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Acta Cryst. (2008). E64, m1132    [ doi:10.1107/S1600536808024793 ]

Hexaaquazinc(II) dichloride bis(hexamethylenetetramine) tetrahydrate

X. J. Yao, Y. W. Xuan and W. Wu

Abstract top

The title compound, [Zn(H2O)6]Cl2·2C6H12N4·4H2O, has been prepared under mild hydrothermal conditions. The ZnII atom, located on a centre of symmetry, is coordinated by six water molecules in a distorted octahedral coordination geometry. The hexamethylenetetramine molecule is not coordinated to ZnII but links the Zn complexes via three O-H...N hydrogen bonds. The remaining N atom of the hexamethylenetetramine molecule is hydrogen-bonded to a solvent water molecule. In the crystal structure, intermolecular O-H...O, O-H...N and O-H...Cl hydrogen bonds link the components into a three-dimensional network.

Comment top

The asymmetric unit (Fig.1) consists of one half of hexaaua ZnII octahedron, one chloride ion, one uncoordinated neutral hexamethylenetetramine and two molecules of water of crystallization. The hexamethylenetetramine molecule is linked to the [Zn(H2O)6]2+ via three O—H···N hydrogen bonds, while atom N3 of hexamethylenetetramine is hydrogen-bonded to O5 of the solvent water molecule. The Cl- anions link to the [Zn(H2O)6]2+ and water of crystallization via O—H···Cl hydrogen bonding, Hydrogen bonding of these anionic and cationic frameworks results in the formation of a three-dimensional network (Table 1, Fig. 2).

Related literature top

For related compounds, see: Zhang et al. (2000).

Experimental top

All the reagents were of AR grade and used without further purification. C6H12N4 (1.401 g, 10 mmol) were dissolved in 50 mL H2O solution, then the resultant solution was added in 10 mL double-distilled water containing ZnCl2 (0.273 g, 2 mmol). The resulting solution was heated at 423 K for 96 h. After cooling to room temperature, block crystals were obtained in a yield up to 21.1%.

Refinement top

H atoms bonded to O atoms were located in a difference map and included in their 'as found' positions with Uiso(H) = 1.5Ueq(O). Other H atoms were positioned geometrically with C—H = 0.97 Å and with Uiso(H)=1.2Ueq(C). All H atoms were treated as riding.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. Plot of an asymmetric unit with the 30% probability ellipsoids.
[Figure 2] Fig. 2. Three-dimensional network of hydrogen-bonding pattern with the motif R44(16) linking the cationic moieties with hexamine which are in turn interwoven with anionic moieties via water molecules.
Hexaaquazinc(II) dichloride bis(hexamethylenetetramine) tetrahydrate top
Crystal data top
[Zn(H2O)6]Cl2·2C6H12N4·4H2OZ = 1
Mr = 596.84F000 = 316
Triclinic, P1Dx = 1.422 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.345 (3) ÅCell parameters from 2143 reflections
b = 9.4176 (15) Åθ = 2.5–25.5º
c = 9.4535 (15) ŵ = 1.13 mm−1
α = 119.5210 (10)ºT = 291 (2) K
β = 94.218 (2)ºBlock, colorless
γ = 100.969 (2)º0.36 × 0.29 × 0.15 mm
V = 697.0 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		2576 independent reflections
Radiation source: fine-focus sealed tube2466 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
Detector resolution: 0 pixels mm-1θmax = 25.5º
T = 291(2) Kθmin = 2.5º
φ and ω scansh = −11→11
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −11→11
Tmin = 0.690, Tmax = 0.849l = −11→11
5184 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)] = 0.038H-atom parameters constrained
wR(F2) = 0.113  w = 1/[σ2(Fo2) + (0.0645P)2 + 0.6988P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2576 reflectionsΔρmax = 0.51 e Å−3
151 parametersΔρmin = −0.67 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(H2O)6]Cl2·2C6H12N4·4H2Oγ = 100.969 (2)º
Mr = 596.84V = 697.0 (3) Å3
Triclinic, P1Z = 1
a = 9.345 (3) ÅMo Kα
b = 9.4176 (15) ŵ = 1.13 mm−1
c = 9.4535 (15) ÅT = 291 (2) K
α = 119.5210 (10)º0.36 × 0.29 × 0.15 mm
β = 94.218 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2576 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2466 reflections with I > 2σ(I)
Tmin = 0.690, Tmax = 0.849Rint = 0.018
5184 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038151 parameters
wR(F2) = 0.113H-atom parameters constrained
S = 1.05Δρmax = 0.51 e Å−3
2576 reflectionsΔρmin = −0.67 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 > 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
Zn10.50000.00000.00000.02942 (16)
Cl10.18939 (10)0.17479 (10)0.43496 (10)0.0530 (2)
O10.3835 (2)0.1347 (2)−0.0573 (2)0.0385 (5)
H1W0.38880.22570.02690.058*
H2W0.30350.0961−0.12350.058*
O20.6192 (2)0.2238 (2)0.1987 (2)0.0445 (5)
H3W0.61760.25210.29640.067*
H4W0.68330.29490.19300.067*
O30.3580 (2)−0.0281 (3)0.1463 (3)0.0449 (5)
H5W0.34050.06290.20780.067*
H6W0.3658−0.08390.19070.067*
O40.1961 (2)0.5028 (3)0.7778 (3)0.0453 (5)
H7W0.20820.42010.69310.068*
H8W0.10530.49390.77840.068*
O50.1487 (3)0.0521 (4)0.7002 (4)0.0734 (8)
H9W0.16990.09500.64310.110*
H10W0.0600−0.00240.67150.110*
N10.3345 (3)0.7407 (3)0.2554 (3)0.0330 (5)
N20.3362 (3)0.6543 (3)0.4602 (3)0.0333 (5)
N30.3418 (3)0.4524 (3)0.1728 (3)0.0321 (5)
N40.1152 (2)0.5427 (3)0.2441 (3)0.0340 (5)
C10.3865 (3)0.7935 (3)0.4289 (3)0.0356 (6)
H1A0.34920.88860.50100.043*
H1B0.49420.83020.45520.043*
C20.3944 (3)0.5116 (3)0.3488 (3)0.0342 (6)
H2A0.36280.41910.36770.041*
H2B0.50220.54660.37430.041*
C30.1782 (3)0.4021 (3)0.1376 (3)0.0381 (6)
H3A0.14400.30880.15460.046*
H3B0.14220.36320.02230.046*
C40.1706 (3)0.6838 (4)0.2176 (4)0.0375 (6)
H4A0.13480.64800.10320.045*
H4B0.13110.77780.28760.045*
C50.3925 (3)0.5955 (4)0.1482 (3)0.0353 (6)
H5A0.35950.55920.03310.042*
H5B0.50030.63060.17290.042*
C60.1728 (3)0.5995 (4)0.4186 (3)0.0369 (6)
H6A0.13330.69250.49100.044*
H6B0.13860.50760.43770.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0395 (3)0.0233 (2)0.0250 (2)0.00991 (17)0.00711 (17)0.01148 (18)
Cl10.0591 (5)0.0399 (4)0.0534 (5)0.0135 (3)0.0246 (4)0.0173 (4)
O10.0604 (11)0.0278 (9)0.0329 (10)0.0192 (8)−0.0009 (8)0.0105 (8)
O20.0710 (13)0.0280 (10)0.0220 (9)−0.0076 (9)0.0009 (9)0.0081 (8)
O30.0675 (14)0.0422 (11)0.0548 (12)0.0327 (10)0.0401 (11)0.0367 (10)
O40.0398 (11)0.0386 (11)0.0417 (11)0.0003 (9)0.0055 (9)0.0130 (9)
O50.0604 (16)0.086 (2)0.0720 (18)0.0027 (14)−0.0156 (13)0.0485 (16)
N10.0423 (12)0.0298 (11)0.0371 (12)0.0160 (10)0.0161 (10)0.0214 (10)
N20.0426 (12)0.0285 (11)0.0242 (10)0.0036 (9)0.0050 (9)0.0125 (9)
N30.0407 (12)0.0255 (11)0.0275 (11)0.0144 (9)0.0046 (9)0.0102 (9)
N40.0345 (11)0.0289 (11)0.0335 (11)0.0088 (9)0.0063 (9)0.0124 (9)
C10.0433 (15)0.0221 (12)0.0348 (14)0.0048 (10)0.0100 (11)0.0110 (11)
C20.0432 (15)0.0284 (13)0.0326 (13)0.0090 (11)0.0007 (11)0.0178 (11)
C30.0417 (15)0.0264 (13)0.0327 (14)0.0086 (11)−0.0005 (11)0.0066 (11)
C40.0443 (15)0.0376 (15)0.0404 (15)0.0219 (12)0.0136 (12)0.0226 (12)
C50.0452 (15)0.0399 (15)0.0314 (13)0.0217 (12)0.0167 (11)0.0214 (12)
C60.0427 (15)0.0337 (14)0.0326 (14)0.0055 (11)0.0128 (11)0.0167 (11)
Geometric parameters (Å, °) top
Zn1—O2i2.0269 (18)N2—C21.476 (3)
Zn1—O22.0269 (18)N2—C11.481 (3)
Zn1—O12.0507 (17)N3—C31.472 (4)
Zn1—O1i2.0507 (17)N3—C51.476 (3)
Zn1—O3i2.0595 (18)N3—C21.477 (3)
Zn1—O32.0595 (18)N4—C41.477 (4)
O1—H1W0.8223N4—C31.478 (3)
O1—H2W0.8281N4—C61.479 (4)
O2—H3W0.8279C1—H1A0.9700
O2—H4W0.8360C1—H1B0.9700
O3—H5W0.8221C2—H2A0.9700
O3—H6W0.8267C2—H2B0.9700
O4—H7W0.8326C3—H3A0.9700
O4—H8W0.8374C3—H3B0.9700
O5—H9W0.8338C4—H4A0.9700
O5—H10W0.8316C4—H4B0.9700
N1—C11.470 (4)C5—H5A0.9700
N1—C41.476 (4)C5—H5B0.9700
N1—C51.479 (3)C6—H6A0.9700
N2—C61.471 (4)C6—H6B0.9700
O2i—Zn1—O2180.00 (11)C3—N4—C6107.8 (2)
O2i—Zn1—O192.66 (8)N1—C1—N2111.7 (2)
O2—Zn1—O187.34 (8)N1—C1—H1A109.3
O2i—Zn1—O1i87.34 (8)N2—C1—H1A109.3
O2—Zn1—O1i92.66 (8)N1—C1—H1B109.3
O1—Zn1—O1i180.00 (12)N2—C1—H1B109.3
O2i—Zn1—O3i89.59 (9)H1A—C1—H1B107.9
O2—Zn1—O3i90.41 (9)N2—C2—N3111.6 (2)
O1—Zn1—O3i86.57 (8)N2—C2—H2A109.3
O1i—Zn1—O3i93.43 (8)N3—C2—H2A109.3
O2i—Zn1—O390.41 (9)N2—C2—H2B109.3
O2—Zn1—O389.59 (9)N3—C2—H2B109.3
O1—Zn1—O393.43 (8)H2A—C2—H2B108.0
O1i—Zn1—O386.57 (8)N3—C3—N4112.2 (2)
O3i—Zn1—O3180.00 (19)N3—C3—H3A109.2
Zn1—O1—H1W109.5N4—C3—H3A109.2
Zn1—O1—H2W126.6N3—C3—H3B109.2
H1W—O1—H2W113.2N4—C3—H3B109.2
Zn1—O2—H3W124.5H3A—C3—H3B107.9
Zn1—O2—H4W124.2N1—C4—N4112.2 (2)
H3W—O2—H4W111.0N1—C4—H4A109.2
Zn1—O3—H5W109.6N4—C4—H4A109.2
Zn1—O3—H6W123.5N1—C4—H4B109.2
H5W—O3—H6W113.5N4—C4—H4B109.2
H7W—O4—H8W110.1H4A—C4—H4B107.9
H9W—O5—H10W111.5N3—C5—N1111.7 (2)
C1—N1—C4108.4 (2)N3—C5—H5A109.3
C1—N1—C5108.2 (2)N1—C5—H5A109.3
C4—N1—C5108.3 (2)N3—C5—H5B109.3
C6—N2—C2108.5 (2)N1—C5—H5B109.3
C6—N2—C1108.5 (2)H5A—C5—H5B108.0
C2—N2—C1108.0 (2)N2—C6—N4112.0 (2)
C3—N3—C5108.7 (2)N2—C6—H6A109.2
C3—N3—C2108.4 (2)N4—C6—H6A109.2
C5—N3—C2107.9 (2)N2—C6—H6B109.2
C4—N4—C3108.0 (2)N4—C6—H6B109.2
C4—N4—C6108.1 (2)H6A—C6—H6B107.9
C4—N1—C1—N258.4 (3)C1—N1—C4—N4−58.6 (3)
C5—N1—C1—N2−58.8 (3)C5—N1—C4—N458.6 (3)
C6—N2—C1—N1−58.6 (3)C3—N4—C4—N1−58.3 (3)
C2—N2—C1—N158.9 (3)C6—N4—C4—N158.1 (3)
C6—N2—C2—N358.3 (3)C3—N3—C5—N158.1 (3)
C1—N2—C2—N3−59.1 (3)C2—N3—C5—N1−59.2 (3)
C3—N3—C2—N2−58.2 (3)C1—N1—C5—N359.2 (3)
C5—N3—C2—N259.4 (3)C4—N1—C5—N3−58.1 (3)
C5—N3—C3—N4−58.3 (3)C2—N2—C6—N4−58.8 (3)
C2—N3—C3—N458.7 (3)C1—N2—C6—N458.4 (3)
C4—N4—C3—N358.0 (3)C4—N4—C6—N2−58.0 (3)
C6—N4—C3—N3−58.6 (3)C3—N4—C6—N258.5 (3)
Symmetry codes: (i) −x+1, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N30.822.052.827 (3)158
O1—H2W···O5ii0.831.942.743 (3)162
O2—H3W···N2iii0.831.992.804 (3)167
O2—H4W···O4iii0.841.902.711 (3)165
O3—H5W···Cl10.822.553.197 (2)137
O3—H6W···N1iv0.832.012.813 (3)165
O4—H7W···Cl10.832.363.175 (2)168
O4—H8W···N4v0.842.002.835 (3)174
O5—H9W···Cl10.832.433.255 (3)168
O5—H10W···Cl1vi0.832.383.213 (3)175
Symmetry codes: (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1; (iv) x, y−1, z; (v) −x, −y+1, −z+1; (vi) −x, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N30.822.052.827 (3)158
O1—H2W···O5i0.831.942.743 (3)162
O2—H3W···N2ii0.831.992.804 (3)167
O2—H4W···O4ii0.841.902.711 (3)165
O3—H5W···Cl10.822.553.197 (2)137
O3—H6W···N1iii0.832.012.813 (3)165
O4—H7W···Cl10.832.363.175 (2)168
O4—H8W···N4iv0.842.002.835 (3)174
O5—H9W···Cl10.832.433.255 (3)168
O5—H10W···Cl1v0.832.383.213 (3)175
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) −x, −y+1, −z+1; (v) −x, −y, −z+1.
Acknowledgements top

We thank the Natural Science Foundation of Henan Province and the Key Discipline Foundation of Zhoukou Normal University for financial support of this research.

references
References top

Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

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

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

Zhang, Y., Li, J., Nishiura, M. & Imamoto, T. (2000). J. Mol. Struct. 523, 257–260.