Quininium tetra-chloridozinc(II).

The asymmetric unit of the title compound {systematic name: 2-[hydr-oxy(6-meth-oxy-quinolin-1-ium-4-yl)meth-yl]-8-vinyl-quinuclidin-1-ium tetra-chlorido-zinc(II)}, (C(20)H(26)N(2)O(2))[ZnCl(4)], consists of a double proton-ated quininium cation and a tetra-chloridozinc(II) anion. The Zn(II) ion is in a slightly distorted tetra-hedral coordination environment. The crystal structure is stabilized by inter-molecular N-H⋯Cl and O-H⋯Cl hydrogen bonds.

Related literature

For ferroelectric behavior, see: Fu et al. (2007 ▶, 2008b ▶). For non-linear optical second harmonic generation, see: Qu et al. (2003b ▶). For transition-metal complexes of quinine, see: Fu et al. (2008a ▶); Qu et al. (2003a ▶); Zhao et al. (2003 ▶).

Experimental

Crystal data

(C20H26N2O2)[ZnCl4]

M = 533.60

Orthorhombic,

a = 9.518 (2) Å

b = 15.680 (5) Å

c = 15.846 (5) Å

V = 2364.8 (12) Å3

Z = 4

Mo Kα radiation

μ = 1.51 mm−1

T = 293 K

0.30 × 0.28 × 0.26 mm

Data collection

Rigaku SCXmini CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.660, T max = 0.695

21856 measured reflections

4631 independent reflections

4325 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.087

S = 1.09

4631 reflections

267 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.83 e Å−3

Δρmin = −0.39 e Å−3

Absolute structure: Flack (1983 ▶), 2005 Friedel pairs

Flack parameter: 0.007 (11)

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035442/hy2224sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035442/hy2224Isup2.hkl

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

(C20H26N2O2)[ZnCl4]	F(000) = 1096
Mr = 533.60	Dx = 1.499 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4325 reflections
a = 9.518 (2) Å	θ = 2.6–26.0°
b = 15.680 (5) Å	µ = 1.51 mm−1
c = 15.846 (5) Å	T = 293 K
V = 2364.8 (12) Å3	Block, colorless
Z = 4	0.30 × 0.28 × 0.26 mm

Rigaku SCXmini CCD diffractometer	4631 independent reflections
Radiation source: fine-focus sealed tube	4325 reflections with I > 2σ(I)
graphite	Rint = 0.038
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0°, θmin = 2.6°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→19
Tmin = 0.660, Tmax = 0.695	l = −19→19
21856 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0449P)2 + 0.0454P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
4631 reflections	Δρmax = 0.83 e Å−3
267 parameters	Δρmin = −0.39 e Å−3
0 restraints	Absolute structure: Flack (1983), 2005 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.007 (11)

	x	y	z	Uiso*/Ueq
C1	−0.0187 (4)	0.4580 (3)	0.6721 (3)	0.0622 (11)
H1A	−0.0926	0.4733	0.7104	0.093*
H1B	0.0314	0.5083	0.6553	0.093*
H1C	0.0448	0.4192	0.6994	0.093*
C2	0.0120 (3)	0.3916 (2)	0.5375 (2)	0.0439 (8)
C3	−0.0535 (4)	0.3493 (3)	0.4687 (3)	0.0565 (10)
H3A	−0.1510	0.3453	0.4672	0.068*
C4	0.1544 (3)	0.4008 (2)	0.53945 (19)	0.0379 (7)
H4A	0.1964	0.4303	0.5837	0.045*
C5	0.0225 (4)	0.3151 (3)	0.4059 (3)	0.0546 (10)
H5A	−0.0219	0.2884	0.3607	0.065*
C6	0.1695 (4)	0.3200 (2)	0.4091 (2)	0.0439 (8)
C7	0.2396 (3)	0.3655 (2)	0.47377 (19)	0.0360 (7)
C8	0.3871 (5)	0.2812 (2)	0.3483 (2)	0.0522 (9)
H8A	0.4358	0.2514	0.3069	0.063*
C9	0.4602 (4)	0.3271 (2)	0.4088 (2)	0.0473 (8)
H9A	0.5579	0.3290	0.4074	0.057*
C10	0.3868 (4)	0.37042 (19)	0.47189 (19)	0.0370 (7)
C11	0.4690 (3)	0.4239 (2)	0.5343 (2)	0.0359 (7)
H11A	0.4266	0.4181	0.5903	0.043*
C12	0.4575 (3)	0.51712 (19)	0.50559 (19)	0.0335 (6)
H12A	0.3577	0.5282	0.4950	0.040*
C13	0.5370 (4)	0.5386 (2)	0.4226 (2)	0.0450 (8)
H13A	0.5877	0.4887	0.4030	0.054*
H13B	0.4703	0.5550	0.3792	0.054*
C14	0.5133 (5)	0.8073 (3)	0.3607 (3)	0.0702 (12)
H14A	0.6090	0.8365	0.3835	0.084*
H14B	0.4720	0.8325	0.3176	0.084*
C15	0.4802 (5)	0.7337 (2)	0.3974 (2)	0.0543 (9)
H15A	0.4002	0.7055	0.3785	0.065*
C16	0.5622 (4)	0.6934 (2)	0.4666 (2)	0.0459 (8)
H16A	0.6324	0.7345	0.4862	0.055*
C17	0.4685 (4)	0.6691 (2)	0.5419 (2)	0.0466 (8)
H17A	0.4823	0.7096	0.5874	0.056*
H17B	0.3705	0.6711	0.5251	0.056*
C18	0.6398 (3)	0.6114 (2)	0.4387 (2)	0.0463 (8)
H18A	0.6929	0.6231	0.3869	0.056*
C19	0.7406 (4)	0.5846 (3)	0.5081 (3)	0.0600 (10)
H19A	0.8157	0.6262	0.5131	0.072*
H19B	0.7820	0.5298	0.4944	0.072*
C20	0.6600 (4)	0.5785 (2)	0.5913 (2)	0.0526 (9)
H20A	0.6838	0.5258	0.6201	0.063*
H20B	0.6849	0.6259	0.6277	0.063*
N1	0.5046 (3)	0.58063 (17)	0.57192 (16)	0.0402 (6)
H1	0.4592	0.5654	0.6278	0.054 (11)*
N2	0.2491 (4)	0.27970 (18)	0.34941 (18)	0.0525 (8)
H2A	0.2064	0.2518	0.3104	0.063*
O1	−0.0779 (2)	0.41778 (18)	0.59904 (17)	0.0549 (6)
O2	0.6096 (2)	0.39639 (15)	0.53783 (16)	0.0474 (5)
H2B	0.623 (4)	0.386 (2)	0.604 (2)	0.050 (10)*
Cl1	0.32557 (9)	0.53094 (5)	0.73304 (5)	0.0476 (2)
Cl2	0.62582 (8)	0.38284 (6)	0.74196 (5)	0.0480 (2)
Cl3	0.27211 (10)	0.29305 (6)	0.72517 (6)	0.0567 (2)
Cl4	0.38062 (10)	0.39886 (6)	0.92702 (5)	0.0538 (2)
Zn1	0.39476 (4)	0.40056 (2)	0.78665 (2)	0.04004 (11)

	U11	U22	U33	U12	U13	U23
C1	0.037 (2)	0.075 (3)	0.074 (3)	0.0023 (19)	0.0023 (18)	−0.016 (2)
C2	0.0350 (17)	0.0454 (19)	0.0514 (19)	−0.0047 (14)	−0.0067 (14)	0.0100 (17)
C3	0.038 (2)	0.060 (2)	0.071 (3)	−0.0166 (16)	−0.0170 (19)	0.013 (2)
C4	0.0322 (16)	0.0390 (16)	0.0424 (16)	−0.0033 (13)	−0.0059 (12)	0.0030 (15)
C5	0.057 (2)	0.058 (2)	0.049 (2)	−0.0198 (19)	−0.0221 (18)	0.0062 (19)
C6	0.056 (2)	0.0389 (17)	0.0373 (17)	−0.0115 (15)	−0.0109 (15)	0.0048 (14)
C7	0.0404 (18)	0.0328 (15)	0.0349 (16)	−0.0069 (13)	−0.0076 (13)	0.0028 (13)
C8	0.070 (3)	0.0444 (19)	0.0419 (19)	−0.0024 (18)	0.0033 (19)	−0.0030 (15)
C9	0.050 (2)	0.0464 (19)	0.0458 (19)	−0.0008 (15)	0.0029 (16)	−0.0048 (16)
C10	0.0435 (18)	0.0342 (15)	0.0332 (15)	−0.0023 (14)	−0.0046 (14)	0.0049 (12)
C11	0.0299 (15)	0.0419 (17)	0.0361 (16)	−0.0032 (12)	0.0003 (13)	−0.0015 (13)
C12	0.0322 (15)	0.0377 (16)	0.0305 (15)	−0.0063 (12)	−0.0002 (12)	−0.0013 (13)
C13	0.057 (2)	0.0420 (18)	0.0358 (18)	−0.0028 (15)	0.0082 (15)	0.0010 (15)
C14	0.101 (3)	0.057 (2)	0.052 (2)	0.012 (2)	0.008 (2)	0.002 (2)
C15	0.063 (2)	0.050 (2)	0.050 (2)	0.0002 (18)	−0.0042 (18)	0.0006 (18)
C16	0.051 (2)	0.0398 (18)	0.0471 (19)	−0.0092 (15)	−0.0009 (15)	−0.0010 (15)
C17	0.053 (2)	0.0382 (18)	0.048 (2)	−0.0040 (15)	0.0082 (16)	−0.0041 (16)
C18	0.0415 (19)	0.0481 (19)	0.0493 (19)	−0.0061 (14)	0.0130 (14)	0.0055 (16)
C19	0.036 (2)	0.062 (3)	0.082 (3)	−0.0065 (16)	0.0003 (18)	0.008 (2)
C20	0.050 (2)	0.052 (2)	0.056 (2)	−0.0138 (16)	−0.0220 (17)	0.0008 (17)
N1	0.0450 (15)	0.0444 (16)	0.0311 (14)	−0.0081 (12)	0.0002 (11)	−0.0049 (12)
N2	0.078 (2)	0.0424 (17)	0.0375 (15)	−0.0137 (15)	−0.0152 (15)	−0.0065 (13)
O1	0.0331 (13)	0.0688 (17)	0.0628 (16)	−0.0017 (11)	−0.0025 (11)	0.0023 (13)
O2	0.0338 (12)	0.0493 (13)	0.0592 (15)	0.0056 (11)	−0.0064 (10)	0.0012 (12)
Cl1	0.0530 (5)	0.0456 (4)	0.0441 (5)	0.0086 (4)	0.0062 (4)	0.0019 (4)
Cl2	0.0369 (4)	0.0630 (5)	0.0440 (4)	0.0088 (4)	0.0028 (3)	−0.0093 (4)
Cl3	0.0517 (5)	0.0551 (5)	0.0632 (6)	−0.0041 (4)	0.0097 (4)	−0.0149 (5)
Cl4	0.0589 (5)	0.0679 (5)	0.0345 (4)	0.0052 (5)	0.0070 (4)	0.0025 (4)
Zn1	0.0409 (2)	0.0449 (2)	0.03432 (18)	0.00593 (17)	0.00545 (15)	−0.00051 (16)

C1—O1	1.433 (5)	C13—H13A	0.9700
C1—H1A	0.9600	C13—H13B	0.9700
C1—H1B	0.9600	C14—C15	1.330 (6)
C1—H1C	0.9600	C14—H14A	1.08
C2—O1	1.361 (4)	C14—H14B	0.88
C2—C4	1.364 (4)	C15—C16	1.486 (5)
C2—C3	1.419 (5)	C15—H15A	0.9300
C3—C5	1.343 (6)	C16—C17	1.537 (5)
C3—H3A	0.9300	C16—C18	1.546 (5)
C4—C7	1.431 (5)	C16—H16A	0.9800
C4—H4A	0.9300	C17—N1	1.506 (5)
C5—C6	1.402 (5)	C17—H17A	0.9700
C5—H5A	0.9300	C17—H17B	0.9700
C6—N2	1.367 (5)	C18—C19	1.519 (5)
C6—C7	1.416 (4)	C18—H18A	0.9800
C7—C10	1.404 (5)	C19—C20	1.529 (5)
C8—N2	1.314 (5)	C19—H19A	0.9700
C8—C9	1.386 (5)	C19—H19B	0.9700
C8—H8A	0.9300	C20—N1	1.511 (5)
C9—C10	1.396 (5)	C20—H20A	0.9700
C9—H9A	0.9300	C20—H20B	0.9700
C10—C11	1.514 (4)	N1—H1	1.01
C11—O2	1.407 (4)	N2—H2A	0.86
C11—C12	1.534 (4)	O2—H2B	1.06 (4)
C11—H11A	0.9800	Cl1—Zn1	2.3097 (10)
C12—N1	1.516 (4)	Cl2—Zn1	2.3271 (10)
C12—C13	1.554 (4)	Cl3—Zn1	2.2701 (11)
C12—H12A	0.9800	Cl4—Zn1	2.2285 (11)
C13—C18	1.525 (5)
O1—C1—H1A	109.5	C15—C14—H14B	128.6
O1—C1—H1B	109.5	H14A—C14—H14B	116.4
H1A—C1—H1B	109.5	C14—C15—C16	124.6 (4)
O1—C1—H1C	109.5	C14—C15—H15A	117.7
H1A—C1—H1C	109.5	C16—C15—H15A	117.7
H1B—C1—H1C	109.5	C15—C16—C17	111.9 (3)
O1—C2—C4	125.2 (3)	C15—C16—C18	113.1 (3)
O1—C2—C3	114.5 (3)	C17—C16—C18	107.1 (3)
C4—C2—C3	120.2 (4)	C15—C16—H16A	108.2
C5—C3—C2	121.3 (4)	C17—C16—H16A	108.2
C5—C3—H3A	119.3	C18—C16—H16A	108.2
C2—C3—H3A	119.3	N1—C17—C16	109.9 (3)
C2—C4—C7	120.3 (3)	N1—C17—H17A	109.7
C2—C4—H4A	119.8	C16—C17—H17A	109.7
C7—C4—H4A	119.8	N1—C17—H17B	109.7
C3—C5—C6	119.2 (4)	C16—C17—H17B	109.7
C3—C5—H5A	120.4	H17A—C17—H17B	108.2
C6—C5—H5A	120.4	C19—C18—C13	108.6 (3)
N2—C6—C5	120.2 (3)	C19—C18—C16	108.9 (3)
N2—C6—C7	118.2 (3)	C13—C18—C16	111.3 (3)
C5—C6—C7	121.6 (4)	C19—C18—H18A	109.3
C10—C7—C6	118.9 (3)	C13—C18—H18A	109.3
C10—C7—C4	124.0 (3)	C16—C18—H18A	109.3
C6—C7—C4	117.1 (3)	C18—C19—C20	109.0 (3)
N2—C8—C9	120.2 (4)	C18—C19—H19A	109.9
N2—C8—H8A	119.9	C20—C19—H19A	109.9
C9—C8—H8A	119.9	C18—C19—H19B	109.9
C8—C9—C10	119.8 (4)	C20—C19—H19B	109.9
C8—C9—H9A	120.1	H19A—C19—H19B	108.3
C10—C9—H9A	120.1	N1—C20—C19	108.3 (3)
C9—C10—C7	119.2 (3)	N1—C20—H20A	110.0
C9—C10—C11	118.6 (3)	C19—C20—H20A	110.0
C7—C10—C11	122.2 (3)	N1—C20—H20B	110.0
O2—C11—C10	110.3 (3)	C19—C20—H20B	110.0
O2—C11—C12	111.8 (2)	H20A—C20—H20B	108.4
C10—C11—C12	107.3 (2)	C17—N1—C20	107.9 (3)
O2—C11—H11A	109.1	C17—N1—C12	108.6 (2)
C10—C11—H11A	109.1	C20—N1—C12	114.5 (3)
C12—C11—H11A	109.1	C17—N1—H1	113.3
N1—C12—C11	113.5 (2)	C20—N1—H1	103.6
N1—C12—C13	107.5 (2)	C12—N1—H1	108.9
C11—C12—C13	115.0 (3)	C8—N2—C6	123.7 (3)
N1—C12—H12A	106.8	C8—N2—H2A	118.1
C11—C12—H12A	106.8	C6—N2—H2A	118.1
C13—C12—H12A	106.8	C2—O1—C1	117.7 (3)
C18—C13—C12	109.4 (3)	C11—O2—H2B	101 (2)
C18—C13—H13A	109.8	Cl4—Zn1—Cl3	112.85 (4)
C12—C13—H13A	109.8	Cl4—Zn1—Cl1	111.13 (4)
C18—C13—H13B	109.8	Cl3—Zn1—Cl1	110.66 (4)
C12—C13—H13B	109.8	Cl4—Zn1—Cl2	111.06 (4)
H13A—C13—H13B	108.2	Cl3—Zn1—Cl2	105.47 (4)
C15—C14—H14A	114.8	Cl1—Zn1—Cl2	105.26 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	1.01	2.17	3.167 (3)	169
N2—H2A···Cl2i	0.86	2.39	3.157 (3)	148
O2—H2B···Cl2	1.06 (4)	2.19 (4)	3.245 (3)	170 (3)

Table 1

Selected bond lengths (Å)

Cl1—Zn1	2.3097 (10)
Cl2—Zn1	2.3271 (10)
Cl3—Zn1	2.2701 (11)
Cl4—Zn1	2.2285 (11)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	1.01	2.17	3.167 (3)	169
N2—H2A⋯Cl2i	0.86	2.39	3.157 (3)	148
O2—H2B⋯Cl2	1.06 (4)	2.19 (4)	3.245 (3)	170 (3)

Symmetry code: (i) .