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Acta Cryst. (2010). E66, m377    [ doi:10.1107/S1600536810007889 ]

2-[(R)-Hydroxy(6-methoxyquinolinium-4-yl)methyl]-8-vinyl-1-azoniabicyclo[2.2.2]octane tetrachloridoferrate(III) chloride monohydrate

L.-Z. Chen and M.-N. Huang

Abstract top

In the title salt, (C20H26N2O2)[FeCl4]Cl·H2O, the FeIII atom exists in a tetrahedral coordination environment. The cation, anions and water molecules are linked by N-H...Cl, O-H...Cl and O-H...O hydrogen bonds into a layer network.

Comment top

The existence of a chiral centre in an organic ligand is very important for the construction noncentrosymmetric or chiral coordination polymers that exhibit desirable physical properties such as ferroelectricity (Fu et al., 2007), Chiral quinine has a chiral centre which have shown tremendous scope in the synthesis of transition-metal complexes (Zhao et al., 2003; Qu 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,C20H26N2O2.FeCl4.Cl.H2O(Fig.1), consists of one protoned quinine and a tetrachloro-ironanion with the FeIII ion in a slightly distorted tetrahedral coordination environment, The crystal structure is stabilized by intermolecular N—H···Cl, O—H···Cl and O—H···O hydrogen bonds.The H-bonds form of1D chain viewedalong the a-axis (Fig.2).

Related literature top

For ferroelectricity and SHG, see: Fu et al. (2007); Qu et al. (2003). For related transition-metal complexes, see: Zhao et al. (2003).

Experimental top

A mixture of quinine (1 mmol, 0.324 g ), FeCl3(1 mmol, 0.156 g) 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, crystals of the title compound were formed after 11 days.

Refinement top

All H atoms of quinine were placed in calculated positions , with C—H = 0.93-0.98 Å O—H = 0.85 Å and N—H = 0.96 Å, and re?ned using a riding model, with Uiso(H)=1.2Ueq(C, N, O) or 1.5 Ueq(C) for methyl H atoms.H3A and H3B were located in difference fourier maps.

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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 30% probability level. Hydrogen atoms have been omitted for clarity.
[Figure 2] Fig. 2. The packing viewed along the c axis. Hydrogen bonds are drawn as dashed lines
2-[(R)-Hydroxy(6-methoxyquinolinium-4-yl)methyl]-8-vinyl-1- azoniabicyclo[2.2.2]octane tetrachloridoferrate(III) chloride monohydrate top
Crystal data top
(C20H26N2O2)[FeCl4]Cl·H2OF(000) = 594
Mr = 577.54Dx = 1.450 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 3650 reflections
a = 6.6838 (10) Åθ = 2.9–26.0°
b = 18.843 (2) ŵ = 1.10 mm−1
c = 10.8716 (10) ÅT = 293 K
β = 104.918 (17)°Block, yellow
V = 1323.1 (3) Å30.30 × 0.26 × 0.22 mm
Z = 2
Data collection top
Rigaku SCXmini
diffractometer		5166 independent reflections
Radiation source: fine-focus sealed tube3650 reflections with I > 2σ(I)
graphiteRint = 0.038
Detector resolution: 13.6612 pixels mm-1θmax = 26.0°, θmin = 2.9°
ω scansh = −8→8
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −23→23
Tmin = 0.82, Tmax = 0.88l = −13→13
12145 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)] = 0.048H-atom parameters constrained
wR(F2) = 0.118 w = 1/[σ2(Fo2) + (0.0558P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
5166 reflectionsΔρmax = 0.32 e Å−3
281 parametersΔρmin = −0.30 e Å−3
1 restraintAbsolute structure: Flack (1983), 2490 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (2)
Crystal data top
(C20H26N2O2)[FeCl4]Cl·H2OV = 1323.1 (3) Å3
Mr = 577.54Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.6838 (10) ŵ = 1.10 mm−1
b = 18.843 (2) ÅT = 293 K
c = 10.8716 (10) Å0.30 × 0.26 × 0.22 mm
β = 104.918 (17)°
Data collection top
Rigaku SCXmini
diffractometer		5166 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		3650 reflections with I > 2σ(I)
Tmin = 0.82, Tmax = 0.88Rint = 0.038
12145 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.118Δρmax = 0.32 e Å−3
S = 1.00Δρmin = −0.30 e Å−3
5166 reflectionsAbsolute structure: Flack (1983), 2490 Friedel pairs
281 parametersFlack parameter: 0.01 (2)
1 restraint
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Å2) top
xyzUiso*/Ueq
C10.1691 (8)0.4587 (3)0.0478 (5)0.0721 (13)
H1A0.07000.43060.07060.087*
C20.2105 (7)0.5255 (3)0.0993 (4)0.0631 (11)
H2A0.13590.54260.15440.076*
C30.3610 (6)0.5673 (2)0.0701 (4)0.0520 (10)
C40.4661 (6)0.5415 (2)−0.0214 (4)0.0508 (9)
C50.4159 (7)0.4721 (3)−0.0707 (4)0.0623 (11)
C60.5180 (8)0.4417 (3)−0.1549 (4)0.0762 (14)
H6A0.48410.3962−0.18650.091*
C70.6682 (8)0.4797 (3)−0.1902 (4)0.0750 (14)
H7A0.73910.4595−0.24470.090*
C80.7173 (8)0.5502 (3)−0.1442 (4)0.0646 (12)
C90.6189 (7)0.5800 (2)−0.0622 (3)0.0567 (10)
H9A0.65210.6260−0.03270.068*
C100.9150 (9)0.6537 (3)−0.1527 (5)0.0857 (16)
H10A1.02180.6701−0.19010.129*
H10B0.96240.6567−0.06160.129*
H10C0.79380.6826−0.18180.129*
C110.4201 (6)0.6379 (2)0.1375 (3)0.0508 (9)
H11A0.45400.67210.07810.061*
C120.6126 (6)0.62488 (19)0.2487 (3)0.0467 (9)
H12A0.70890.59590.21560.056*
C130.5696 (7)0.5844 (2)0.3628 (4)0.0565 (10)
H13A0.42290.58610.35830.068*
H13B0.60980.53510.36010.068*
C140.6917 (7)0.6182 (3)0.4861 (4)0.0622 (11)
H14A0.67830.58930.55850.075*
C150.6009 (9)0.6922 (3)0.4946 (5)0.0815 (14)
H15A0.45750.68810.49760.098*
H15B0.67740.71570.57180.098*
C160.6143 (8)0.7356 (3)0.3786 (5)0.0770 (14)
H16A0.47630.74770.32850.092*
H16B0.68940.77930.40580.092*
C170.9372 (7)0.6747 (3)0.3784 (4)0.0672 (12)
H17A1.01080.71800.41080.081*
H17B1.01370.65060.32610.081*
C180.9227 (7)0.6269 (3)0.4897 (4)0.0667 (12)
H18A0.99090.65130.56890.080*
C191.0326 (9)0.5569 (3)0.4871 (6)0.0859 (16)
H19A0.98330.52740.41720.103*
C201.1894 (11)0.5353 (4)0.5747 (7)0.126 (3)
H20A1.24280.56340.64590.151*
H20B1.24930.49150.56670.151*
N10.2684 (6)0.4343 (2)−0.0331 (4)0.0677 (10)
H1B0.23530.3875−0.06730.081*
N20.7244 (6)0.69263 (18)0.2997 (3)0.0574 (9)
H2C0.73730.72110.22890.069*
O10.8655 (5)0.5813 (2)−0.1892 (3)0.0807 (10)
O20.2546 (5)0.66425 (17)0.1827 (3)0.0638 (8)
H2B0.22110.70510.15090.096*
Cl50.2012 (3)0.27667 (8)−0.07702 (16)0.1153 (6)
Cl30.8401 (4)0.35869 (11)0.53267 (16)0.1329 (7)
Cl40.6722 (3)0.24251 (8)0.26529 (17)0.1000 (5)
Cl20.3307 (3)0.37297 (11)0.3350 (2)0.1408 (9)
Fe10.64976 (11)0.35002 (3)0.33590 (7)0.0748 (2)
Cl10.7554 (2)0.42527 (7)0.21006 (13)0.0801 (4)
O30.2399 (9)0.7902 (3)0.0442 (6)0.156 (2)
H3B0.19000.81900.08870.234*
H3A0.14290.7743−0.01620.234*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.073 (3)0.061 (3)0.081 (3)−0.006 (2)0.017 (3)−0.003 (3)
C20.062 (3)0.068 (3)0.064 (3)0.005 (2)0.026 (2)−0.002 (2)
C30.056 (2)0.056 (2)0.043 (2)0.0083 (18)0.0107 (19)0.0022 (18)
C40.056 (2)0.052 (2)0.040 (2)0.0091 (18)0.0052 (19)0.0009 (18)
C50.070 (3)0.065 (3)0.048 (2)0.010 (2)0.008 (2)0.000 (2)
C60.089 (4)0.073 (3)0.065 (3)0.011 (3)0.017 (3)−0.015 (3)
C70.083 (4)0.094 (4)0.045 (2)0.018 (3)0.012 (3)−0.015 (2)
C80.075 (3)0.082 (3)0.038 (2)0.010 (2)0.015 (2)−0.004 (2)
C90.068 (3)0.064 (3)0.038 (2)0.005 (2)0.013 (2)−0.0013 (19)
C100.090 (4)0.110 (5)0.063 (3)−0.019 (3)0.033 (3)0.002 (3)
C110.060 (3)0.051 (2)0.042 (2)0.0082 (18)0.0150 (19)0.0027 (18)
C120.059 (2)0.0405 (19)0.0438 (19)0.0040 (16)0.0192 (18)−0.0006 (16)
C130.056 (2)0.065 (3)0.046 (2)−0.003 (2)0.0091 (19)0.010 (2)
C140.063 (3)0.080 (3)0.044 (2)0.002 (2)0.014 (2)0.009 (2)
C150.095 (4)0.083 (4)0.073 (3)0.011 (3)0.034 (3)−0.015 (3)
C160.094 (4)0.056 (3)0.080 (3)0.010 (2)0.020 (3)−0.019 (2)
C170.065 (3)0.073 (3)0.064 (3)−0.012 (2)0.017 (2)−0.004 (2)
C180.063 (3)0.079 (3)0.049 (2)0.002 (2)−0.003 (2)−0.010 (2)
C190.068 (3)0.087 (4)0.094 (4)0.002 (3)0.006 (3)0.001 (3)
C200.107 (5)0.117 (5)0.140 (6)0.028 (4)0.006 (5)0.027 (5)
N10.076 (3)0.053 (2)0.071 (2)−0.0045 (19)0.012 (2)−0.006 (2)
N20.069 (2)0.0482 (19)0.057 (2)−0.0006 (16)0.0193 (18)0.0030 (16)
O10.085 (2)0.109 (3)0.0543 (18)−0.005 (2)0.0304 (17)−0.0106 (19)
O20.0635 (18)0.0644 (19)0.0641 (17)0.0230 (15)0.0178 (15)−0.0030 (15)
Cl50.1995 (19)0.0617 (8)0.1125 (12)0.0004 (9)0.0904 (13)−0.0178 (8)
Cl30.201 (2)0.1015 (12)0.0886 (10)0.0237 (14)0.0246 (11)0.0161 (10)
Cl40.1138 (11)0.0722 (8)0.1292 (13)0.0163 (8)0.0588 (10)0.0050 (8)
Cl20.1171 (13)0.1379 (16)0.203 (2)0.0635 (11)0.1064 (14)0.0824 (15)
Fe10.0851 (5)0.0634 (4)0.0877 (5)0.0254 (4)0.0437 (4)0.0243 (4)
Cl10.0798 (8)0.0780 (8)0.0897 (8)0.0127 (6)0.0352 (7)0.0281 (7)
O30.163 (5)0.090 (3)0.211 (6)0.004 (3)0.040 (4)0.019 (4)
Geometric parameters (Å, °) top
C1—N11.314 (6)C13—H13B0.9700
C1—C21.377 (7)C14—C151.533 (7)
C1—H1A0.9300C14—C181.543 (7)
C2—C31.378 (6)C14—H14A0.9800
C2—H2A0.9300C15—C161.525 (7)
C3—C41.442 (6)C15—H15A0.9700
C3—C111.521 (6)C15—H15B0.9700
C4—C91.414 (6)C16—N21.503 (6)
C4—C51.420 (6)C16—H16A0.9700
C5—N11.362 (6)C16—H16B0.9700
C5—C61.397 (6)C17—N21.497 (6)
C6—C71.367 (7)C17—C181.531 (7)
C6—H6A0.9300C17—H17A0.9700
C7—C81.428 (7)C17—H17B0.9700
C7—H7A0.9300C18—C191.513 (7)
C8—O11.346 (6)C18—H18A0.9800
C8—C91.358 (6)C19—C201.288 (8)
C9—H9A0.9300C19—H19A0.9300
C10—O11.435 (7)C20—H20A0.9300
C10—H10A0.9600C20—H20B0.9300
C10—H10B0.9600N1—H1B0.9599
C10—H10C0.9600N2—H2C0.9601
C11—O21.411 (5)O2—H2B0.8499
C11—C121.541 (5)Cl3—Fe12.196 (2)
C11—H11A0.9800Cl4—Fe12.1852 (16)
C12—N21.511 (5)Cl2—Fe12.1734 (17)
C12—C131.545 (5)Fe1—Cl12.2085 (13)
C12—H12A0.9800O3—H3B0.8501
C13—C141.517 (6)O3—H3A0.8499
C13—H13A0.9700
N1—C1—C2120.6 (5)C15—C14—C18108.1 (4)
N1—C1—H1A119.7C13—C14—H14A109.7
C2—C1—H1A119.7C15—C14—H14A109.7
C1—C2—C3120.8 (4)C18—C14—H14A109.7
C1—C2—H2A119.6C16—C15—C14109.2 (4)
C3—C2—H2A119.6C16—C15—H15A109.8
C2—C3—C4118.7 (4)C14—C15—H15A109.8
C2—C3—C11120.2 (4)C16—C15—H15B109.8
C4—C3—C11121.0 (4)C14—C15—H15B109.8
C9—C4—C5118.3 (4)H15A—C15—H15B108.3
C9—C4—C3124.2 (4)N2—C16—C15108.9 (4)
C5—C4—C3117.5 (4)N2—C16—H16A109.9
N1—C5—C6119.7 (5)C15—C16—H16A109.9
N1—C5—C4119.2 (4)N2—C16—H16B109.9
C6—C5—C4121.1 (5)C15—C16—H16B109.9
C7—C6—C5119.1 (5)H16A—C16—H16B108.3
C7—C6—H6A120.4N2—C17—C18109.9 (4)
C5—C6—H6A120.4N2—C17—H17A109.7
C6—C7—C8120.6 (4)C18—C17—H17A109.7
C6—C7—H7A119.7N2—C17—H17B109.7
C8—C7—H7A119.7C18—C17—H17B109.7
O1—C8—C9125.8 (5)H17A—C17—H17B108.2
O1—C8—C7113.7 (4)C19—C18—C17111.6 (4)
C9—C8—C7120.5 (5)C19—C18—C14113.2 (4)
C8—C9—C4120.3 (4)C17—C18—C14108.0 (4)
C8—C9—H9A119.8C19—C18—H18A107.9
C4—C9—H9A119.8C17—C18—H18A107.9
O1—C10—H10A109.5C14—C18—H18A107.9
O1—C10—H10B109.5C20—C19—C18124.7 (6)
H10A—C10—H10B109.5C20—C19—H19A117.7
O1—C10—H10C109.5C18—C19—H19A117.7
H10A—C10—H10C109.5C19—C20—H20A120.0
H10B—C10—H10C109.5C19—C20—H20B120.0
O2—C11—C3110.2 (4)H20A—C20—H20B120.0
O2—C11—C12110.7 (3)C1—N1—C5123.2 (4)
C3—C11—C12107.4 (3)C1—N1—H1B118.4
O2—C11—H11A109.5C5—N1—H1B118.4
C3—C11—H11A109.5C17—N2—C16109.1 (3)
C12—C11—H11A109.5C17—N2—C12109.1 (3)
N2—C12—C11112.8 (3)C16—N2—C12113.4 (4)
N2—C12—C13107.4 (3)C17—N2—H2C108.4
C11—C12—C13114.7 (3)C16—N2—H2C108.4
N2—C12—H12A107.2C12—N2—H2C108.4
C11—C12—H12A107.2C8—O1—C10116.8 (4)
C13—C12—H12A107.2C11—O2—H2B109.0
C14—C13—C12109.5 (3)Cl2—Fe1—Cl4109.81 (9)
C14—C13—H13A109.8Cl2—Fe1—Cl3108.14 (9)
C12—C13—H13A109.8Cl4—Fe1—Cl3109.65 (7)
C14—C13—H13B109.8Cl2—Fe1—Cl1109.82 (6)
C12—C13—H13B109.8Cl4—Fe1—Cl1108.41 (6)
H13A—C13—H13B108.2Cl3—Fe1—Cl1111.00 (8)
C13—C14—C15107.7 (4)H3B—O3—H3A109.5
C13—C14—C18112.0 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl50.962.103.023 (4)161
N2—H2C···Cl5i0.962.083.039 (4)173
O2—H2B···O30.852.002.799 (6)156
O3—H3B···Cl5ii0.852.713.070 (6)108
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) −x, y+1/2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···Cl50.962.103.023 (4)161
N2—H2C···Cl5i0.962.083.039 (4)173
O2—H2B···O30.852.002.799 (6)156
O3—H3B···Cl5ii0.852.713.070 (6)108
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) −x, y+1/2, −z.
Acknowledgements top

This work was supported by a start-up grant from Jiangsu University of Science and Technology

references
References top

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