Bis(phenyl­ammonium) tetra­chlorido­zincate(II) monohydrate

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 π–π stacking is present between adjacent phenyl­ammonium cations (centroid–centroid distance = 3.672 Å).

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.033
• wR factor = 0.074
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C6 H8 N

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.99

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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 U_iso(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 U_iso(H) = 1.2 (1.5 for methyl groups) times U_eq(C).

Computing details

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

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	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

Crystal data

(C6H8N)[ZnCl4]·H2O	Z = 2
Mr = 413.45	F(000) = 420
Triclinic, P1	Dx = 1.594 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5594 (3) Å	Cell parameters from 10379 reflections
b = 9.8406 (3) Å	θ = 1.0–27.9°
c = 13.0494 (4) Å	µ = 2.04 mm^−1
α = 95.559 (2)°	T = 173 K
β = 102.980 (2)°	Block, colorless
γ = 111.7002 (17)°	0.2 × 0.2 × 0.15 mm
V = 861.36 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3525 independent reflections
Radiation source: fine-focus sealed tube	2964 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.662, Tmax = 0.731	k = −12→10
6199 measured reflections	l = −15→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.023P)^2 + 0.7185P] where P = (Fo^2 + 2Fc^2)/3
3525 reflections	(Δ/σ)max < 0.001
207 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

Special details

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.39838 (5)	0.66322 (3)	0.65645 (2)	0.02118 (10)
Cl1	0.25725 (10)	0.70110 (7)	0.78706 (5)	0.02594 (15)
Cl2	0.37065 (10)	0.83134 (7)	0.55119 (5)	0.02404 (15)
Cl3	0.72039 (10)	0.70842 (8)	0.72409 (6)	0.03091 (16)
Cl4	0.21253 (12)	0.43307 (7)	0.55340 (5)	0.03313 (18)
O1	0.7752 (4)	0.8859 (3)	0.48763 (18)	0.0356 (5)
H1A	1.161 (6)	1.009 (4)	0.635 (3)	0.053*
H1B	0.990 (6)	0.912 (4)	0.658 (3)	0.053*
H1C	1.177 (6)	0.900 (4)	0.696 (3)	0.053*
H2B	0.797 (6)	0.369 (4)	0.608 (3)	0.053*
H2C	0.957 (6)	0.480 (4)	0.685 (3)	0.053*
H2D	0.770 (6)	0.495 (4)	0.665 (3)	0.053*
N1	1.1214 (4)	0.9670 (3)	0.68468 (19)	0.0276 (5)
C1	1.1729 (4)	1.0783 (3)	0.7830 (2)	0.0225 (6)
C2	1.2276 (4)	1.2263 (3)	0.7763 (2)	0.0304 (6)
H2A	1.2312	1.2559	0.7110	0.037*
C3	1.2775 (5)	1.3303 (3)	0.8690 (3)	0.0370 (7)
H3A	1.3147	1.4309	0.8663	0.044*
C4	1.2716 (5)	1.2844 (3)	0.9656 (2)	0.0348 (7)
H4A	1.3056	1.3544	1.0277	0.042*
C5	1.2156 (4)	1.1353 (3)	0.9701 (2)	0.0316 (7)
H5A	1.2128	1.1054	1.0353	0.038*
C6	1.1637 (4)	1.0302 (3)	0.8782 (2)	0.0272 (6)
H6A	1.1235	0.9293	0.8806	0.033*
C7	0.7857 (4)	0.3408 (3)	0.7537 (2)	0.0218 (5)
C8	0.8080 (4)	0.4193 (3)	0.8526 (2)	0.0286 (6)
H8A	0.8530	0.5227	0.8656	0.034*
C9	0.7616 (5)	0.3402 (3)	0.9319 (2)	0.0329 (7)
H9A	0.7745	0.3910	0.9989	0.039*
C10	0.6963 (4)	0.1864 (3)	0.9124 (2)	0.0313 (7)
H10A	0.6646	0.1342	0.9660	0.038*
C11	0.6783 (5)	0.1108 (3)	0.8134 (2)	0.0336 (7)
H11A	0.6358	0.0075	0.8005	0.040*
C12	0.7234 (4)	0.1884 (3)	0.7330 (2)	0.0283 (6)
H12A	0.7116	0.1380	0.6660	0.034*
N2	0.8335 (4)	0.4257 (3)	0.66876 (19)	0.0269 (5)
H1	0.747 (8)	0.786 (6)	0.479 (4)	0.100 (18)*
H2	0.678 (7)	0.892 (5)	0.502 (4)	0.073 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02679 (18)	0.01853 (16)	0.02121 (16)	0.01000 (13)	0.01001 (13)	0.00611 (12)
Cl1	0.0323 (4)	0.0261 (3)	0.0229 (3)	0.0118 (3)	0.0140 (3)	0.0057 (3)
Cl2	0.0348 (4)	0.0179 (3)	0.0217 (3)	0.0111 (3)	0.0101 (3)	0.0071 (2)
Cl3	0.0276 (4)	0.0347 (4)	0.0344 (4)	0.0161 (3)	0.0094 (3)	0.0089 (3)
Cl4	0.0506 (5)	0.0172 (3)	0.0283 (3)	0.0108 (3)	0.0101 (3)	0.0038 (3)
O1	0.0429 (14)	0.0299 (12)	0.0435 (13)	0.0189 (11)	0.0216 (11)	0.0108 (10)
N1	0.0323 (14)	0.0290 (13)	0.0236 (12)	0.0136 (12)	0.0099 (11)	0.0048 (10)
C1	0.0246 (14)	0.0250 (14)	0.0223 (13)	0.0138 (12)	0.0086 (11)	0.0046 (11)
C2	0.0347 (17)	0.0310 (16)	0.0282 (15)	0.0151 (13)	0.0088 (12)	0.0103 (12)
C3	0.0443 (19)	0.0228 (15)	0.0450 (18)	0.0151 (14)	0.0121 (15)	0.0073 (13)
C4	0.0395 (18)	0.0325 (17)	0.0321 (16)	0.0164 (14)	0.0100 (14)	−0.0018 (13)
C5	0.0361 (17)	0.0385 (17)	0.0252 (14)	0.0182 (14)	0.0126 (13)	0.0065 (12)
C6	0.0315 (16)	0.0245 (14)	0.0293 (14)	0.0125 (12)	0.0122 (12)	0.0081 (11)
C7	0.0213 (14)	0.0230 (13)	0.0206 (13)	0.0079 (11)	0.0061 (10)	0.0065 (10)
C8	0.0366 (17)	0.0241 (14)	0.0272 (14)	0.0131 (13)	0.0121 (12)	0.0038 (11)
C9	0.0416 (18)	0.0383 (17)	0.0239 (14)	0.0204 (15)	0.0117 (13)	0.0058 (12)
C10	0.0316 (16)	0.0399 (17)	0.0251 (14)	0.0143 (14)	0.0081 (12)	0.0181 (13)
C11	0.0387 (18)	0.0213 (15)	0.0330 (16)	0.0064 (13)	0.0033 (13)	0.0095 (12)
C12	0.0358 (17)	0.0218 (14)	0.0207 (13)	0.0069 (12)	0.0042 (12)	0.0032 (11)
N2	0.0351 (15)	0.0195 (12)	0.0225 (12)	0.0054 (11)	0.0112 (11)	0.0037 (10)

Geometric parameters (Å, º)

Zn1—Cl3	2.2497 (10)	C5—C6	1.381 (4)
Zn1—Cl4	2.2626 (13)	C5—H5A	0.9300
Zn1—Cl1	2.2737 (9)	C6—H6A	0.9300
Zn1—Cl2	2.2880 (9)	C7—C12	1.373 (4)
O1—H1	0.91 (6)	C7—C8	1.379 (4)
O1—H2	0.82 (5)	C7—N2	1.481 (3)
N1—C1	1.478 (3)	C8—C9	1.385 (4)
N1—H1A	0.85 (4)	C8—H8A	0.9300
N1—H1B	0.90 (4)	C9—C10	1.384 (4)
N1—H1C	0.91 (4)	C9—H9A	0.9300
C1—C2	1.377 (4)	C10—C11	1.379 (4)
C1—C6	1.380 (4)	C10—H10A	0.9300
C2—C3	1.388 (4)	C11—C12	1.387 (4)
C2—H2A	0.9300	C11—H11A	0.9300
C3—C4	1.384 (4)	C12—H12A	0.9300
C3—H3A	0.9300	N2—H2B	0.85 (4)
C4—C5	1.380 (4)	N2—H2C	0.85 (4)
C4—H4A	0.9300	N2—H2D	0.97 (4)
Cl3—Zn1—Cl4	114.11 (4)	C1—C6—C5	118.4 (3)
Cl3—Zn1—Cl1	111.96 (4)	C1—C6—H6A	120.8
Cl4—Zn1—Cl1	109.28 (4)	C5—C6—H6A	120.8
Cl3—Zn1—Cl2	109.65 (4)	C12—C7—C8	122.0 (3)
Cl4—Zn1—Cl2	106.88 (4)	C12—C7—N2	119.8 (2)
Cl1—Zn1—Cl2	104.38 (3)	C8—C7—N2	118.1 (2)
H1—O1—H2	104 (4)	C7—C8—C9	118.3 (3)
C1—N1—H1A	111 (3)	C7—C8—H8A	120.8
C1—N1—H1B	113 (2)	C9—C8—H8A	120.8
H1A—N1—H1B	107 (3)	C10—C9—C8	120.7 (3)
C1—N1—H1C	112 (2)	C10—C9—H9A	119.7
H1A—N1—H1C	108 (3)	C8—C9—H9A	119.7
H1B—N1—H1C	105 (3)	C11—C10—C9	119.9 (3)
C2—C1—C6	122.2 (3)	C11—C10—H10A	120.1
C2—C1—N1	118.9 (2)	C9—C10—H10A	120.1
C6—C1—N1	118.9 (2)	C10—C11—C12	120.2 (3)
C1—C2—C3	118.6 (3)	C10—C11—H11A	119.9
C1—C2—H2A	120.7	C12—C11—H11A	119.9
C3—C2—H2A	120.7	C7—C12—C11	118.9 (3)
C4—C3—C2	120.0 (3)	C7—C12—H12A	120.5
C4—C3—H3A	120.0	C11—C12—H12A	120.5
C2—C3—H3A	120.0	C7—N2—H2B	112 (3)
C5—C4—C3	120.3 (3)	C7—N2—H2C	110 (3)
C5—C4—H4A	119.9	H2B—N2—H2C	110 (3)
C3—C4—H4A	119.9	C7—N2—H2D	109 (2)
C4—C5—C6	120.5 (3)	H2B—N2—H2D	110 (3)
C4—C5—H5A	119.8	H2C—N2—H2D	105 (3)
C6—C5—H5A	119.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl4^i	0.92 (6)	2.30 (6)	3.172 (3)	159 (6)
O1—H2···Cl2	0.82 (5)	2.43 (5)	3.215 (4)	162 (5)
N1—H1A···O1^ii	0.85 (4)	2.04 (4)	2.889 (4)	173 (4)
N1—H1B···O1	0.90 (4)	2.37 (4)	3.022 (4)	130 (3)
N1—H1B···Cl3	0.90 (4)	2.64 (4)	3.343 (3)	135 (3)
N1—H1C···Cl1^iii	0.91 (4)	2.57 (4)	3.426 (3)	156 (3)
N2—H2B···Cl2^i	0.85 (4)	2.45 (4)	3.276 (3)	167 (4)
N2—H2C···Cl1^iii	0.85 (5)	2.47 (4)	3.246 (3)	153 (4)
N2—H2D···Cl3	0.97 (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.