Bis[μ-5-(2-pyrid-yl)tetra-zolato]-κN,N:N;κN:N,N-bis-[triaqua-zinc(II)] bis-(trifluoro-acetate) monohydrate.

The title compound, [Zn(2)(C(6)H(4)N(5))(2)(H(2)O)(6)](CF(3)CO(2))(2)·H(2)O, was synthesized by hydro-thermal reaction of ZnBr(2), CF(3)COOH and 2-(2H-tetra-zol-5-yl)pyridine. The Zn(II) cation is coordinated by one N atom from the 5-(2-pyrid-yl)tetra-zolate anion, two N atoms from another 5-(2-pyrid-yl)tetra-zolate anion and three O atoms from three water mol-ecules in a distorted octa-hedral geometry. The tetra-zole ligands bridge the metal ions of the dimeric structure, and the dimers are located on crystallographic inversion centers. An inter-stitial solvent water mol-ecule is located on a crystallographic mirror plane, and the CF(3)COO(-) 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, carboxyl-ate O atoms and tetra-zole N atoms. The inter-actions link the mol-ecules 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 = 775.18

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.089

S = 1.12

3197 reflections

253 parameters

251 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.49 e Å−3

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn2(C6H4N5)2(H2O)6](C2F3O2)2·H2O	F(000) = 1560
Mr = 775.18	Dx = 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

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

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(Fo2) + (0.0331P)2 + 2.0898P] where P = (Fo2 + 2Fc2)/3
3197 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.35 e Å−3
251 restraints	Δρmin = −0.49 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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···O5iv	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···O4v	0.81 (2)	2.02 (2)	2.791 (3)	158 (4)

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⋯O4iv	0.809 (18)	2.02 (2)	2.791 (3)	158 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .