Bis(4-meth-oxy-3,4-di-hydro-quinazolin-1-ium) chloranilate.

IN THE TITLE COMPOUND [SYSTEMATIC NAME: bis-(4-meth-oxy-3,4-di-hydro-quinazolin-1-ium) 2,5-di-chloro-3,6-dioxo-cyclo-hexa-1,4-diene-1,4-diolate], 2C9H11N2O(+)·C6Cl2O4 (2-), the chloranil-ate anion lies about an inversion center. The 4-meth-oxy-3,4-di-hydro-quinazolin-1-ium cations are linked on both sides of the anion via bifurcated N-H⋯(O,O) and weak C-H⋯O hydrogen bonds, giving a centrosymmetric 2:1 aggregate. The 2:1 aggregates are linked by another N-H⋯O hydrogen bond into a tape running along [1-10]. The tapes are further linked by a C-H⋯O hydrogen bond into a layer parallel to the ab plane.

Related literature

For NMR and nuclear quadrupole resonance (NQR) studies on proton-transfer in the short hydrogen-bond of the diazine–chloranilic acid (2:1) system, see: Nihei et al. (2000 ▶); Seliger et al. (2009 ▶). For a related structure, see: Gotoh & Ishida (2011 ▶). For the double π system of the chloranilate anion, see: Andersen (1967 ▶); Benchekroun & Savariault (1995 ▶).

Experimental

Crystal data

2C9H11N2O+·C6Cl2O4 2−

M = 533.37

Triclinic,

a = 4.9971 (4) Å

b = 8.6363 (4) Å

c = 13.5808 (9) Å

α = 97.869 (4)°

β = 91.660 (6)°

γ = 100.968 (5)°

V = 569.06 (7) Å3

Z = 1

Mo Kα radiation

μ = 0.34 mm−1

T = 200 K

0.45 × 0.35 × 0.04 mm

Data collection

Rigaku R-AXIS RAPID II diffractometer

Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T min = 0.887, T max = 0.987

7422 measured reflections

2692 independent reflections

1913 reflections with I > 2σ(I)

R int = 0.199

Refinement

R[F 2 > 2σ(F 2)] = 0.082

wR(F 2) = 0.177

S = 0.84

2692 reflections

172 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.89 e Å−3

Δρmin = −0.54 e Å−3

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: CrystalStructure and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536813023635/hg5342sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813023635/hg5342Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813023635/hg5342Isup3.cml

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

2C9H11N2O+·C6Cl2O42−	Z = 1
Mr = 533.37	F(000) = 276.00
Triclinic, P1	Dx = 1.556 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 4.9971 (4) Å	Cell parameters from 6359 reflections
b = 8.6363 (4) Å	θ = 3.0–28.0°
c = 13.5808 (9) Å	µ = 0.34 mm−1
α = 97.869 (4)°	T = 200 K
β = 91.660 (6)°	Platelet, brown
γ = 100.968 (5)°	0.45 × 0.35 × 0.04 mm
V = 569.06 (7) Å3

Rigaku R-AXIS RAPID II diffractometer	1913 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1	Rint = 0.199
ω scans	θmax = 27.9°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −6→6
Tmin = 0.887, Tmax = 0.987	k = −11→11
7422 measured reflections	l = −17→17
2692 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.082	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3
2692 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.89 e Å−3
0 restraints	Δρmin = −0.54 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.92850 (10)	−0.01581 (6)	0.33371 (4)	0.0289 (2)
O1	0.6877 (3)	0.26227 (17)	0.41520 (12)	0.0253 (4)
O2	0.6806 (3)	−0.27488 (17)	0.44963 (13)	0.0273 (4)
O3	0.0538 (3)	0.67492 (19)	0.17432 (13)	0.0325 (4)
N1	0.3013 (4)	0.3978 (2)	0.33662 (15)	0.0238 (4)
N2	0.0001 (4)	0.5674 (2)	0.32482 (16)	0.0264 (4)
C1	0.6067 (4)	0.1368 (2)	0.45169 (16)	0.0202 (5)
C2	0.6949 (4)	−0.0070 (2)	0.42490 (16)	0.0216 (5)
C3	0.6061 (4)	−0.1443 (2)	0.46922 (16)	0.0208 (5)
C4	0.1661 (4)	0.5056 (2)	0.37648 (17)	0.0239 (5)
H4	0.1907	0.5399	0.4462	0.029*
C5	−0.0403 (4)	0.5353 (3)	0.21674 (18)	0.0276 (5)
H5	−0.2413	0.5032	0.2003	0.033*
C6	0.0872 (4)	0.3967 (3)	0.17605 (18)	0.0252 (5)
C7	0.0414 (5)	0.3326 (3)	0.07619 (19)	0.0329 (5)
H7	−0.0787	0.3723	0.0350	0.039*
C8	0.1683 (6)	0.2118 (3)	0.0362 (2)	0.0375 (6)
H8	0.1365	0.1689	−0.0323	0.045*
C9	0.3429 (5)	0.1532 (3)	0.0965 (2)	0.0367 (6)
H9	0.4315	0.0707	0.0688	0.044*
C10	0.3890 (5)	0.2130 (3)	0.19591 (19)	0.0305 (5)
H10	0.5075	0.1721	0.2370	0.037*
C11	0.2585 (4)	0.3353 (3)	0.23554 (17)	0.0234 (5)
C12	0.3396 (6)	0.7357 (3)	0.1882 (2)	0.0405 (6)
H12A	0.3821	0.8406	0.1661	0.061*
H12B	0.4377	0.6626	0.1493	0.061*
H12C	0.3958	0.7459	0.2589	0.061*
H1	0.413 (6)	0.351 (3)	0.377 (2)	0.037 (7)*
H2	−0.097 (6)	0.628 (4)	0.362 (2)	0.043 (8)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0312 (3)	0.0265 (4)	0.0301 (4)	0.0090 (2)	0.0144 (2)	0.0008 (3)
O1	0.0295 (8)	0.0181 (7)	0.0299 (9)	0.0075 (6)	0.0073 (6)	0.0041 (7)
O2	0.0324 (8)	0.0188 (8)	0.0327 (9)	0.0111 (6)	0.0113 (7)	0.0006 (7)
O3	0.0428 (10)	0.0251 (8)	0.0326 (10)	0.0131 (7)	0.0048 (7)	0.0057 (8)
N1	0.0288 (9)	0.0188 (9)	0.0246 (10)	0.0091 (7)	0.0052 (7)	−0.0013 (8)
N2	0.0314 (10)	0.0213 (9)	0.0281 (11)	0.0106 (8)	0.0125 (8)	0.0000 (9)
C1	0.0219 (9)	0.0162 (10)	0.0217 (11)	0.0032 (8)	0.0015 (8)	0.0005 (9)
C2	0.0234 (10)	0.0189 (10)	0.0223 (11)	0.0066 (8)	0.0073 (8)	−0.0020 (9)
C3	0.0219 (9)	0.0189 (10)	0.0217 (11)	0.0073 (8)	0.0033 (8)	−0.0019 (9)
C4	0.0289 (10)	0.0197 (10)	0.0230 (12)	0.0050 (8)	0.0097 (8)	0.0002 (10)
C5	0.0269 (10)	0.0238 (11)	0.0327 (13)	0.0090 (9)	0.0040 (9)	−0.0004 (10)
C6	0.0264 (10)	0.0198 (10)	0.0282 (12)	0.0033 (8)	0.0053 (8)	−0.0004 (10)
C7	0.0397 (13)	0.0296 (12)	0.0275 (13)	0.0038 (10)	0.0021 (10)	0.0015 (11)
C8	0.0561 (16)	0.0282 (13)	0.0248 (13)	0.0053 (11)	0.0078 (11)	−0.0054 (11)
C9	0.0522 (15)	0.0258 (12)	0.0325 (14)	0.0127 (11)	0.0153 (12)	−0.0040 (12)
C10	0.0366 (12)	0.0235 (11)	0.0333 (14)	0.0117 (10)	0.0092 (10)	0.0011 (11)
C11	0.0259 (10)	0.0195 (10)	0.0236 (12)	0.0035 (8)	0.0074 (8)	−0.0003 (9)
C12	0.0478 (15)	0.0276 (13)	0.0449 (16)	0.0002 (11)	0.0088 (12)	0.0095 (12)

Cl1—C2	1.730 (2)	C5—C6	1.508 (3)
O1—C1	1.255 (3)	C5—H5	1.0000
O2—C3	1.251 (2)	C6—C11	1.384 (3)
O3—C5	1.413 (3)	C6—C7	1.388 (4)
O3—C12	1.422 (3)	C7—C8	1.379 (3)
N1—C4	1.319 (2)	C7—H7	0.9500
N1—C11	1.399 (3)	C8—C9	1.389 (4)
N1—H1	0.95 (3)	C8—H8	0.9500
N2—C4	1.305 (3)	C9—C10	1.374 (4)
N2—C5	1.457 (3)	C9—H9	0.9500
N2—H2	0.90 (3)	C10—C11	1.398 (3)
C1—C2	1.401 (3)	C10—H10	0.9500
C1—C3i	1.537 (3)	C12—H12A	0.9800
C2—C3	1.405 (3)	C12—H12B	0.9800
C3—C1i	1.537 (3)	C12—H12C	0.9800
C4—H4	0.9500
C5—O3—C12	115.09 (18)	C11—C6—C7	118.93 (19)
C4—N1—C11	120.69 (19)	C11—C6—C5	121.3 (2)
C4—N1—H1	120.9 (17)	C7—C6—C5	119.7 (2)
C11—N1—H1	118.0 (17)	C8—C7—C6	120.7 (2)
C4—N2—C5	124.17 (18)	C8—C7—H7	119.7
C4—N2—H2	114.4 (19)	C6—C7—H7	119.7
C5—N2—H2	121.4 (19)	C7—C8—C9	119.7 (2)
O1—C1—C2	124.72 (19)	C7—C8—H8	120.2
O1—C1—C3i	116.54 (16)	C9—C8—H8	120.2
C2—C1—C3i	118.73 (18)	C10—C9—C8	120.8 (2)
C1—C2—C3	123.38 (19)	C10—C9—H9	119.6
C1—C2—Cl1	118.46 (16)	C8—C9—H9	119.6
C3—C2—Cl1	118.15 (14)	C9—C10—C11	118.9 (2)
O2—C3—C2	126.28 (19)	C9—C10—H10	120.6
O2—C3—C1i	115.86 (18)	C11—C10—H10	120.6
C2—C3—C1i	117.85 (16)	C6—C11—C10	121.0 (2)
N2—C4—N1	123.2 (2)	C6—C11—N1	119.03 (18)
N2—C4—H4	118.4	C10—C11—N1	120.0 (2)
N1—C4—H4	118.4	O3—C12—H12A	109.5
O3—C5—N2	110.61 (19)	O3—C12—H12B	109.5
O3—C5—C6	113.51 (18)	H12A—C12—H12B	109.5
N2—C5—C6	110.36 (18)	O3—C12—H12C	109.5
O3—C5—H5	107.4	H12A—C12—H12C	109.5
N2—C5—H5	107.4	H12B—C12—H12C	109.5
C6—C5—H5	107.4
O1—C1—C2—C3	178.1 (2)	O3—C5—C6—C7	−63.7 (3)
C3i—C1—C2—C3	−2.3 (3)	N2—C5—C6—C7	171.5 (2)
O1—C1—C2—Cl1	−1.1 (3)	C11—C6—C7—C8	−1.3 (4)
C3i—C1—C2—Cl1	178.50 (14)	C5—C6—C7—C8	176.3 (2)
C1—C2—C3—O2	−178.8 (2)	C6—C7—C8—C9	0.3 (4)
Cl1—C2—C3—O2	0.4 (3)	C7—C8—C9—C10	0.6 (4)
C1—C2—C3—C1i	2.3 (3)	C8—C9—C10—C11	−0.5 (4)
Cl1—C2—C3—C1i	−178.52 (14)	C7—C6—C11—C10	1.4 (3)
C5—N2—C4—N1	−5.1 (3)	C5—C6—C11—C10	−176.1 (2)
C11—N1—C4—N2	−4.4 (3)	C7—C6—C11—N1	−178.9 (2)
C12—O3—C5—N2	64.7 (2)	C5—C6—C11—N1	3.6 (3)
C12—O3—C5—C6	−60.0 (3)	C9—C10—C11—C6	−0.5 (3)
C4—N2—C5—O3	−114.4 (2)	C9—C10—C11—N1	179.8 (2)
C4—N2—C5—C6	12.1 (3)	C4—N1—C11—C6	4.8 (3)
O3—C5—C6—C11	113.8 (2)	C4—N1—C11—C10	−175.5 (2)
N2—C5—C6—C11	−11.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.95 (3)	1.79 (3)	2.706 (2)	160 (3)
N1—H1···O2i	0.95 (3)	2.56 (3)	3.229 (3)	127 (2)
N2—H2···O2ii	0.90 (3)	1.87 (3)	2.762 (3)	171 (3)
C4—H4···O1iii	0.95	2.34	3.214 (3)	152
C10—H10···O1	0.95	2.52	3.230 (3)	131

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.95 (3)	1.79 (3)	2.706 (2)	160 (3)
N1—H1⋯O2i	0.95 (3)	2.56 (3)	3.229 (3)	127 (2)
N2—H2⋯O2ii	0.90 (3)	1.87 (3)	2.762 (3)	171 (3)
C4—H4⋯O1iii	0.95	2.34	3.214 (3)	152
C10—H10⋯O1	0.95	2.52	3.230 (3)	131

Symmetry codes: (i) ; (ii) ; (iii) .