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Acta Cryst. (2007). E63, m2571    [ doi:10.1107/S1600536807044674 ]

Bis(phenylammonium) tetrachloridozincate(II) monohydrate

N. Guo, J. Yi, Y. Chen, S. Liao and Z. Fu

Abstract top

In the crystal structure of the title compound, (C6H8N)[ZnCl4]·H2O, the Zn atom has a tetrahedral geometry and is coordinated by four Cl atoms. The water molecule and phenylammonium cations interact with two [ZnCl4]2- anions, forming discrete structural motifs via O-H...Cl and N-H...Cl/O interactions. Intermolecular [pi]-[pi] stacking is present between adjacent phenylammonium cations (centroid-centroid distance = 3.672 Å).

Comment top

Organic-inorganic hybrid materials are interesting for their potential application in photography and drug delivery (Bringley & Rajeswaran, 2006). In these complexes, the frameworks of the organoammonium cation and the counter inorganic anionic species are stabilized by the hydrogen bonds and coulombic attractions. The analogous complexes bis(p-toluidinium) tetrachlorozincate(II) (Rademeyer, 2005) and p-phenylenediammonium tetrachlorozincate(II) (Bringley & Rajeswaran, 2006) had been reported with different supramolecular structural motifs. Here, a new member of this family, the title compound is presented, which is obtained during our studies of the preparation of new zinc phosphates. As shown in Fig 1, the crystal structure of the title compound contains a [ZnCl4]2− tetrahedral anion unit, two phenylammonium cations and a water molecule. The Zn atom has a tetrahedral coordination sphere surrounded by four Cl atoms. The bond angles Cl—Zn—Cl vary from 104.38 (4) to 114.11 (4)°, and the bond length of Zn—Cl lie in the range from 2.2498 (10) Å to 2.2880 (9) Å. These values indicate that the anionic [ZnCl4]2− tetrahedra is slightly distorted. The inorganic species are isolated by the organic phenylammonium cations (Fig 2). Two water molecules hydrogen bond to two [ZnCl4]2− anions via O—H···Cl interactions, forming a ring with chair conformation and the N atom of the phenylammonium cation participates in two hydrogen bonds with two Cl acceptors in two neighboring [ZnCl4]2− anions via N—H···Cl interactions. These connections results a discrete cluster supramolecular structural feature, different with the layer motifs in its analogous complexes. The intermolecular π-π stacking is evident between the adjacent phenylammonium cations.

Related literature top

Analogous complexes have been reported by Rademeyer (2005) and Bringley & Rajeswaran (2006).

Experimental top

The title compound (I) was obtained unintentionally in the synthesis of zinc phosphate with ZnCl2, phenyltrichloroiminophosphorane and toluene as started materials under hydrothermal reaction conditions.

Refinement top

The H atoms bonded to the O atoms of the water molecules were located in a difference map and refined with distance restraints of O—H = 0.82 (5) Å, and with Uiso(H) = 1.2Ueq(O). The remaining H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXTL (Siemens, 1994).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of (I), viewed down the a axis, showing the N—H···Cl and O—H···Cl hydrogen bonds between the phenylammonium cations, water molecule and [ZnCl4]2− anions.
Bis(phenylammonium) tetrachloridozincate(II) monohydrate top
Crystal data top
(C6H8N)[ZnCl4]·H2OZ = 2
Mr = 413.45F000 = 420
Triclinic, P1Dx = 1.594 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.5594 (3) ÅCell parameters from 10379 reflections
b = 9.8406 (3) Åθ = 1.0–27.9º
c = 13.0494 (4) ŵ = 2.04 mm−1
α = 95.559 (2)ºT = 173 (2) K
β = 102.980 (2)ºBlock, colorless
γ = 111.7002 (17)º0.2 × 0.2 × 0.15 mm
V = 861.36 (5) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		3525 independent reflections
Radiation source: fine-focus sealed tube2964 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
T = 173(2) Kθmax = 26.4º
ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.662, Tmax = 0.731k = −12→10
6199 measured reflectionsl = −15→16
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)] = 0.033H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.074  w = 1/[σ2(Fo2) + (0.023P)2 + 0.7185P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
3525 reflectionsΔρmax = 0.58 e Å−3
207 parametersΔρmin = −0.51 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C6H8N)[ZnCl4]·H2Oγ = 111.7002 (17)º
Mr = 413.45V = 861.36 (5) Å3
Triclinic, P1Z = 2
a = 7.5594 (3) ÅMo Kα
b = 9.8406 (3) ŵ = 2.04 mm−1
c = 13.0494 (4) ÅT = 173 (2) K
α = 95.559 (2)º0.2 × 0.2 × 0.15 mm
β = 102.980 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3525 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2964 reflections with I > 2σ(I)
Tmin = 0.662, Tmax = 0.731Rint = 0.029
6199 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033207 parameters
wR(F2) = 0.074H atoms treated by a mixture of
independent and constrained refinement
S = 1.06Δρmax = 0.58 e Å−3
3525 reflectionsΔρmin = −0.51 e Å−3
Special details top

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 > 2sigma(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
Zn10.39838 (5)0.66322 (3)0.65645 (2)0.02118 (10)
Cl10.25725 (10)0.70110 (7)0.78706 (5)0.02594 (15)
Cl20.37065 (10)0.83134 (7)0.55119 (5)0.02404 (15)
Cl30.72039 (10)0.70842 (8)0.72409 (6)0.03091 (16)
Cl40.21253 (12)0.43307 (7)0.55340 (5)0.03313 (18)
O10.7752 (4)0.8859 (3)0.48763 (18)0.0356 (5)
H1A1.161 (6)1.009 (4)0.635 (3)0.053*
H1B0.990 (6)0.912 (4)0.658 (3)0.053*
H1C1.177 (6)0.900 (4)0.696 (3)0.053*
H2B0.797 (6)0.369 (4)0.608 (3)0.053*
H2C0.957 (6)0.480 (4)0.685 (3)0.053*
H2D0.770 (6)0.495 (4)0.665 (3)0.053*
N11.1214 (4)0.9670 (3)0.68468 (19)0.0276 (5)
C11.1729 (4)1.0783 (3)0.7830 (2)0.0225 (6)
C21.2276 (4)1.2263 (3)0.7763 (2)0.0304 (6)
H2A1.23121.25590.71100.037*
C31.2775 (5)1.3303 (3)0.8690 (3)0.0370 (7)
H3A1.31471.43090.86630.044*
C41.2716 (5)1.2844 (3)0.9656 (2)0.0348 (7)
H4A1.30561.35441.02770.042*
C51.2156 (4)1.1353 (3)0.9701 (2)0.0316 (7)
H5A1.21281.10541.03530.038*
C61.1637 (4)1.0302 (3)0.8782 (2)0.0272 (6)
H6A1.12350.92930.88060.033*
C70.7857 (4)0.3408 (3)0.7537 (2)0.0218 (5)
C80.8080 (4)0.4193 (3)0.8526 (2)0.0286 (6)
H8A0.85300.52270.86560.034*
C90.7616 (5)0.3402 (3)0.9319 (2)0.0329 (7)
H9A0.77450.39100.99890.039*
C100.6963 (4)0.1864 (3)0.9124 (2)0.0313 (7)
H10A0.66460.13420.96600.038*
C110.6783 (5)0.1108 (3)0.8134 (2)0.0336 (7)
H11A0.63580.00750.80050.040*
C120.7234 (4)0.1884 (3)0.7330 (2)0.0283 (6)
H12A0.71160.13800.66600.034*
N20.8335 (4)0.4257 (3)0.66876 (19)0.0269 (5)
H10.747 (8)0.786 (6)0.479 (4)0.100 (18)*
H20.678 (7)0.892 (5)0.502 (4)0.073 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02679 (18)0.01853 (16)0.02121 (16)0.01000 (13)0.01001 (13)0.00611 (12)
Cl10.0323 (4)0.0261 (3)0.0229 (3)0.0118 (3)0.0140 (3)0.0057 (3)
Cl20.0348 (4)0.0179 (3)0.0217 (3)0.0111 (3)0.0101 (3)0.0071 (2)
Cl30.0276 (4)0.0347 (4)0.0344 (4)0.0161 (3)0.0094 (3)0.0089 (3)
Cl40.0506 (5)0.0172 (3)0.0283 (3)0.0108 (3)0.0101 (3)0.0038 (3)
O10.0429 (14)0.0299 (12)0.0435 (13)0.0189 (11)0.0216 (11)0.0108 (10)
N10.0323 (14)0.0290 (13)0.0236 (12)0.0136 (12)0.0099 (11)0.0048 (10)
C10.0246 (14)0.0250 (14)0.0223 (13)0.0138 (12)0.0086 (11)0.0046 (11)
C20.0347 (17)0.0310 (16)0.0282 (15)0.0151 (13)0.0088 (12)0.0103 (12)
C30.0443 (19)0.0228 (15)0.0450 (18)0.0151 (14)0.0121 (15)0.0073 (13)
C40.0395 (18)0.0325 (17)0.0321 (16)0.0164 (14)0.0100 (14)−0.0018 (13)
C50.0361 (17)0.0385 (17)0.0252 (14)0.0182 (14)0.0126 (13)0.0065 (12)
C60.0315 (16)0.0245 (14)0.0293 (14)0.0125 (12)0.0122 (12)0.0081 (11)
C70.0213 (14)0.0230 (13)0.0206 (13)0.0079 (11)0.0061 (10)0.0065 (10)
C80.0366 (17)0.0241 (14)0.0272 (14)0.0131 (13)0.0121 (12)0.0038 (11)
C90.0416 (18)0.0383 (17)0.0239 (14)0.0204 (15)0.0117 (13)0.0058 (12)
C100.0316 (16)0.0399 (17)0.0251 (14)0.0143 (14)0.0081 (12)0.0181 (13)
C110.0387 (18)0.0213 (15)0.0330 (16)0.0064 (13)0.0033 (13)0.0095 (12)
C120.0358 (17)0.0218 (14)0.0207 (13)0.0069 (12)0.0042 (12)0.0032 (11)
N20.0351 (15)0.0195 (12)0.0225 (12)0.0054 (11)0.0112 (11)0.0037 (10)
Geometric parameters (Å, °) top
Zn1—Cl32.2497 (10)C5—C61.381 (4)
Zn1—Cl42.2626 (13)C5—H5A0.9300
Zn1—Cl12.2737 (9)C6—H6A0.9300
Zn1—Cl22.2880 (9)C7—C121.373 (4)
O1—H10.91 (6)C7—C81.379 (4)
O1—H20.82 (5)C7—N21.481 (3)
N1—C11.478 (3)C8—C91.385 (4)
N1—H1A0.85 (4)C8—H8A0.9300
N1—H1B0.90 (4)C9—C101.384 (4)
N1—H1C0.91 (4)C9—H9A0.9300
C1—C21.377 (4)C10—C111.379 (4)
C1—C61.380 (4)C10—H10A0.9300
C2—C31.388 (4)C11—C121.387 (4)
C2—H2A0.9300C11—H11A0.9300
C3—C41.384 (4)C12—H12A0.9300
C3—H3A0.9300N2—H2B0.85 (4)
C4—C51.380 (4)N2—H2C0.85 (4)
C4—H4A0.9300N2—H2D0.97 (4)
Cl3—Zn1—Cl4114.11 (4)C1—C6—C5118.4 (3)
Cl3—Zn1—Cl1111.96 (4)C1—C6—H6A120.8
Cl4—Zn1—Cl1109.28 (4)C5—C6—H6A120.8
Cl3—Zn1—Cl2109.65 (4)C12—C7—C8122.0 (3)
Cl4—Zn1—Cl2106.88 (4)C12—C7—N2119.8 (2)
Cl1—Zn1—Cl2104.38 (3)C8—C7—N2118.1 (2)
H1—O1—H2104 (4)C7—C8—C9118.3 (3)
C1—N1—H1A111 (3)C7—C8—H8A120.8
C1—N1—H1B113 (2)C9—C8—H8A120.8
H1A—N1—H1B107 (3)C10—C9—C8120.7 (3)
C1—N1—H1C112 (2)C10—C9—H9A119.7
H1A—N1—H1C108 (3)C8—C9—H9A119.7
H1B—N1—H1C105 (3)C11—C10—C9119.9 (3)
C2—C1—C6122.2 (3)C11—C10—H10A120.1
C2—C1—N1118.9 (2)C9—C10—H10A120.1
C6—C1—N1118.9 (2)C10—C11—C12120.2 (3)
C1—C2—C3118.6 (3)C10—C11—H11A119.9
C1—C2—H2A120.7C12—C11—H11A119.9
C3—C2—H2A120.7C7—C12—C11118.9 (3)
C4—C3—C2120.0 (3)C7—C12—H12A120.5
C4—C3—H3A120.0C11—C12—H12A120.5
C2—C3—H3A120.0C7—N2—H2B112 (3)
C5—C4—C3120.3 (3)C7—N2—H2C110 (3)
C5—C4—H4A119.9H2B—N2—H2C110 (3)
C3—C4—H4A119.9C7—N2—H2D109 (2)
C4—C5—C6120.5 (3)H2B—N2—H2D110 (3)
C4—C5—H5A119.8H2C—N2—H2D105 (3)
C6—C5—H5A119.8
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl4i0.92 (6)2.30 (6)3.172 (3)159 (6)
O1—H2···Cl20.82 (5)2.43 (5)3.215 (4)162 (5)
N1—H1A···O1ii0.85 (4)2.04 (4)2.889 (4)173 (4)
N1—H1B···O10.90 (4)2.37 (4)3.022 (4)130 (3)
N1—H1B···Cl30.90 (4)2.64 (4)3.343 (3)135 (3)
N1—H1C···Cl1iii0.91 (4)2.57 (4)3.426 (3)156 (3)
N2—H2B···Cl2i0.85 (4)2.45 (4)3.276 (3)167 (4)
N2—H2C···Cl1iii0.85 (5)2.47 (4)3.246 (3)153 (4)
N2—H2D···Cl30.97 (4)2.35 (4)3.262 (3)156 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+2, −z+1; (iii) x+1, y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl4i0.92 (6)2.30 (6)3.172 (3)159 (6)
O1—H2···Cl20.82 (5)2.43 (5)3.215 (4)162 (5)
N1—H1A···O1ii0.85 (4)2.04 (4)2.889 (4)173 (4)
N1—H1B···O10.90 (4)2.37 (4)3.022 (4)130 (3)
N1—H1B···Cl30.90 (4)2.64 (4)3.343 (3)135 (3)
N1—H1C···Cl1iii0.91 (4)2.57 (4)3.426 (3)156 (3)
N2—H2B···Cl2i0.85 (4)2.45 (4)3.276 (3)167 (4)
N2—H2C···Cl1iii0.85 (5)2.47 (4)3.246 (3)153 (4)
N2—H2D···Cl30.97 (4)2.35 (4)3.262 (3)156 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+2, −z+1; (iii) x+1, y, z.
Acknowledgements top

The authors thank the National Science Foundation (20673040) of China for financial support.

references
References top

Bringley, J. F. & Rajeswaran, M. (2006). Acta Cryst. E62, m1304–m1305.

Rademeyer, M. (2005). Acta Cryst. E61, m304–m306.

Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.

Siemens (1994). SAINT and SHELXTL. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Should SAINT be omitted here?

Siemens (1996). SMART. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Or Bruker XSCANS (PLEASE GIVE DATE)?