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Acta Cryst. (2009). E65, m1172    [ doi:10.1107/S1600536809035442 ]

Quininium tetrachloridozinc(II)

L.-Z. Chen

Abstract top

The asymmetric unit of the title compound {systematic name: 2-[hydroxy(6-methoxyquinolin-1-ium-4-yl)methyl]-8-vinylquinuclidin-1-ium tetrachloridozinc(II)}, (C20H26N2O2)[ZnCl4], consists of a double protonated quininium cation and a tetrachloridozinc(II) anion. The ZnII ion is in a slightly distorted tetrahedral coordination environment. The crystal structure is stabilized by intermolecular N-H...Cl and O-H...Cl hydrogen bonds.

Comment top

The existence of a chiral centre in an organic ligand is very important for the construction of noncentrosymmetric or chiral coordination polymers that exhibit desirable physical properties, such as ferroelectricity (Fu et al., 2007, 2008b) and nonlinear optical second harmonic generation (Qu et al., 2003b). Quinine has a chiral centre, which has shown tremendous scope in the synthesis of transition-metal complexes (Fu et al., 2008a; Qu et al., 2003a; Zhao et al., 2003). The construction of new members of this family of ligands is an important direction in the development of modern coordination chemistry. We report here the crystal structure of the title compound.

The asymmetric unit of the title compound consists of a double protonated quininium cation and a tetrachloridozinc anion (Fig. 1). The ZnII ion is in a slightly distorted tetrahedral coordination environment (Table 1). Intermolecular N—H···Cl and O—H···Cl hydrogen bonds lead to a one-dimensional chain along the a axis (Table 2 and Fig. 2).

Related literature top

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 top

A mixture of quinine (0.324 g, 1 mmol), ZnCl2(0.136 g, 1 mmol) and 10% aqueous HCl (6 ml) were mixed and dissolved in 20 ml water by heating to 353 K (0.5 h), forming a clear solution. The reaction mixture was cooled slowly to room temperature and crystals of the title compound were formed after 5 d.

Refinement top

All H atoms were placed in calculated positions, except H1, H2B, H14A and H14B, and refined using a riding model, with C—H = 0.93–0.98 Å and N—H = 0.86 Å and with Uiso(H) = 1.2(or 1.5 for methyl)Ueq(C, N). H1, H2B, H14A and H14B were located in difference Fourier maps. The coordinates of H1 atom were fixed and the Uiso(H1) parameter was refined. H2B atom was refined isotropically. H14A and H14B atoms were fixed with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids were drawn at the 30% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The packing diagram viewed along the c axis. Hydrogen bonds are drawn as dashed lines.
2-[hydroxy(6-methoxyquinolin-1-ium-4-yl)methyl]-8-vinylquinuclidin-1-ium tetrachloridozinc(II) top
Crystal data top
(C20H26N2O2)[ZnCl4]F(000) = 1096
Mr = 533.60Dx = 1.499 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 4325 reflections
a = 9.518 (2) Åθ = 2.6–26.0°
b = 15.680 (5) ŵ = 1.51 mm−1
c = 15.846 (5) ÅT = 293 K
V = 2364.8 (12) Å3Block, colorless
Z = 40.30 × 0.28 × 0.26 mm
Data collection top
Rigaku SCXmini CCD
diffractometer		4631 independent reflections
Radiation source: fine-focus sealed tube4325 reflections with I > 2σ(I)
graphiteRint = 0.038
Detector resolution: 13.6612 pixels mm-1θmax = 26.0°, θmin = 2.6°
ω scansh = −11→11
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −19→19
Tmin = 0.660, Tmax = 0.695l = −19→19
21856 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H 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 reflectionsΔρmax = 0.83 e Å−3
267 parametersΔρmin = −0.39 e Å−3
0 restraintsAbsolute structure: Flack (1983), 2005 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.007 (11)
Crystal data top
(C20H26N2O2)[ZnCl4]V = 2364.8 (12) Å3
Mr = 533.60Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 9.518 (2) ŵ = 1.51 mm−1
b = 15.680 (5) ÅT = 293 K
c = 15.846 (5) Å0.30 × 0.28 × 0.26 mm
Data collection top
Rigaku SCXmini CCD
diffractometer		4631 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		4325 reflections with I > 2σ(I)
Tmin = 0.660, Tmax = 0.695Rint = 0.038
21856 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087Δρmax = 0.83 e Å−3
S = 1.09Δρmin = −0.39 e Å−3
4631 reflectionsAbsolute structure: Flack (1983), 2005 Friedel pairs
267 parametersFlack parameter: 0.007 (11)
0 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1−0.0187 (4)0.4580 (3)0.6721 (3)0.0622 (11)
H1A−0.09260.47330.71040.093*
H1B0.03140.50830.65530.093*
H1C0.04480.41920.69940.093*
C20.0120 (3)0.3916 (2)0.5375 (2)0.0439 (8)
C3−0.0535 (4)0.3493 (3)0.4687 (3)0.0565 (10)
H3A−0.15100.34530.46720.068*
C40.1544 (3)0.4008 (2)0.53945 (19)0.0379 (7)
H4A0.19640.43030.58370.045*
C50.0225 (4)0.3151 (3)0.4059 (3)0.0546 (10)
H5A−0.02190.28840.36070.065*
C60.1695 (4)0.3200 (2)0.4091 (2)0.0439 (8)
C70.2396 (3)0.3655 (2)0.47377 (19)0.0360 (7)
C80.3871 (5)0.2812 (2)0.3483 (2)0.0522 (9)
H8A0.43580.25140.30690.063*
C90.4602 (4)0.3271 (2)0.4088 (2)0.0473 (8)
H9A0.55790.32900.40740.057*
C100.3868 (4)0.37042 (19)0.47189 (19)0.0370 (7)
C110.4690 (3)0.4239 (2)0.5343 (2)0.0359 (7)
H11A0.42660.41810.59030.043*
C120.4575 (3)0.51712 (19)0.50559 (19)0.0335 (6)
H12A0.35770.52820.49500.040*
C130.5370 (4)0.5386 (2)0.4226 (2)0.0450 (8)
H13A0.58770.48870.40300.054*
H13B0.47030.55500.37920.054*
C140.5133 (5)0.8073 (3)0.3607 (3)0.0702 (12)
H14A0.60900.83650.38350.084*
H14B0.47200.83250.31760.084*
C150.4802 (5)0.7337 (2)0.3974 (2)0.0543 (9)
H15A0.40020.70550.37850.065*
C160.5622 (4)0.6934 (2)0.4666 (2)0.0459 (8)
H16A0.63240.73450.48620.055*
C170.4685 (4)0.6691 (2)0.5419 (2)0.0466 (8)
H17A0.48230.70960.58740.056*
H17B0.37050.67110.52510.056*
C180.6398 (3)0.6114 (2)0.4387 (2)0.0463 (8)
H18A0.69290.62310.38690.056*
C190.7406 (4)0.5846 (3)0.5081 (3)0.0600 (10)
H19A0.81570.62620.51310.072*
H19B0.78200.52980.49440.072*
C200.6600 (4)0.5785 (2)0.5913 (2)0.0526 (9)
H20A0.68380.52580.62010.063*
H20B0.68490.62590.62770.063*
N10.5046 (3)0.58063 (17)0.57192 (16)0.0402 (6)
H10.45920.56540.62780.054 (11)*
N20.2491 (4)0.27970 (18)0.34941 (18)0.0525 (8)
H2A0.20640.25180.31040.063*
O1−0.0779 (2)0.41778 (18)0.59904 (17)0.0549 (6)
O20.6096 (2)0.39639 (15)0.53783 (16)0.0474 (5)
H2B0.623 (4)0.386 (2)0.604 (2)0.050 (10)*
Cl10.32557 (9)0.53094 (5)0.73304 (5)0.0476 (2)
Cl20.62582 (8)0.38284 (6)0.74196 (5)0.0480 (2)
Cl30.27211 (10)0.29305 (6)0.72517 (6)0.0567 (2)
Cl40.38062 (10)0.39886 (6)0.92702 (5)0.0538 (2)
Zn10.39476 (4)0.40056 (2)0.78665 (2)0.04004 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.037 (2)0.075 (3)0.074 (3)0.0023 (19)0.0023 (18)−0.016 (2)
C20.0350 (17)0.0454 (19)0.0514 (19)−0.0047 (14)−0.0067 (14)0.0100 (17)
C30.038 (2)0.060 (2)0.071 (3)−0.0166 (16)−0.0170 (19)0.013 (2)
C40.0322 (16)0.0390 (16)0.0424 (16)−0.0033 (13)−0.0059 (12)0.0030 (15)
C50.057 (2)0.058 (2)0.049 (2)−0.0198 (19)−0.0221 (18)0.0062 (19)
C60.056 (2)0.0389 (17)0.0373 (17)−0.0115 (15)−0.0109 (15)0.0048 (14)
C70.0404 (18)0.0328 (15)0.0349 (16)−0.0069 (13)−0.0076 (13)0.0028 (13)
C80.070 (3)0.0444 (19)0.0419 (19)−0.0024 (18)0.0033 (19)−0.0030 (15)
C90.050 (2)0.0464 (19)0.0458 (19)−0.0008 (15)0.0029 (16)−0.0048 (16)
C100.0435 (18)0.0342 (15)0.0332 (15)−0.0023 (14)−0.0046 (14)0.0049 (12)
C110.0299 (15)0.0419 (17)0.0361 (16)−0.0032 (12)0.0003 (13)−0.0015 (13)
C120.0322 (15)0.0377 (16)0.0305 (15)−0.0063 (12)−0.0002 (12)−0.0013 (13)
C130.057 (2)0.0420 (18)0.0358 (18)−0.0028 (15)0.0082 (15)0.0010 (15)
C140.101 (3)0.057 (2)0.052 (2)0.012 (2)0.008 (2)0.002 (2)
C150.063 (2)0.050 (2)0.050 (2)0.0002 (18)−0.0042 (18)0.0006 (18)
C160.051 (2)0.0398 (18)0.0471 (19)−0.0092 (15)−0.0009 (15)−0.0010 (15)
C170.053 (2)0.0382 (18)0.048 (2)−0.0040 (15)0.0082 (16)−0.0041 (16)
C180.0415 (19)0.0481 (19)0.0493 (19)−0.0061 (14)0.0130 (14)0.0055 (16)
C190.036 (2)0.062 (3)0.082 (3)−0.0065 (16)0.0003 (18)0.008 (2)
C200.050 (2)0.052 (2)0.056 (2)−0.0138 (16)−0.0220 (17)0.0008 (17)
N10.0450 (15)0.0444 (16)0.0311 (14)−0.0081 (12)0.0002 (11)−0.0049 (12)
N20.078 (2)0.0424 (17)0.0375 (15)−0.0137 (15)−0.0152 (15)−0.0065 (13)
O10.0331 (13)0.0688 (17)0.0628 (16)−0.0017 (11)−0.0025 (11)0.0023 (13)
O20.0338 (12)0.0493 (13)0.0592 (15)0.0056 (11)−0.0064 (10)0.0012 (12)
Cl10.0530 (5)0.0456 (4)0.0441 (5)0.0086 (4)0.0062 (4)0.0019 (4)
Cl20.0369 (4)0.0630 (5)0.0440 (4)0.0088 (4)0.0028 (3)−0.0093 (4)
Cl30.0517 (5)0.0551 (5)0.0632 (6)−0.0041 (4)0.0097 (4)−0.0149 (5)
Cl40.0589 (5)0.0679 (5)0.0345 (4)0.0052 (5)0.0070 (4)0.0025 (4)
Zn10.0409 (2)0.0449 (2)0.03432 (18)0.00593 (17)0.00545 (15)−0.00051 (16)
Geometric parameters (Å, °) top
C1—O11.433 (5)C13—H13A0.9700
C1—H1A0.9600C13—H13B0.9700
C1—H1B0.9600C14—C151.330 (6)
C1—H1C0.9600C14—H14A1.08
C2—O11.361 (4)C14—H14B0.88
C2—C41.364 (4)C15—C161.486 (5)
C2—C31.419 (5)C15—H15A0.9300
C3—C51.343 (6)C16—C171.537 (5)
C3—H3A0.9300C16—C181.546 (5)
C4—C71.431 (5)C16—H16A0.9800
C4—H4A0.9300C17—N11.506 (5)
C5—C61.402 (5)C17—H17A0.9700
C5—H5A0.9300C17—H17B0.9700
C6—N21.367 (5)C18—C191.519 (5)
C6—C71.416 (4)C18—H18A0.9800
C7—C101.404 (5)C19—C201.529 (5)
C8—N21.314 (5)C19—H19A0.9700
C8—C91.386 (5)C19—H19B0.9700
C8—H8A0.9300C20—N11.511 (5)
C9—C101.396 (5)C20—H20A0.9700
C9—H9A0.9300C20—H20B0.9700
C10—C111.514 (4)N1—H11.01
C11—O21.407 (4)N2—H2A0.86
C11—C121.534 (4)O2—H2B1.06 (4)
C11—H11A0.9800Cl1—Zn12.3097 (10)
C12—N11.516 (4)Cl2—Zn12.3271 (10)
C12—C131.554 (4)Cl3—Zn12.2701 (11)
C12—H12A0.9800Cl4—Zn12.2285 (11)
C13—C181.525 (5)
O1—C1—H1A109.5C15—C14—H14B128.6
O1—C1—H1B109.5H14A—C14—H14B116.4
H1A—C1—H1B109.5C14—C15—C16124.6 (4)
O1—C1—H1C109.5C14—C15—H15A117.7
H1A—C1—H1C109.5C16—C15—H15A117.7
H1B—C1—H1C109.5C15—C16—C17111.9 (3)
O1—C2—C4125.2 (3)C15—C16—C18113.1 (3)
O1—C2—C3114.5 (3)C17—C16—C18107.1 (3)
C4—C2—C3120.2 (4)C15—C16—H16A108.2
C5—C3—C2121.3 (4)C17—C16—H16A108.2
C5—C3—H3A119.3C18—C16—H16A108.2
C2—C3—H3A119.3N1—C17—C16109.9 (3)
C2—C4—C7120.3 (3)N1—C17—H17A109.7
C2—C4—H4A119.8C16—C17—H17A109.7
C7—C4—H4A119.8N1—C17—H17B109.7
C3—C5—C6119.2 (4)C16—C17—H17B109.7
C3—C5—H5A120.4H17A—C17—H17B108.2
C6—C5—H5A120.4C19—C18—C13108.6 (3)
N2—C6—C5120.2 (3)C19—C18—C16108.9 (3)
N2—C6—C7118.2 (3)C13—C18—C16111.3 (3)
C5—C6—C7121.6 (4)C19—C18—H18A109.3
C10—C7—C6118.9 (3)C13—C18—H18A109.3
C10—C7—C4124.0 (3)C16—C18—H18A109.3
C6—C7—C4117.1 (3)C18—C19—C20109.0 (3)
N2—C8—C9120.2 (4)C18—C19—H19A109.9
N2—C8—H8A119.9C20—C19—H19A109.9
C9—C8—H8A119.9C18—C19—H19B109.9
C8—C9—C10119.8 (4)C20—C19—H19B109.9
C8—C9—H9A120.1H19A—C19—H19B108.3
C10—C9—H9A120.1N1—C20—C19108.3 (3)
C9—C10—C7119.2 (3)N1—C20—H20A110.0
C9—C10—C11118.6 (3)C19—C20—H20A110.0
C7—C10—C11122.2 (3)N1—C20—H20B110.0
O2—C11—C10110.3 (3)C19—C20—H20B110.0
O2—C11—C12111.8 (2)H20A—C20—H20B108.4
C10—C11—C12107.3 (2)C17—N1—C20107.9 (3)
O2—C11—H11A109.1C17—N1—C12108.6 (2)
C10—C11—H11A109.1C20—N1—C12114.5 (3)
C12—C11—H11A109.1C17—N1—H1113.3
N1—C12—C11113.5 (2)C20—N1—H1103.6
N1—C12—C13107.5 (2)C12—N1—H1108.9
C11—C12—C13115.0 (3)C8—N2—C6123.7 (3)
N1—C12—H12A106.8C8—N2—H2A118.1
C11—C12—H12A106.8C6—N2—H2A118.1
C13—C12—H12A106.8C2—O1—C1117.7 (3)
C18—C13—C12109.4 (3)C11—O2—H2B101 (2)
C18—C13—H13A109.8Cl4—Zn1—Cl3112.85 (4)
C12—C13—H13A109.8Cl4—Zn1—Cl1111.13 (4)
C18—C13—H13B109.8Cl3—Zn1—Cl1110.66 (4)
C12—C13—H13B109.8Cl4—Zn1—Cl2111.06 (4)
H13A—C13—H13B108.2Cl3—Zn1—Cl2105.47 (4)
C15—C14—H14A114.8Cl1—Zn1—Cl2105.26 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl11.012.173.167 (3)169
N2—H2A···Cl2i0.862.393.157 (3)148
O2—H2B···Cl21.06 (4)2.19 (4)3.245 (3)170 (3)
Symmetry codes: (i) x−1/2, −y+1/2, −z+1.
Table 1
Selected geometric parameters (Å) top
Cl1—Zn12.3097 (10)Cl3—Zn12.2701 (11)
Cl2—Zn12.3271 (10)Cl4—Zn12.2285 (11)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl11.012.173.167 (3)169
N2—H2A···Cl2i0.862.393.157 (3)148
O2—H2B···Cl21.06 (4)2.19 (4)3.245 (3)170 (3)
Symmetry codes: (i) x−1/2, −y+1/2, −z+1.
Acknowledgements top

This work was supported by the start-up grant from Southeast University to Professor Ren-Gen Xiong.

references
References top

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S. D. (2007). J. Am. Chem. Soc. 129, 5346–5347.

Fu, D.-W., Ye, H.-Y., Ye, Q., Pan, K.-J. & Xiong, R.-G. (2008a). Dalton Trans. pp. 874–877.

Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008b). Dalton Trans. pp. 3946–3948.

Qu, Z.-R., Chen, Z.-F., Zhang, J., Xiong, R.-G., Abrahams, B. F. & Xue, Z.-L. (2003a). Organometallics, 22, 2814–2816.

Qu, Z.-R., Zhao, H., Wang, X.-S., Li, Y.-H., Song, Y.-M., Lui, Y.-J., Ye, Q., Xiong, R.-G., Abrahams, B. F., Xue, Z.-L. & You, X.-Z. (2003b). Inorg. Chem. 42, 7710–7712.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zhao, H., Qu, Z.-R., Ye, Q., Abrahams, B. F., Wang, Y.-P., Liu, Z. G., Xue, Z.-L., Xiong, R.-G. & You, X.-Z. (2003). Chem. Mater. 15, 4166–4168.