7-Chloro-4-[(E)-(3-chloro-benzyl-idene)hydrazinyl]-1λ-quinolinium 3-chloro-benzoate.

The title salt, C(16)H(12)Cl(2)N(3) (+)·C(7)H(4)ClO(2) (-), features a non-planar cation, the dihedral angle between the quinolinium and benzene residues being 18.98 (10)°. The cation adopts an E conformation about the C-N bond, and the amine group is oriented towards the quinolinium residue. In the crystal, N-H⋯O hydrogen bonds link two cations with two anions, forming a 20-membered {⋯OCO⋯HNC(3)NH}(2) synthon. The dimeric units are connected into a linear supra-molecular chain along [100] via π-π inter-actions [centroid-centroid distance = 3.5625 (13) Å].

Related literature

For background information on the pharmacological activity of quinoline derivatives, see: Elslager et al. (1969 ▶); Font et al. (1997 ▶); Kaminsky & Meltzer (1968 ▶); Musiol et al. (2006 ▶); n class="Chemical">Nakamura et al. (1999 ▶); Palmer et al. (1993 ▶); Ridley (2002 ▶); Sloboda et al. (1991 ▶); Tanenbaum & Tuffanelli (1980 ▶); Warshakoon et al. (2006 ▶). For recent studies into quinoline-based anti-malarials, see: Andrade et al. (2007 ▶); Cunico et al. (2006 ▶); da Silva et al. (2003 ▶); de Souza (2005 ▶). For a related crystallographic study on neutral species related to the title compound, see: Kaiser et al. (2009 ▶).

Experimental

Crystal data

C16H12Cl2N3 +·n class="Chemical">C7H4ClO2 −

M = 472.74

Triclinic,

a = 8.8777 (2) Å

b = 10.7064 (3) Å

c = 11.9807 (3) Å

α = 112.5318 (12)°

β = 91.6382 (15)°

γ = 97.4362 (15)°

V = 1039.17 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.47 mm−1

T = 120 K

0.06 × 0.04 × 0.03 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.922, T max = 1.000

16836 measured reflections

4746 independent reflections

3949 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.104

S = 1.07

4746 reflections

283 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.45 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DEn class="Chemical">NZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049794/hg2605sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049794/hg2605Isup2.hkl

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

C16H12Cl2N3+·C7H4ClO2−	Z = 2
Mr = 472.74	F(000) = 484
Triclinic, P1	Dx = 1.511 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8777 (2) Å	Cell parameters from 16230 reflections
b = 10.7064 (3) Å	θ = 2.9–27.5°
c = 11.9807 (3) Å	µ = 0.47 mm−1
α = 112.5318 (12)°	T = 120 K
β = 91.6382 (15)°	Block, yellow
γ = 97.4362 (15)°	0.06 × 0.04 × 0.03 mm
V = 1039.17 (5) Å3

Nonius KappaCCD area-detector diffractometer	4746 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	3949 reflections with I > 2σ(I)
10 cm confocal mirrors	Rint = 0.044
Detector resolution: 9.091 pixels mm-1	θmax = 27.5°, θmin = 3.1°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −13→13
Tmin = 0.922, Tmax = 1.000	l = −15→15
16836 measured 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0078P)2 + 1.9095P] where P = (Fo2 + 2Fc2)/3
4746 reflections	(Δ/σ)max = 0.001
283 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	−0.20629 (7)	−0.15682 (6)	0.12224 (5)	0.02306 (14)
Cl2	0.85051 (7)	0.10932 (6)	1.02577 (5)	0.02465 (15)
N1	0.0669 (2)	−0.2783 (2)	0.43607 (18)	0.0167 (4)
H1N	−0.007 (3)	−0.349 (3)	0.417 (2)	0.020*
N2	0.3644 (2)	0.08652 (19)	0.57378 (17)	0.0161 (4)
H2N	0.3580	0.1499	0.5448	0.019*
N3	0.4690 (2)	0.1101 (2)	0.67007 (17)	0.0165 (4)
C1	0.1764 (3)	−0.2566 (2)	0.5229 (2)	0.0176 (5)
H1	0.1815	−0.3246	0.5550	0.021*
C2	0.2826 (3)	−0.1393 (2)	0.5677 (2)	0.0169 (5)
H2	0.3619	−0.1290	0.6269	0.020*
C3	0.2724 (2)	−0.0350 (2)	0.5250 (2)	0.0150 (4)
C4	0.1584 (2)	−0.0590 (2)	0.4281 (2)	0.0152 (4)
C5	0.1406 (3)	0.0354 (2)	0.3736 (2)	0.0160 (4)
H5	0.2070	0.1203	0.4012	0.019*
C6	0.0291 (3)	0.0063 (2)	0.2819 (2)	0.0178 (5)
H6	0.0173	0.0709	0.2469	0.021*
C7	−0.0678 (3)	−0.1204 (2)	0.2400 (2)	0.0174 (5)
C8	−0.0558 (3)	−0.2149 (2)	0.2900 (2)	0.0163 (4)
H8	−0.1226	−0.2996	0.2607	0.020*
C9	0.0570 (2)	−0.1842 (2)	0.3852 (2)	0.0148 (4)
C10	0.5321 (3)	0.2345 (2)	0.7240 (2)	0.0183 (5)
H10	0.5072	0.3008	0.6948	0.022*
C11	0.6420 (3)	0.2766 (2)	0.8300 (2)	0.0190 (5)
C12	0.6897 (3)	0.1816 (2)	0.8718 (2)	0.0178 (5)
H12	0.6519	0.0869	0.8313	0.021*
C13	0.7928 (3)	0.2280 (2)	0.9730 (2)	0.0197 (5)
C14	0.8501 (3)	0.3651 (3)	1.0350 (2)	0.0262 (6)
H14	0.9208	0.3945	1.1043	0.031*
C15	0.8015 (3)	0.4585 (3)	0.9931 (2)	0.0316 (6)
H15	0.8388	0.5532	1.0346	0.038*
C16	0.6988 (3)	0.4153 (3)	0.8908 (2)	0.0274 (6)
H16	0.6673	0.4803	0.8625	0.033*
Cl3	0.12274 (6)	0.37851 (6)	0.30843 (6)	0.02426 (14)
O1	0.67939 (19)	0.66372 (16)	0.43847 (15)	0.0212 (4)
O2	0.84256 (18)	0.51324 (17)	0.36860 (16)	0.0216 (4)
C17	0.7100 (3)	0.5460 (2)	0.3827 (2)	0.0165 (5)
C18	0.5784 (3)	0.4312 (2)	0.3217 (2)	0.0164 (4)
C19	0.4291 (3)	0.4533 (2)	0.3442 (2)	0.0173 (5)
H19	0.4091	0.5382	0.4019	0.021*
C20	0.3100 (3)	0.3500 (2)	0.2816 (2)	0.0182 (5)
C21	0.3357 (3)	0.2254 (2)	0.1967 (2)	0.0218 (5)
H21	0.2526	0.1564	0.1535	0.026*
C22	0.4848 (3)	0.2028 (3)	0.1756 (2)	0.0243 (5)
H22	0.5041	0.1175	0.1183	0.029*
C23	0.6058 (3)	0.3051 (2)	0.2385 (2)	0.0206 (5)
H23	0.7077	0.2889	0.2245	0.025*

	U11	U22	U33	U12	U13	U23
Cl1	0.0229 (3)	0.0245 (3)	0.0229 (3)	−0.0014 (2)	−0.0066 (2)	0.0127 (2)
Cl2	0.0323 (3)	0.0204 (3)	0.0219 (3)	0.0074 (2)	−0.0037 (2)	0.0082 (2)
N1	0.0171 (10)	0.0126 (9)	0.0215 (10)	0.0015 (7)	0.0001 (8)	0.0081 (8)
N2	0.0163 (9)	0.0142 (9)	0.0183 (10)	0.0005 (7)	−0.0038 (7)	0.0080 (8)
N3	0.0153 (9)	0.0180 (10)	0.0158 (9)	0.0014 (7)	−0.0011 (7)	0.0067 (8)
C1	0.0199 (11)	0.0147 (11)	0.0211 (12)	0.0062 (9)	0.0018 (9)	0.0092 (9)
C2	0.0163 (11)	0.0156 (11)	0.0181 (11)	0.0020 (9)	−0.0011 (9)	0.0061 (9)
C3	0.0127 (10)	0.0143 (11)	0.0177 (11)	0.0041 (8)	0.0035 (8)	0.0051 (9)
C4	0.0141 (10)	0.0159 (11)	0.0165 (11)	0.0047 (8)	0.0028 (8)	0.0065 (9)
C5	0.0173 (11)	0.0125 (10)	0.0178 (11)	0.0025 (8)	0.0033 (9)	0.0052 (9)
C6	0.0210 (12)	0.0159 (11)	0.0188 (11)	0.0043 (9)	0.0030 (9)	0.0087 (9)
C7	0.0162 (11)	0.0200 (12)	0.0156 (11)	0.0033 (9)	0.0003 (9)	0.0067 (9)
C8	0.0161 (11)	0.0132 (10)	0.0177 (11)	−0.0001 (8)	0.0014 (9)	0.0048 (9)
C9	0.0159 (11)	0.0128 (10)	0.0162 (11)	0.0025 (8)	0.0019 (8)	0.0060 (9)
C10	0.0195 (11)	0.0164 (11)	0.0195 (12)	0.0004 (9)	−0.0005 (9)	0.0085 (9)
C11	0.0211 (12)	0.0179 (11)	0.0179 (11)	0.0009 (9)	−0.0007 (9)	0.0075 (9)
C12	0.0183 (11)	0.0150 (11)	0.0177 (11)	−0.0006 (9)	−0.0001 (9)	0.0050 (9)
C13	0.0231 (12)	0.0198 (12)	0.0190 (12)	0.0044 (9)	0.0018 (9)	0.0103 (10)
C14	0.0321 (14)	0.0227 (13)	0.0207 (12)	−0.0044 (11)	−0.0088 (10)	0.0083 (10)
C15	0.0453 (17)	0.0165 (12)	0.0277 (14)	−0.0068 (11)	−0.0131 (12)	0.0077 (11)
C16	0.0376 (15)	0.0193 (12)	0.0257 (13)	−0.0007 (11)	−0.0082 (11)	0.0115 (11)
Cl3	0.0161 (3)	0.0240 (3)	0.0307 (3)	0.0009 (2)	−0.0005 (2)	0.0094 (3)
O1	0.0227 (9)	0.0133 (8)	0.0253 (9)	0.0007 (6)	−0.0033 (7)	0.0061 (7)
O2	0.0170 (8)	0.0168 (8)	0.0296 (10)	0.0006 (6)	−0.0019 (7)	0.0085 (7)
C17	0.0195 (11)	0.0154 (11)	0.0166 (11)	0.0018 (9)	−0.0025 (9)	0.0092 (9)
C18	0.0180 (11)	0.0145 (11)	0.0175 (11)	−0.0012 (8)	−0.0011 (9)	0.0085 (9)
C19	0.0208 (11)	0.0145 (11)	0.0165 (11)	0.0020 (9)	−0.0003 (9)	0.0065 (9)
C20	0.0168 (11)	0.0195 (12)	0.0205 (11)	0.0012 (9)	0.0002 (9)	0.0108 (9)
C21	0.0222 (12)	0.0180 (12)	0.0208 (12)	−0.0049 (9)	−0.0012 (10)	0.0054 (10)
C22	0.0279 (13)	0.0158 (11)	0.0233 (13)	−0.0006 (10)	0.0033 (10)	0.0024 (10)
C23	0.0208 (12)	0.0195 (12)	0.0211 (12)	0.0019 (9)	0.0029 (9)	0.0077 (10)

Cl1—C7	1.735 (2)	C11—C16	1.395 (3)
Cl2—C13	1.744 (2)	C11—C12	1.398 (3)
N1—C1	1.334 (3)	C12—C13	1.383 (3)
N1—C9	1.373 (3)	C12—H12	0.9500
N1—H1N	0.89 (3)	C13—C14	1.384 (3)
N2—C3	1.348 (3)	C14—C15	1.386 (4)
N2—N3	1.383 (3)	C14—H14	0.9500
N2—H2N	0.8800	C15—C16	1.392 (4)
N3—C10	1.277 (3)	C15—H15	0.9500
C1—C2	1.379 (3)	C16—H16	0.9500
C1—H1	0.9500	Cl3—C20	1.745 (2)
C2—C3	1.407 (3)	O1—C17	1.250 (3)
C2—H2	0.9500	O2—C17	1.269 (3)
C3—C4	1.440 (3)	C17—C18	1.517 (3)
C4—C9	1.416 (3)	C18—C19	1.392 (3)
C4—C5	1.420 (3)	C18—C23	1.394 (3)
C5—C6	1.371 (3)	C19—C20	1.385 (3)
C5—H5	0.9500	C19—H19	0.9500
C6—C7	1.408 (3)	C20—C21	1.385 (3)
C6—H6	0.9500	C21—C22	1.389 (4)
C7—C8	1.372 (3)	C21—H21	0.9500
C8—C9	1.405 (3)	C22—C23	1.392 (3)
C8—H8	0.9500	C22—H22	0.9500
C10—C11	1.465 (3)	C23—H23	0.9500
C10—H10	0.9500
C1—N1—C9	120.8 (2)	C16—C11—C10	118.8 (2)
C1—N1—H1N	119.7 (17)	C12—C11—C10	121.6 (2)
C9—N1—H1N	119.0 (17)	C13—C12—C11	118.9 (2)
C3—N2—N3	119.06 (18)	C13—C12—H12	120.6
C3—N2—H2N	120.5	C11—C12—H12	120.6
N3—N2—H2N	120.5	C12—C13—C14	122.4 (2)
C10—N3—N2	114.66 (19)	C12—C13—Cl2	118.72 (18)
N1—C1—C2	122.5 (2)	C14—C13—Cl2	118.83 (19)
N1—C1—H1	118.8	C13—C14—C15	118.2 (2)
C2—C1—H1	118.8	C13—C14—H14	120.9
C1—C2—C3	119.4 (2)	C15—C14—H14	120.9
C1—C2—H2	120.3	C14—C15—C16	120.9 (2)
C3—C2—H2	120.3	C14—C15—H15	119.6
N2—C3—C2	121.7 (2)	C16—C15—H15	119.6
N2—C3—C4	119.7 (2)	C15—C16—C11	120.0 (2)
C2—C3—C4	118.6 (2)	C15—C16—H16	120.0
C9—C4—C5	117.9 (2)	C11—C16—H16	120.0
C9—C4—C3	118.0 (2)	O1—C17—O2	125.9 (2)
C5—C4—C3	124.1 (2)	O1—C17—C18	118.0 (2)
C6—C5—C4	121.1 (2)	O2—C17—C18	116.1 (2)
C6—C5—H5	119.4	C19—C18—C23	119.6 (2)
C4—C5—H5	119.4	C19—C18—C17	120.1 (2)
C5—C6—C7	119.3 (2)	C23—C18—C17	120.1 (2)
C5—C6—H6	120.4	C20—C19—C18	119.3 (2)
C7—C6—H6	120.4	C20—C19—H19	120.4
C8—C7—C6	121.8 (2)	C18—C19—H19	120.4
C8—C7—Cl1	119.40 (18)	C19—C20—C21	121.6 (2)
C6—C7—Cl1	118.75 (17)	C19—C20—Cl3	119.25 (18)
C7—C8—C9	118.8 (2)	C21—C20—Cl3	119.13 (18)
C7—C8—H8	120.6	C20—C21—C22	119.1 (2)
C9—C8—H8	120.6	C20—C21—H21	120.5
N1—C9—C8	118.6 (2)	C22—C21—H21	120.5
N1—C9—C4	120.5 (2)	C21—C22—C23	120.0 (2)
C8—C9—C4	120.9 (2)	C21—C22—H22	120.0
N3—C10—C11	121.2 (2)	C23—C22—H22	120.0
N3—C10—H10	119.4	C22—C23—C18	120.4 (2)
C11—C10—H10	119.4	C22—C23—H23	119.8
C16—C11—C12	119.6 (2)	C18—C23—H23	119.8
C3—N2—N3—C10	−168.3 (2)	C11—C12—C13—C14	0.3 (4)
C9—N1—C1—C2	1.3 (3)	C11—C12—C13—Cl2	179.37 (18)
N1—C1—C2—C3	2.9 (3)	C12—C13—C14—C15	0.0 (4)
N3—N2—C3—C2	−1.5 (3)	Cl2—C13—C14—C15	−179.1 (2)
N3—N2—C3—C4	177.33 (19)	C13—C14—C15—C16	−0.5 (4)
C1—C2—C3—N2	173.8 (2)	C14—C15—C16—C11	0.7 (4)
C1—C2—C3—C4	−5.1 (3)	C12—C11—C16—C15	−0.4 (4)
N2—C3—C4—C9	−175.6 (2)	C10—C11—C16—C15	178.9 (2)
C2—C3—C4—C9	3.3 (3)	O1—C17—C18—C19	−10.0 (3)
N2—C3—C4—C5	3.8 (3)	O2—C17—C18—C19	172.1 (2)
C2—C3—C4—C5	−177.3 (2)	O1—C17—C18—C23	166.8 (2)
C9—C4—C5—C6	−0.3 (3)	O2—C17—C18—C23	−11.1 (3)
C3—C4—C5—C6	−179.7 (2)	C23—C18—C19—C20	−1.1 (3)
C4—C5—C6—C7	−0.9 (3)	C17—C18—C19—C20	175.7 (2)
C5—C6—C7—C8	1.2 (3)	C18—C19—C20—C21	−0.3 (3)
C5—C6—C7—Cl1	−178.96 (18)	C18—C19—C20—Cl3	−179.20 (17)
C6—C7—C8—C9	−0.3 (3)	C19—C20—C21—C22	1.2 (4)
Cl1—C7—C8—C9	179.89 (17)	Cl3—C20—C21—C22	−179.88 (19)
C1—N1—C9—C8	176.9 (2)	C20—C21—C22—C23	−0.7 (4)
C1—N1—C9—C4	−3.2 (3)	C21—C22—C23—C18	−0.7 (4)
C7—C8—C9—N1	179.0 (2)	C19—C18—C23—C22	1.7 (4)
C7—C8—C9—C4	−1.0 (3)	C17—C18—C23—C22	−175.2 (2)
C5—C4—C9—N1	−178.7 (2)	C2—C3—N2—N3	−1.5 (3)
C3—C4—C9—N1	0.8 (3)	C4—C3—N2—N3	177.33 (19)
C5—C4—C9—C8	1.3 (3)	N3—C10—C11—C12	4.1 (4)
C3—C4—C9—C8	−179.3 (2)	N3—C10—C11—C16	−175.2 (2)
N2—N3—C10—C11	178.2 (2)	C19—C18—C17—O1	−10.0 (3)
N3—C10—C11—C16	−175.2 (2)	C19—C18—C17—O2	172.1 (2)
N3—C10—C11—C12	4.1 (4)	C23—C18—C17—O1	166.8 (2)
C16—C11—C12—C13	−0.1 (4)	C23—C18—C17—O2	−11.1 (3)
C10—C11—C12—C13	−179.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O2i	0.89 (3)	1.76 (3)	2.641 (3)	175 (3)
N2—H2n···O1ii	0.88	2.00	2.809 (3)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O2i	0.89 (3)	1.76 (3)	2.641 (3)	175 (3)
N2—H2n⋯O1ii	0.88	2.00	2.809 (3)	152

Symmetry codes: (i) ; (ii) .