Bis[μ-5-(2-pyrid­yl)tetra­zolato]-κ3N1,N5:N2;κ3N2:N1,N5-bis­[triaqua­zinc(II)] bis­(trifluoro­acetate) monohydrate

Zhang, L.

doi:10.1107/S1600536809025112

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m871-m872

doi:10.1107/S1600536809025112

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Bis[μ-5-(2-pyridyl)tetrazolato]-κ³N¹,N⁵:N²;κ³N²:N¹,N⁵-bis[triaquazinc(II)] bis(trifluoroacetate) monohydrate

Li Zhang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 26 June 2009; accepted 29 June 2009; online 4 July 2009)

The title compound, [Zn₂(C₆H₄N₅)₂(H₂O)₆](CF₃CO₂)₂·H₂O, was synthesized by hydrothermal reaction of ZnBr₂, CF₃COOH and 2-(2H-tetrazol-5-yl)pyridine. The Zn^II cation is coordinated by one N atom from the 5-(2-pyridyl)tetrazolate anion, two N atoms from another 5-(2-pyridyl)tetrazolate anion and three O atoms from three water molecules in a distorted octahedral geometry. The tetrazole ligands bridge the metal ions of the dimeric structure, and the dimers are located on crystallographic inversion centers. An interstitial solvent water molecule is located on a crystallographic mirror plane, and the CF₃COO⁻ counter-anions are also not coordinated to the metal complex. The F atoms of the anions are disordered with the F atoms statistically distributed over two positions in a 0.56 (3)/0.44 (3) ratio. All the water H atoms are involved in O—H⋯N and O—H⋯O hydrogen bonds with uncoordinated water O atoms, carboxylate O atoms and tetrazole N atoms. The interactions link the molecules into a three-dimensional network.

Related literature

For general background to metal-organic coordination compounds, see: Fu et al. (2007 ); Georgiev & MacGillivray (2007 ). For the crystal structures of related compounds, see: Zhao et al. (2008 ); Fu et al. (2008 ).

Experimental

Crystal data

[Zn₂(C₆H₄N₅)₂(H₂O)₆](C₂F₃O₂)₂·H₂O
M_r = 775.18
Orthorhombic, P b c n
a = 9.1750 (18) Å
b = 14.722 (3) Å
c = 20.657 (4) Å
V = 2790.3 (10) Å³
Z = 4
Mo Kα radiation
μ = 1.83 mm⁻¹
T = 298 K
0.13 × 0.10 × 0.10 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.708, T_max = 0.833
27226 measured reflections
3197 independent reflections
2470 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.089
S = 1.12
3197 reflections
253 parameters
251 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3WB⋯O1W	0.809 (18)	2.03 (2)	2.788 (3)	156 (4)
O1—H1WA⋯O4	0.842 (18)	1.965 (19)	2.800 (3)	171 (4)
O3—H3WA⋯O5ⁱ	0.818 (18)	1.956 (19)	2.771 (3)	174 (4)
O2—H2WB⋯N3ⁱⁱ	0.825 (18)	2.08 (2)	2.856 (3)	156 (4)
O2—H2WA⋯O5ⁱⁱⁱ	0.815 (18)	1.956 (19)	2.769 (3)	175 (4)
O1—H1WB⋯N2ⁱⁱ	0.818 (18)	2.02 (2)	2.821 (3)	165 (4)
O1W—H1W⋯O4^iv	0.809 (18)	2.02 (2)	2.791 (3)	158 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iv) $[-x+1, y, -z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025112/zl2226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025112/zl2226Isup2.hkl

checkCIF report

Comment top

The construction of metal-organic coordination compounds has attracted much attention owing to their potential functions, such as permittivity, fluorescence and optical properties (Fu et al., 2007; Georgiev et al., 2007). Tetrazole compounds are a class of ligands excellently suited for the construction of such metal-organic coordination compounds because of the various coordination modes they exhibit towards metal ions (Zhao, et al. 2008; Fu et al., 2008). We report here the crystal structure of one such metal-organic coordination compound, bis[(µ₂-pyridinio-2-(2H-tetrazolato)- κ³N¹,N²:N⁵)-hexa-aqua-di-zinc(II)]di-trifluoroacetate monohydrate.

In the title compound, each Zn^II cation is coordinated by one N atom from a 5-(2-pyridyl)tetrazolate anion, two N,N-chelating N atoms from another 5-(2-pyridyl)tetrazolate anion and three O atoms from three water molecules in a distorted octahedral geometry. The tetrazole groups act as µ₂-bridges to link the Zn^II ions into dimers, which are located on crystallographic inversion centers. An interstitial solvate water molecule is located on a crystallographic mirror plane, and the CF₃COO^- counter anions are also not coordinated to the metal complex. The F atoms of the anions are rotationally disordered with the F atoms statistically distributed over two positions with a 0.56 (3)/0.44 (3) ratio. The pyridine and tetrazole rings are nearly coplanar with each other and are twisted against each other by only 6.31 (1)°. The geometric parameters of the tetrazolate ring are comparable to those in related molecules (Zhao, et al. 2008; Fu et al., 2008).

In the crystal structure, all the aqua H atoms are involved in O—H···N and O—H···O hydrogen bonds with the solvate aqua O (O1W), carboxyl O (O4, O5) and the tetrazole N (N2, N3) atoms. The interactions link the molecules into a three-dimensional network (Table 1 and Fig.2).

Related literature top

For general background to metal-organic coordination compounds, see: Fu et al. (2007); Georgiev et al. (2007). For the crystal structures of related compounds, see: Zhao et al. (2008); Fu et al. (2008).

Experimental top

A mixture of 2-(2H-tetrazol-5-yl)pyridine (0.2 mmol), ZnBr₂ (0.4 mmol), distilled water (1 ml) and CF₃COOH (0.4 ml) was sealed in a glass tube and maintained at 323 K. Pure colorless block-shaped crystals suitable for X-ray analysis were obtained after 3 d, yield 55% based on ligand. Anal. Calcd. for C₁₆ H₂₂ F₆ N₁₀ O₁₁ Zn₂: C, 24.77%; H, 2.84%; N, 18.06%. Found: C, 24.69%; H, 2.79%; N, 17.98%. IR (KBr pellet, cm^-1): 3421 (s), 3075 (w), 1726 (s), 1635 (s), 1610 (s), 1561 (w), 1475 (w), 1432 (w), 1367 (s), 1283 (s), 1257 (s), 1181 (w), 765 (w), 721 (w), 687 (w).

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

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis, showing the three dimensionnal hydrogen-bonding network (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

Bis[µ-5-(2-pyridyl)tetrazolato]-κ³N¹,N⁵:N²;κ³N²:N¹,N⁵- bis[triaquazinc(II)] bis(trifluoroacetate) monohydrate top

Crystal data top

[Zn₂(C₆H₄N₅)₂(H₂O)₆](C₂F₃O₂)₂·H₂O	F(000) = 1560
M_r = 775.18	D_x = 1.845 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2470 reflections
a = 9.1750 (18) Å	θ = 3.3–27.5°
b = 14.722 (3) Å	µ = 1.83 mm⁻¹
c = 20.657 (4) Å	T = 298 K
V = 2790.3 (10) Å³	Block, colorless
Z = 4	0.13 × 0.10 × 0.10 mm

Data collection top

Rigaku Mercury2 diffractometer	3197 independent reflections
Radiation source: fine-focus sealed tube	2470 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.074
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
CCD profile fitting scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→19
T_min = 0.708, T_max = 0.833	l = −26→26
27226 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0331P)² + 2.0898P] where P = (F_o² + 2F_c²)/3
3197 reflections	(Δ/σ)_max < 0.001
253 parameters	Δρ_max = 0.35 e Å⁻³
251 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Zn₂(C₆H₄N₅)₂(H₂O)₆](C₂F₃O₂)₂·H₂O	V = 2790.3 (10) Å³
M_r = 775.18	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 9.1750 (18) Å	µ = 1.83 mm⁻¹
b = 14.722 (3) Å	T = 298 K
c = 20.657 (4) Å	0.13 × 0.10 × 0.10 mm

Data collection top

Rigaku Mercury2 diffractometer	3197 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2470 reflections with I > 2σ(I)
T_min = 0.708, T_max = 0.833	R_int = 0.074
27226 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	251 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.35 e Å⁻³
3197 reflections	Δρ_min = −0.49 e Å⁻³
253 parameters

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 > 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.56081 (3)	0.12025 (2)	0.447600 (15)	0.02154 (11)
N1	0.7732 (3)	0.12660 (15)	0.40077 (12)	0.0269 (5)
N5	0.6601 (2)	−0.00968 (15)	0.47213 (11)	0.0227 (5)
C1	0.8615 (3)	0.05501 (18)	0.41119 (13)	0.0242 (6)
C3	1.0585 (4)	0.1271 (2)	0.35717 (17)	0.0431 (8)
H3	1.1547	0.1278	0.3430	0.052*
C2	1.0043 (3)	0.0530 (2)	0.39017 (15)	0.0328 (7)
H2	1.0628	0.0026	0.3981	0.039*
C4	0.9684 (4)	0.1997 (2)	0.34563 (17)	0.0439 (9)
H4	1.0023	0.2500	0.3228	0.053*
C5	0.8276 (4)	0.1973 (2)	0.36817 (16)	0.0359 (7)
H5	0.7675	0.2470	0.3604	0.043*
N2	0.8487 (3)	−0.10045 (16)	0.46066 (12)	0.0308 (6)
C6	0.7937 (3)	−0.01880 (18)	0.44738 (13)	0.0232 (6)
N3	0.7445 (3)	−0.14277 (16)	0.49503 (13)	0.0306 (6)
N4	0.6325 (2)	−0.08873 (15)	0.50152 (11)	0.0234 (5)
O1W	0.5000	0.1758 (2)	0.2500	0.0401 (8)
H1W	0.563 (3)	0.212 (2)	0.241 (2)	0.060*
O4	0.3097 (2)	0.29375 (15)	0.31366 (11)	0.0390 (5)
O5	0.1974 (3)	0.41373 (15)	0.35629 (11)	0.0439 (6)
C7	0.2553 (3)	0.3704 (2)	0.31174 (15)	0.0285 (6)
O1	0.4894 (3)	0.24792 (13)	0.41823 (11)	0.0339 (5)
H1WA	0.428 (3)	0.260 (2)	0.3893 (14)	0.051*
H1WB	0.522 (4)	0.2972 (16)	0.4296 (18)	0.051*
O2	0.6523 (3)	0.18073 (14)	0.52952 (11)	0.0394 (6)
H2WA	0.670 (4)	0.151 (2)	0.5621 (13)	0.059*
H2WB	0.697 (4)	0.2292 (18)	0.5291 (19)	0.059*
O3	0.4655 (3)	0.07205 (15)	0.36187 (11)	0.0382 (6)
H3WA	0.420 (4)	0.0246 (17)	0.3576 (18)	0.057*
H3WB	0.490 (4)	0.089 (2)	0.3263 (12)	0.057*
C8	0.2574 (4)	0.4177 (2)	0.24534 (16)	0.0383 (8)
F1	0.3505 (12)	0.3818 (7)	0.2048 (5)	0.067 (2)	0.56 (3)
F2	0.286 (2)	0.5036 (5)	0.2486 (8)	0.099 (4)	0.56 (3)
F3	0.1294 (9)	0.4106 (11)	0.2175 (6)	0.101 (4)	0.56 (3)
F1'	0.3771 (14)	0.4040 (15)	0.2124 (8)	0.114 (5)	0.44 (3)
F2'	0.241 (2)	0.5056 (6)	0.2495 (9)	0.081 (4)	0.44 (3)
F3'	0.1517 (15)	0.3909 (10)	0.2077 (8)	0.081 (4)	0.44 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02240 (17)	0.01646 (16)	0.02576 (18)	−0.00013 (13)	0.00141 (14)	0.00342 (13)
N1	0.0262 (12)	0.0216 (12)	0.0329 (13)	−0.0012 (10)	0.0054 (10)	0.0065 (10)
N5	0.0239 (12)	0.0162 (11)	0.0281 (12)	0.0025 (9)	0.0040 (10)	0.0033 (9)
C1	0.0240 (15)	0.0228 (14)	0.0258 (15)	−0.0029 (12)	0.0039 (12)	−0.0014 (11)
C3	0.0308 (17)	0.046 (2)	0.052 (2)	−0.0089 (16)	0.0140 (16)	−0.0024 (16)
C2	0.0266 (15)	0.0314 (16)	0.0406 (19)	0.0002 (14)	0.0058 (14)	−0.0002 (14)
C4	0.041 (2)	0.0367 (18)	0.054 (2)	−0.0119 (15)	0.0144 (17)	0.0106 (16)
C5	0.0365 (17)	0.0273 (16)	0.0438 (19)	−0.0011 (14)	0.0071 (15)	0.0111 (14)
N2	0.0278 (13)	0.0239 (13)	0.0406 (15)	0.0073 (10)	0.0087 (11)	0.0063 (10)
C6	0.0227 (14)	0.0217 (13)	0.0251 (14)	0.0026 (11)	0.0024 (12)	−0.0013 (11)
N3	0.0323 (14)	0.0203 (12)	0.0394 (15)	0.0073 (11)	0.0085 (12)	0.0063 (11)
N4	0.0236 (12)	0.0166 (11)	0.0301 (13)	0.0023 (10)	0.0024 (10)	0.0026 (9)
O1W	0.054 (2)	0.0308 (18)	0.0356 (19)	0.000	0.0115 (17)	0.000
O4	0.0455 (14)	0.0298 (11)	0.0418 (13)	0.0104 (10)	0.0031 (11)	0.0040 (10)
O5	0.0642 (16)	0.0362 (12)	0.0314 (12)	0.0172 (12)	0.0148 (11)	0.0070 (10)
C7	0.0260 (15)	0.0286 (16)	0.0311 (15)	−0.0017 (12)	−0.0020 (13)	0.0027 (13)
O1	0.0426 (13)	0.0163 (10)	0.0428 (14)	−0.0028 (10)	−0.0170 (11)	0.0042 (9)
O2	0.0622 (16)	0.0264 (12)	0.0296 (12)	−0.0194 (11)	−0.0146 (12)	0.0060 (9)
O3	0.0556 (16)	0.0317 (12)	0.0272 (12)	−0.0181 (11)	−0.0036 (11)	−0.0010 (10)
C8	0.046 (2)	0.0387 (18)	0.0302 (18)	0.0042 (16)	0.0016 (15)	0.0037 (15)
F1	0.114 (6)	0.055 (4)	0.032 (3)	0.011 (3)	0.026 (3)	−0.003 (3)
F2	0.204 (11)	0.037 (4)	0.055 (6)	−0.035 (5)	0.039 (6)	0.006 (4)
F3	0.061 (4)	0.169 (10)	0.073 (6)	0.012 (5)	−0.030 (3)	0.057 (6)
F1'	0.072 (6)	0.177 (13)	0.093 (10)	0.055 (7)	0.056 (6)	0.088 (8)
F2'	0.175 (11)	0.033 (4)	0.035 (6)	0.015 (5)	−0.010 (7)	0.011 (4)
F3'	0.129 (8)	0.066 (5)	0.048 (5)	−0.017 (6)	−0.038 (6)	−0.018 (4)

Geometric parameters (Å, º) top

Zn1—O1	2.081 (2)	N2—N3	1.344 (3)
Zn1—O2	2.088 (2)	N3—N4	1.307 (3)
Zn1—O3	2.098 (2)	N4—Zn1ⁱ	2.113 (2)
Zn1—N4ⁱ	2.113 (2)	O1W—H1W	0.809 (18)
Zn1—N1	2.177 (2)	O4—C7	1.235 (3)
Zn1—N5	2.179 (2)	O5—C7	1.239 (4)
N1—C5	1.336 (4)	C7—C8	1.538 (4)
N1—C1	1.347 (3)	O1—H1WA	0.842 (18)
N5—C6	1.335 (3)	O1—H1WB	0.818 (18)
N5—N4	1.337 (3)	O2—H2WA	0.815 (18)
C1—C2	1.380 (4)	O2—H2WB	0.825 (18)
C1—C6	1.459 (4)	O3—H3WA	0.818 (18)
C3—C4	1.373 (5)	O3—H3WB	0.809 (18)
C3—C2	1.379 (4)	C8—F2	1.294 (8)
C3—H3	0.9300	C8—F3'	1.304 (9)
C2—H2	0.9300	C8—F2'	1.306 (9)
C4—C5	1.374 (4)	C8—F1'	1.307 (9)
C4—H4	0.9300	C8—F1	1.308 (7)
C5—H5	0.9300	C8—F3	1.312 (7)
N2—C6	1.332 (4)

O1—Zn1—O2	88.72 (9)	N2—C6—N5	111.1 (2)
O1—Zn1—O3	85.89 (9)	N2—C6—C1	128.0 (2)
O2—Zn1—O3	174.52 (9)	N5—C6—C1	120.9 (2)
O1—Zn1—N4ⁱ	94.53 (9)	N4—N3—N2	109.4 (2)
O2—Zn1—N4ⁱ	91.59 (9)	N3—N4—N5	109.5 (2)
O3—Zn1—N4ⁱ	89.76 (9)	N3—N4—Zn1ⁱ	125.28 (17)
O1—Zn1—N1	96.52 (9)	N5—N4—Zn1ⁱ	125.18 (17)
O2—Zn1—N1	88.98 (10)	O4—C7—O5	128.3 (3)
O3—Zn1—N1	90.71 (10)	O4—C7—C8	115.9 (3)
N4ⁱ—Zn1—N1	168.94 (9)	O5—C7—C8	115.8 (3)
O1—Zn1—N5	173.03 (9)	Zn1—O1—H1WA	128 (3)
O2—Zn1—N5	91.03 (9)	Zn1—O1—H1WB	127 (3)
O3—Zn1—N5	94.22 (9)	H1WA—O1—H1WB	105 (4)
N4ⁱ—Zn1—N5	92.44 (8)	Zn1—O2—H2WA	121 (3)
N1—Zn1—N5	76.51 (8)	Zn1—O2—H2WB	124 (3)
C5—N1—C1	117.7 (2)	H2WA—O2—H2WB	112 (4)
C5—N1—Zn1	126.3 (2)	Zn1—O3—H3WA	126 (3)
C1—N1—Zn1	115.72 (17)	Zn1—O3—H3WB	123 (3)
C6—N5—N4	105.1 (2)	H3WA—O3—H3WB	108 (4)
C6—N5—Zn1	112.54 (17)	F2—C8—F3'	118.4 (11)
N4—N5—Zn1	142.25 (17)	F3'—C8—F2'	104.6 (8)
N1—C1—C2	122.5 (3)	F2—C8—F1'	90.5 (13)
N1—C1—C6	114.1 (2)	F3'—C8—F1'	105.5 (8)
C2—C1—C6	123.4 (3)	F2'—C8—F1'	106.5 (9)
C4—C3—C2	119.0 (3)	F2—C8—F1	107.3 (8)
C4—C3—H3	120.5	F3'—C8—F1	88.9 (9)
C2—C3—H3	120.5	F2'—C8—F1	121.2 (12)
C3—C2—C1	118.7 (3)	F2—C8—F3	106.3 (8)
C3—C2—H2	120.6	F2'—C8—F3	90.2 (11)
C1—C2—H2	120.6	F1'—C8—F3	120.8 (10)
C3—C4—C5	119.1 (3)	F1—C8—F3	105.8 (6)
C3—C4—H4	120.4	F2—C8—C7	113.5 (8)
C5—C4—H4	120.4	F3'—C8—C7	112.7 (9)
N1—C5—C4	122.8 (3)	F2'—C8—C7	112.8 (8)
N1—C5—H5	118.6	F1'—C8—C7	113.9 (8)
C4—C5—H5	118.6	F1—C8—C7	113.4 (6)
C6—N2—N3	104.9 (2)	F3—C8—C7	110.1 (6)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3WB···O1W	0.81 (2)	2.03 (2)	2.788 (3)	156 (4)
O1—H1WA···O4	0.84 (2)	1.97 (2)	2.800 (3)	171 (4)
O3—H3WA···O5ⁱⁱ	0.82 (2)	1.96 (2)	2.771 (3)	174 (4)
O2—H2WB···N3ⁱⁱⁱ	0.83 (2)	2.08 (2)	2.856 (3)	156 (4)
O2—H2WA···O5^iv	0.82 (2)	1.96 (2)	2.769 (3)	175 (4)
O1—H1WB···N2ⁱⁱⁱ	0.82 (2)	2.02 (2)	2.821 (3)	165 (4)
O1W—H1W···O4^v	0.81 (2)	2.02 (2)	2.791 (3)	158 (4)

Symmetry codes: (ii) −x+1/2, y−1/2, z; (iii) −x+3/2, y+1/2, z; (iv) x+1/2, −y+1/2, −z+1; (v) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₆H₄N₅)₂(H₂O)₆](C₂F₃O₂)₂·H₂O
M_r	775.18
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	298
a, b, c (Å)	9.1750 (18), 14.722 (3), 20.657 (4)
V (Å³)	2790.3 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.83
Crystal size (mm)	0.13 × 0.10 × 0.10

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.708, 0.833
No. of measured, independent and observed [I > 2σ(I)] reflections	27226, 3197, 2470
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.089, 1.12
No. of reflections	3197
No. of parameters	253
No. of restraints	251
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.49

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3WB···O1W	0.809 (18)	2.03 (2)	2.788 (3)	156 (4)
O1—H1WA···O4	0.842 (18)	1.965 (19)	2.800 (3)	171 (4)
O3—H3WA···O5ⁱ	0.818 (18)	1.956 (19)	2.771 (3)	174 (4)
O2—H2WB···N3ⁱⁱ	0.825 (18)	2.08 (2)	2.856 (3)	156 (4)
O2—H2WA···O5ⁱⁱⁱ	0.815 (18)	1.956 (19)	2.769 (3)	175 (4)
O1—H1WB···N2ⁱⁱ	0.818 (18)	2.02 (2)	2.821 (3)	165 (4)
O1W—H1W···O4^iv	0.809 (18)	2.02 (2)	2.791 (3)	158 (4)

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x+3/2, y+1/2, z; (iii) x+1/2, −y+1/2, −z+1; (iv) −x+1, y, −z+1/2.

Acknowledgements

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

References

Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S.-P. (2007). J. Am. Chem. Soc. 129, 5346–5347. Web of Science CSD CrossRef PubMed CAS Google Scholar
Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461–3464. Web of Science CSD CrossRef CAS Google Scholar
Georgiev, I. G. & MacGillivray, L. R. (2007). Chem. Soc. Rev. 36, 1239–1248. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, H., Qu, Z.-R., Ye, H.-Y. & Xiong, R.-G. (2008). Chem. Soc. Rev. 37, 84–100. Web of Science CrossRef PubMed Google Scholar

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