Triaqua­(5-methyl-1H-tetra­zolato-κN¹)zinc(II) perchlorate

The title compound, [Zn(C₂H₃N₄)(H₂O)₃]ClO₄, consists of one Zn^II complex cation and one uncoordinated perchlorate anion. Both anion and cation lie on mirror planes. The Zn^II ion displays a distorted tetra­hedral geometry and is coordinated by three O atoms and one N atom. Classical O—H...O and O—H...N hydrogen-bond inter­actions connect cations and anions to form a one-dimensional chain along [010].

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.049
• wR factor = 0.114
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

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Alert level C
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C2

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.72

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 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
   1 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

The tetrazole functional group has found a wide range of applications as ligand in coordination chemistry, in medicinal chemistry as a metabolically stable surrogate for a carboxylic acid group, and in material sciences as high density energy materials (Carlucci et al., 1999; Demko & Sharpless, 2001). Recently, we have successfully trapped and structurally characterized many intermediates in which organic part contains one or two cyano groups, affording mono-tetrazolyl or bi-tetrazolyl organic ligands (Xiong et al., 2002). Herein, we report the crystal structure of a simple tetrazole coordination compound, (I), synthesized in-situ by hydrothermal method.

The crystal structure shows that the title compound presents a novel structure consisting of two distinct units: the coordination Zn^II complex cation and the perchlorate anion, both lying on a mirror plane. For the cation, atoms in special positions are C1/C2/N1/N2/N3/N4/Zn1/O2, while O1 is in general position. The Zn^II ion is in a distorted tetrahedral geometry and is coordinated to three O atoms from water molecules and one N atom from the tetrazolate ring (Fig.1). It should be noted that there are classical O—H···O and O—H···N hydrogen bond interactions in the crystal structure (Table 1, Fig. 2). Owning to the intermolecular hydrogen bonding interactions, the cations and the anions are linked into a one-dimensional (one-dimensional) backbone chain along [010] axis (Fig, 3). Finally, adjacent chains are further extended into a three-dimensional (three-dimensional) network structure through weak contacts.

Related literature

For related literature, see: Carlucci et al. (1999); Demko & Sharpless (2001); Xiong et al. (2002).

S2. Experimental

The hydrothermal treatment of acetonitrile (8.2 mg, 0.2 mmol), Zn(ClO₄)₂ (26.4 mg, 0.1 mmol), and NaN₃ (32.5 mg, 0.5 mmol) in water (2 ml) for 1 day at 1473 K afforded colourless crystals of the title complex.

S3. Refinement

H atoms bonded to O atoms were located in a difference map and refined with free coordinates and U_iso(H) = 1.2U_eq(carrier O). The methyl H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C2).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (i) x, -1/2 - y, z; (ii) x, 1/2 - y, z.
	Fig. 2. View of the hydrogen bond interactions in the crystal structure. Symmetry codes: (iii) x + 1, y - 1, z; (iv) x + 1, y, z; (v) x, y - 1, z.
	Fig. 3. View of the one-dimensional helix chain along axis [010].

Triaqua(5-methyl-1H-tetrazolato-κN¹)zinc(II) perchlorate

Crystal data

[Zn(C2H3N4)(H2O)3]ClO4	F(000) = 304
Mr = 301.95	Dx = 1.880 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 746 reflections
a = 6.1055 (5) Å	θ = 2.1–23.6°
b = 7.6413 (6) Å	µ = 2.58 mm^−1
c = 11.6547 (9) Å	T = 291 K
β = 101.220 (2)°	Block, colourless
V = 533.35 (7) Å^3	0.18 × 0.14 × 0.12 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer	1133 independent reflections
Radiation source: sealed tube	1034 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
φ and ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→7
Tmin = 0.66, Tmax = 0.73	k = −9→9
3060 measured reflections	l = −14→10

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 0.88P] where P = (Fo^2 + 2Fc^2)/3
1133 reflections	(Δ/σ)max < 0.001
94 parameters	Δρmax = 0.70 e Å^−3
0 restraints	Δρmin = −0.61 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.4977 (10)	0.2500	0.5068 (6)	0.0331 (13)
C2	0.7244 (10)	0.2500	0.5742 (5)	0.0360 (15)
H2A	0.8278	0.2500	0.5218	0.054*
H2B	0.7477	0.3526	0.6227	0.054*
Cl1	0.2413 (2)	0.7500	0.08687 (14)	0.0362 (4)
N1	0.4385 (9)	0.2500	0.3991 (5)	0.0353 (12)
N2	0.2200 (8)	0.2500	0.3701 (4)	0.0345 (12)
N3	0.1563 (9)	0.2500	0.4728 (5)	0.0404 (14)
N4	0.3248 (9)	0.2500	0.5603 (4)	0.0334 (12)
O1	0.7816 (6)	0.0291 (5)	0.2642 (4)	0.0466 (9)
H1B	0.840 (10)	0.025 (9)	0.203 (6)	0.056*
H1A	0.885 (10)	0.032 (9)	0.325 (5)	0.056*
O2	0.3480 (8)	0.2500	0.1219 (4)	0.0449 (12)
H2C	0.291 (9)	0.152 (9)	0.091 (5)	0.054*
O3	0.1365 (6)	0.8932 (5)	0.1446 (3)	0.0489 (9)
O4	0.4596 (8)	0.7500	0.1194 (4)	0.0454 (12)
O5	0.1834 (8)	0.7500	−0.0279 (5)	0.0467 (12)
Zn1	0.59689 (11)	0.2500	0.25880 (6)	0.0268 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.024 (3)	0.041 (4)	0.034 (3)	0.000	0.005 (2)	0.000
C2	0.035 (3)	0.048 (4)	0.022 (3)	0.000	−0.004 (2)	0.000
Cl1	0.0311 (7)	0.0386 (9)	0.0352 (8)	0.000	−0.0024 (6)	0.000
N1	0.041 (3)	0.039 (3)	0.027 (3)	0.000	0.011 (2)	0.000
N2	0.029 (2)	0.050 (3)	0.022 (2)	0.000	0.000 (2)	0.000
N3	0.034 (3)	0.054 (4)	0.038 (3)	0.000	0.019 (2)	0.000
N4	0.032 (3)	0.045 (3)	0.024 (2)	0.000	0.007 (2)	0.000
O1	0.0413 (19)	0.042 (2)	0.058 (2)	0.0146 (16)	0.0145 (16)	−0.0136 (18)
O2	0.031 (2)	0.068 (4)	0.034 (3)	0.000	0.002 (2)	0.000
O3	0.053 (2)	0.049 (2)	0.051 (2)	−0.0228 (17)	0.0246 (17)	−0.0069 (17)
O4	0.052 (3)	0.042 (3)	0.047 (3)	0.000	0.022 (2)	0.000
O5	0.043 (3)	0.052 (3)	0.045 (3)	0.000	0.007 (2)	0.000
Zn1	0.0265 (4)	0.0311 (4)	0.0236 (4)	0.000	0.0071 (2)	0.000

Geometric parameters (Å, º)

C1—N1	1.237 (8)	N1—Zn1	2.055 (5)
C1—N4	1.326 (8)	N2—N3	1.330 (8)
C1—C2	1.453 (8)	N3—N4	1.300 (8)
C2—H2A	0.9600	O1—Zn1	2.024 (3)
C2—H2B	0.9600	O1—H1B	0.86 (7)
Cl1—O4	1.313 (5)	O1—H1A	0.85 (6)
Cl1—O5	1.315 (5)	O2—Zn1	1.977 (5)
Cl1—O3	1.493 (4)	O2—H2C	0.87 (6)
Cl1—O3^i	1.493 (4)	Zn1—O1^ii	2.024 (3)
N1—N2	1.311 (7)
N1—C1—N4	112.0 (6)	N2—N1—Zn1	114.1 (4)
N1—C1—C2	127.5 (6)	N1—N2—N3	103.2 (5)
N4—C1—C2	120.5 (6)	N4—N3—N2	112.4 (5)
C1—C2—H2A	109.3	N3—N4—C1	102.3 (5)
C1—C2—H2B	109.5	Zn1—O1—H1B	109 (5)
H2A—C2—H2B	109.5	Zn1—O1—H1A	109 (5)
O4—Cl1—O5	110.5 (3)	H1B—O1—H1A	109 (6)
O4—Cl1—O3	111.7 (2)	Zn1—O2—H2C	121 (4)
O5—Cl1—O3	113.9 (2)	O2—Zn1—O1^ii	111.18 (13)
O4—Cl1—O3^i	111.7 (2)	O2—Zn1—O1	111.18 (13)
O5—Cl1—O3^i	113.9 (2)	O1^ii—Zn1—O1	113.0 (2)
O3—Cl1—O3^i	94.3 (3)	O2—Zn1—N1	103.6 (2)
C1—N1—N2	110.1 (5)	O1^ii—Zn1—N1	108.70 (14)
C1—N1—Zn1	135.9 (5)	O1—Zn1—N1	108.70 (14)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2C···O3^iii	0.87 (6)	2.33 (6)	3.050 (4)	140 (5)
O1—H1A···N2^iv	0.85 (6)	2.61 (6)	3.202 (6)	127 (5)
O1—H1B···O3^v	0.86 (7)	2.29 (7)	2.982 (5)	138 (5)

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