1,2,3,4-Tetra­hydro­quinolinium hydrogen chloranilate

In the title compound, C₉H₁₂N⁺·C₆HCl₂O₄⁻, two chloranilate ions are connected by O—H...O hydrogen bonds to form a dimeric unit. The 1,2,3,4-tetra­hydro­quinolinium ions are linked on both sides of the dimer via an N—H...O hydrogen bond to give a 2:2 complex of chloranilic acid and tetra­hydro­quinoline. The 2:2 complexes are held together by an N—H...O hydrogen bond and a π–π stacking interaction to give a molecular tape.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.042
• wR factor = 0.121
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT333_ALERT_2_C Large Average Benzene C-C Dist.  C1     -C6            1.44 Ang.
PLAT335_ALERT_2_C Large Benzene C-C Range          C1     -C6            0.20 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C3     -   C4     ...       1.55 Ang.

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

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

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Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

(I)

Crystal data

C9H12N^+·C6HCl2O4^−	F(000) = 1408
Mr = 342.16	Dx = 1.538 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 25.840 (8) Å	θ = 11.5–12.5°
b = 7.0633 (10) Å	µ = 0.46 mm^−1
c = 17.107 (5) Å	T = 298 K
β = 108.79 (3)°	Prism, brown
V = 2955.9 (14) Å^3	0.40 × 0.30 × 0.30 mm
Z = 8

Data collection

Rigaku AFC-5R diffractometer	2498 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode	Rint = 0.015
Graphite monochromator	θmax = 27.5°, θmin = 1.7°
ω–2θ scans	h = −2→33
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
Tmin = 0.783, Tmax = 0.872	l = −22→21
3771 measured reflections	3 standard reflections every 97 reflections
3395 independent reflections	intensity decay: 0.2%

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.067P)^2 + 1.1P] where P = (Fo^2 + 2Fc^2)/3
3395 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3
0 constraints

Special details

Experimental. The scan width was (1.57 + 0.30tanθ)° with an ω scan speed of 6° per minute (up to 4 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

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	0.34526 (2)	0.40579 (10)	0.52845 (3)	0.04241 (17)
Cl2	0.58195 (2)	0.16961 (9)	0.52962 (4)	0.04317 (17)
O1	0.44826 (6)	0.3578 (2)	0.67302 (8)	0.0364 (4)
O2	0.38233 (6)	0.3434 (3)	0.38271 (9)	0.0426 (4)
O3	0.48340 (6)	0.2510 (3)	0.38367 (9)	0.0466 (4)
O4	0.54607 (6)	0.2552 (3)	0.67284 (9)	0.0399 (4)
N	0.38474 (7)	0.3619 (3)	0.22434 (11)	0.0335 (4)
C1	0.45193 (8)	0.3308 (3)	0.60226 (12)	0.0278 (4)
C2	0.40986 (8)	0.3482 (3)	0.52748 (12)	0.0286 (4)
C3	0.41800 (8)	0.3235 (3)	0.45046 (12)	0.0299 (4)
C4	0.47592 (8)	0.2676 (3)	0.45027 (12)	0.0301 (4)
C5	0.51810 (8)	0.2407 (3)	0.52868 (12)	0.0291 (4)
C6	0.50741 (8)	0.2727 (3)	0.59976 (12)	0.0282 (4)
C7	0.40313 (11)	0.1878 (4)	0.19134 (17)	0.0561 (7)
C8	0.36387 (13)	0.0326 (4)	0.1829 (2)	0.0631 (8)
C9	0.30810 (12)	0.0842 (4)	0.12204 (18)	0.0564 (7)
C10	0.23445 (10)	0.3256 (4)	0.11574 (17)	0.0528 (7)
C11	0.21712 (11)	0.4965 (5)	0.13567 (18)	0.0569 (7)
C12	0.25393 (11)	0.6201 (4)	0.18672 (18)	0.0504 (6)
C13	0.30855 (10)	0.5727 (3)	0.21646 (14)	0.0398 (5)
C14	0.32553 (8)	0.4019 (3)	0.19319 (11)	0.0289 (4)
C15	0.28928 (9)	0.2732 (3)	0.14344 (13)	0.0371 (5)
H1	0.5346 (15)	0.280 (6)	0.715 (3)	0.119 (15)*
H2	0.3949 (10)	0.352 (4)	0.2786 (17)	0.042 (7)*
H3	0.4019 (11)	0.463 (4)	0.2127 (17)	0.047 (7)*
H4	0.4069	0.2153	0.1379	0.084*
H5	0.4386	0.1494	0.2283	0.084*
H6	0.3775	−0.0804	0.1639	0.095*
H7	0.3601	0.0051	0.2364	0.095*
H8	0.3104	0.0889	0.0666	0.085*
H9	0.2817	−0.0124	0.1232	0.085*
H10	0.2088	0.2420	0.0827	0.063*
H11	0.1804	0.5292	0.1147	0.068*
H12	0.2420	0.7351	0.2011	0.060*
H13	0.3337	0.6543	0.2517	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0305 (3)	0.0643 (4)	0.0328 (3)	0.0094 (3)	0.0107 (2)	0.0023 (3)
Cl2	0.0335 (3)	0.0510 (4)	0.0485 (3)	0.0073 (2)	0.0181 (2)	0.0006 (3)
O1	0.0361 (8)	0.0530 (10)	0.0201 (7)	0.0039 (7)	0.0091 (6)	0.0004 (6)
O2	0.0382 (8)	0.0655 (12)	0.0217 (7)	0.0041 (8)	0.0064 (6)	0.0034 (7)
O3	0.0468 (9)	0.0685 (12)	0.0291 (8)	0.0033 (9)	0.0187 (7)	−0.0026 (8)
O4	0.0306 (7)	0.0598 (11)	0.0263 (7)	0.0051 (7)	0.0049 (6)	−0.0004 (7)
N	0.0331 (9)	0.0424 (11)	0.0260 (9)	−0.0040 (8)	0.0107 (7)	−0.0005 (8)
C1	0.0296 (10)	0.0298 (10)	0.0240 (9)	−0.0009 (8)	0.0087 (7)	0.0003 (8)
C2	0.0270 (9)	0.0342 (11)	0.0250 (9)	0.0020 (8)	0.0089 (7)	0.0011 (8)
C3	0.0329 (10)	0.0321 (11)	0.0235 (9)	−0.0006 (8)	0.0075 (8)	0.0015 (8)
C4	0.0368 (10)	0.0302 (11)	0.0254 (9)	−0.0032 (9)	0.0128 (8)	−0.0014 (8)
C5	0.0276 (9)	0.0315 (11)	0.0302 (10)	0.0008 (8)	0.0121 (8)	−0.0011 (8)
C6	0.0271 (9)	0.0301 (11)	0.0252 (9)	−0.0007 (8)	0.0052 (7)	0.0008 (8)
C7	0.0477 (14)	0.071 (2)	0.0480 (14)	0.0142 (14)	0.0134 (12)	−0.0147 (14)
C8	0.0734 (19)	0.0473 (16)	0.0633 (18)	0.0149 (15)	0.0146 (15)	−0.0065 (14)
C9	0.0631 (17)	0.0401 (14)	0.0548 (15)	−0.0010 (13)	0.0032 (13)	−0.0108 (12)
C10	0.0393 (13)	0.0545 (16)	0.0522 (15)	−0.0079 (12)	−0.0024 (11)	−0.0015 (13)
C11	0.0385 (13)	0.0636 (19)	0.0623 (17)	0.0068 (13)	0.0073 (12)	0.0069 (15)
C12	0.0552 (15)	0.0436 (14)	0.0589 (15)	0.0092 (12)	0.0274 (13)	0.0019 (13)
C13	0.0452 (12)	0.0370 (13)	0.0391 (12)	−0.0056 (10)	0.0162 (10)	−0.0053 (10)
C14	0.0310 (10)	0.0345 (11)	0.0223 (9)	−0.0018 (8)	0.0103 (7)	0.0016 (8)
C15	0.0402 (11)	0.0370 (12)	0.0309 (10)	−0.0049 (10)	0.0070 (9)	0.0009 (9)

Geometric parameters (Å, º)

Cl1—C2	1.723 (2)	C8—C9	1.525 (4)
Cl2—C5	1.720 (2)	C9—C15	1.506 (4)
O1—C1	1.259 (2)	C10—C11	1.368 (4)
O2—C3	1.235 (2)	C10—C15	1.391 (3)
O3—C4	1.221 (2)	C11—C12	1.376 (4)
O4—C6	1.331 (2)	C12—C13	1.378 (4)
O4—H1	0.88 (4)	C13—C14	1.385 (3)
N—C14	1.476 (3)	C14—C15	1.383 (3)
N—C7	1.493 (3)	C7—H4	0.97
N—H2	0.88 (3)	C7—H5	0.97
N—H3	0.89 (3)	C8—H6	0.97
C1—C2	1.392 (3)	C8—H7	0.97
C1—C6	1.505 (3)	C9—H8	0.97
C2—C3	1.411 (3)	C9—H9	0.97
C3—C4	1.549 (3)	C10—H10	0.93
C4—C5	1.443 (3)	C11—H11	0.93
C5—C6	1.350 (3)	C12—H12	0.93
C7—C8	1.469 (4)	C13—H13	0.93
O1···O4^i	2.693 (2)	O3···C7	3.306 (3)
O1···N^ii	2.883 (3)	O3···C1^iii	3.364 (3)
O1···O1^i	3.090 (2)	O3···C6^iii	3.378 (3)
O2···N	2.733 (2)	C3···C5^iii	3.457 (3)
O2···C14	3.126 (3)	C4···C6^iii	3.420 (3)
O2···C13	3.295 (3)	C4···C5^iii	3.490 (3)
O3···N	3.173 (3)	C5···C5^iv	3.579 (3)
C6—O4—H1	114 (3)	C7—C8—C9	111.0 (3)
C14—N—C7	116.10 (18)	C7—C8—H6	109.4
C14—N—H2	108.6 (16)	C9—C8—H6	109.4
C7—N—H2	107.9 (17)	C7—C8—H7	109.4
C14—N—H3	107.3 (17)	C9—C8—H7	109.4
C7—N—H3	109.3 (17)	H6—C8—H7	108.0
H2—N—H3	107 (2)	C15—C9—C8	110.7 (2)
O1—C1—C2	126.28 (18)	C15—C9—H8	109.5
O1—C1—C6	115.86 (17)	C8—C9—H8	109.5
C2—C1—C6	117.86 (17)	C15—C9—H9	109.5
C1—C2—C3	122.69 (18)	C8—C9—H9	109.5
C1—C2—Cl1	118.97 (15)	H8—C9—H9	108.1
C3—C2—Cl1	118.33 (15)	C11—C10—C15	121.9 (2)
O2—C3—C2	124.88 (19)	C11—C10—H10	119.0
O2—C3—C4	117.18 (17)	C15—C10—H10	119.0
C2—C3—C4	117.94 (16)	C10—C11—C12	120.2 (2)
O3—C4—C5	123.76 (19)	C10—C11—H11	119.9
O3—C4—C3	118.02 (18)	C12—C11—H11	119.9
C5—C4—C3	118.21 (16)	C11—C12—C13	119.8 (2)
C6—C5—C4	120.19 (18)	C11—C12—H12	120.1
C6—C5—Cl2	120.97 (16)	C13—C12—H12	120.1
C4—C5—Cl2	118.84 (14)	C12—C13—C14	119.1 (2)
O4—C6—C5	121.40 (18)	C12—C13—H13	120.4
O4—C6—C1	115.61 (17)	C14—C13—H13	120.4
C5—C6—C1	122.99 (17)	C15—C14—C13	122.3 (2)
C8—C7—N	111.0 (2)	C15—C14—N	120.94 (19)
C8—C7—H4	109.4	C13—C14—N	116.74 (19)
N—C7—H4	109.4	C14—C15—C10	116.6 (2)
C8—C7—H5	109.4	C14—C15—C9	121.6 (2)
N—C7—H5	109.4	C10—C15—C9	121.8 (2)
H4—C7—H5	108.0
O1—C1—C2—C3	177.1 (2)	C2—C1—C6—O4	−179.01 (19)
C6—C1—C2—C3	−3.4 (3)	O1—C1—C6—C5	−179.2 (2)
O1—C1—C2—Cl1	−1.9 (3)	C2—C1—C6—C5	1.2 (3)
C6—C1—C2—Cl1	177.59 (15)	C14—N—C7—C8	−38.9 (3)
C1—C2—C3—O2	−177.6 (2)	N—C7—C8—C9	61.7 (3)
Cl1—C2—C3—O2	1.4 (3)	C7—C8—C9—C15	−51.3 (3)
C1—C2—C3—C4	2.3 (3)	C15—C10—C11—C12	−2.2 (4)
Cl1—C2—C3—C4	−178.72 (15)	C10—C11—C12—C13	1.3 (4)
O2—C3—C4—O3	1.8 (3)	C11—C12—C13—C14	1.0 (4)
C2—C3—C4—O3	−178.1 (2)	C12—C13—C14—C15	−2.5 (3)
O2—C3—C4—C5	−179.1 (2)	C12—C13—C14—N	177.7 (2)
C2—C3—C4—C5	1.0 (3)	C7—N—C14—C15	6.7 (3)
O3—C4—C5—C6	176.0 (2)	C7—N—C14—C13	−173.5 (2)
C3—C4—C5—C6	−3.1 (3)	C13—C14—C15—C10	1.6 (3)
O3—C4—C5—Cl2	−3.4 (3)	N—C14—C15—C10	−178.6 (2)
C3—C4—C5—Cl2	177.50 (15)	C13—C14—C15—C9	−177.1 (2)
C4—C5—C6—O4	−177.7 (2)	N—C14—C15—C9	2.7 (3)
Cl2—C5—C6—O4	1.7 (3)	C11—C10—C15—C14	0.8 (4)
C4—C5—C6—C1	2.0 (3)	C11—C10—C15—C9	179.4 (3)
Cl2—C5—C6—C1	−178.58 (16)	C8—C9—C15—C14	19.3 (4)
O1—C1—C6—O4	0.6 (3)	C8—C9—C15—C10	−159.3 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O1	0.88 (5)	2.18 (4)	2.630 (2)	111 (4)
O4—H1···O1^i	0.88 (5)	1.90 (5)	2.693 (2)	148 (4)
N—H2···O2	0.88 (3)	1.91 (3)	2.733 (2)	154 (3)
N—H2···O3	0.88 (3)	2.51 (3)	3.173 (3)	132 (2)
N—H3···O1^v	0.90 (3)	2.01 (3)	2.883 (3)	166 (3)

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