 (10)	0.0082 (10)	0.0003 (11)
N2	0.0240 (13)	0.0355 (17)	0.0148 (12)	0.0021 (12)	0.0089 (11)	0.0035 (12)
N3	0.0251 (13)	0.0289 (15)	0.0147 (12)	0.0052 (11)	0.0106 (11)	0.0061 (11)
N4	0.0191 (12)	0.0225 (14)	0.0107 (11)	0.0023 (10)	0.0074 (10)	0.0021 (10)
N5	0.0173 (12)	0.0213 (14)	0.0104 (12)	−0.0010 (10)	0.0029 (10)	−0.0017 (10)
C1	0.0154 (13)	0.0267 (16)	0.0135 (13)	−0.0013 (12)	0.0088 (11)	−0.0040 (12)
C2	0.0167 (13)	0.0237 (17)	0.0151 (13)	0.0009 (12)	0.0104 (11)	−0.0009 (12)
C3	0.0182 (14)	0.0282 (18)	0.0166 (14)	−0.0047 (12)	0.0105 (12)	−0.0053 (13)
C4	0.0237 (15)	0.0227 (17)	0.0253 (16)	−0.0048 (13)	0.0166 (13)	−0.0063 (13)
C5	0.0214 (14)	0.0236 (17)	0.0257 (15)	0.0044 (12)	0.0184 (13)	0.0044 (13)
C6	0.0178 (14)	0.0259 (17)	0.0165 (14)	0.0015 (12)	0.0101 (12)	0.0001 (12)
C7	0.0162 (13)	0.0204 (16)	0.0171 (13)	−0.0006 (11)	0.0113 (11)	−0.0016 (12)
C8	0.0174 (13)	0.0207 (16)	0.0135 (13)	−0.0005 (12)	0.0079 (11)	0.0006 (12)
C9	0.0288 (16)	0.0279 (18)	0.0178 (14)	−0.0080 (14)	0.0122 (13)	−0.0009 (13)
C10	0.0240 (15)	0.0300 (19)	0.0195 (15)	0.0002 (13)	0.0130 (13)	−0.0006 (13)

Geometric parameters (Å, º)

Cl1—C5	1.739 (3)	C3—H3A	0.9300
N1—C1	1.326 (4)	C4—C5	1.396 (4)
N1—N2	1.369 (4)	C4—H4A	0.9300
N2—N3	1.297 (4)	C5—C6	1.374 (4)
N3—N4	1.349 (3)	C6—C7	1.394 (4)
N4—C1	1.334 (4)	C6—H6A	0.9300
N4—C8	1.489 (3)	C8—C9	1.511 (4)
N5—C7	1.386 (4)	C8—C10	1.525 (4)
N5—C8	1.458 (4)	C9—H9A	0.9600
N5—H1N5	0.85 (4)	C9—H9B	0.9600
C1—C2	1.445 (4)	C9—H9C	0.9600
C2—C3	1.397 (4)	C10—H10A	0.9600
C2—C7	1.413 (4)	C10—H10B	0.9600
C3—C4	1.378 (4)	C10—H10C	0.9600
C1—N1—N2	104.8 (2)	C5—C6—C7	119.2 (3)
N3—N2—N1	111.6 (2)	C5—C6—H6A	120.4
N2—N3—N4	105.5 (3)	C7—C6—H6A	120.4
C1—N4—N3	109.3 (2)	N5—C7—C6	121.0 (3)
C1—N4—C8	126.8 (2)	N5—C7—C2	119.8 (3)
N3—N4—C8	123.7 (2)	C6—C7—C2	119.0 (3)
C7—N5—C8	122.4 (2)	N5—C8—N4	104.6 (2)
C7—N5—H1N5	113 (3)	N5—C8—C9	109.6 (2)
C8—N5—H1N5	113 (3)	N4—C8—C9	109.5 (2)
N1—C1—N4	108.8 (3)	N5—C8—C10	112.2 (2)
N1—C1—C2	131.4 (3)	N4—C8—C10	108.1 (2)
N4—C1—C2	119.8 (2)	C9—C8—C10	112.4 (3)
C3—C2—C7	120.2 (3)	C8—C9—H9A	109.5
C3—C2—C1	124.0 (3)	C8—C9—H9B	109.5
C7—C2—C1	115.7 (3)	H9A—C9—H9B	109.5
C4—C3—C2	120.6 (3)	C8—C9—H9C	109.5
C4—C3—H3A	119.7	H9A—C9—H9C	109.5
C2—C3—H3A	119.7	H9B—C9—H9C	109.5
C3—C4—C5	118.3 (3)	C8—C10—H10A	109.5
C3—C4—H4A	120.9	C8—C10—H10B	109.5
C5—C4—H4A	120.9	H10A—C10—H10B	109.5
C6—C5—C4	122.7 (3)	C8—C10—H10C	109.5
C6—C5—Cl1	118.8 (2)	H10A—C10—H10C	109.5
C4—C5—Cl1	118.5 (2)	H10B—C10—H10C	109.5
C1—N1—N2—N3	−0.1 (3)	C4—C5—C6—C7	−0.8 (4)
N1—N2—N3—N4	0.4 (3)	Cl1—C5—C6—C7	179.5 (2)
N2—N3—N4—C1	−0.7 (3)	C8—N5—C7—C6	−153.7 (3)
N2—N3—N4—C8	−175.8 (2)	C8—N5—C7—C2	31.3 (4)
N2—N1—C1—N4	−0.3 (3)	C5—C6—C7—N5	−174.1 (3)
N2—N1—C1—C2	179.9 (3)	C5—C6—C7—C2	1.0 (4)
N3—N4—C1—N1	0.6 (3)	C3—C2—C7—N5	174.4 (3)
C8—N4—C1—N1	175.6 (2)	C1—C2—C7—N5	−4.6 (4)
N3—N4—C1—C2	−179.6 (2)	C3—C2—C7—C6	−0.7 (4)
C8—N4—C1—C2	−4.6 (4)	C1—C2—C7—C6	−179.7 (2)
N1—C1—C2—C3	−7.2 (5)	C7—N5—C8—N4	−38.5 (3)
N4—C1—C2—C3	173.0 (3)	C7—N5—C8—C9	−155.9 (3)
N1—C1—C2—C7	171.7 (3)	C7—N5—C8—C10	78.4 (3)
N4—C1—C2—C7	−8.0 (4)	C1—N4—C8—N5	25.7 (4)
C7—C2—C3—C4	0.2 (4)	N3—N4—C8—N5	−159.9 (2)
C1—C2—C3—C4	179.2 (3)	C1—N4—C8—C9	143.2 (3)
C2—C3—C4—C5	−0.1 (4)	N3—N4—C8—C9	−42.5 (4)
C3—C4—C5—C6	0.4 (4)	C1—N4—C8—C10	−94.0 (3)
C3—C4—C5—Cl1	−179.9 (2)	N3—N4—C8—C10	80.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H1N5···N1^i	0.85 (4)	2.35 (4)	3.190 (3)	173 (6)
N5—H1N5···N2^i	0.85 (4)	2.57 (4)	3.326 (3)	150 (4)

Symmetry code: (i) x+1, y, z+1.