Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029297/bh2109sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029297/bh2109Isup2.hkl |
CCDC reference: 654795
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.009 Å
- R factor = 0.049
- wR factor = 0.114
- Data-to-parameter ratio = 12.1
checkCIF/PLATON results
No syntax errors found
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
For related literature, see: Carlucci et al. (1999); Demko & Sharpless (2001); Xiong et al. (2002).
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.
H atoms bonded to O atoms were located in a difference map and refined with free coordinates and Uiso(H) = 1.2Ueq(carrier O). The methyl H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C2).
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 ZnII 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 ZnII 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.
For related literature, see: Carlucci et al. (1999); Demko & Sharpless (2001); Xiong et al. (2002).
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.
[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) Å3 | 0.18 × 0.14 × 0.12 mm |
Z = 2 |
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 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.88P] where P = (Fo2 + 2Fc2)/3 |
1133 reflections | (Δ/σ)max < 0.001 |
94 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Zn(C2H3N4)(H2O)3]ClO4 | V = 533.35 (7) Å3 |
Mr = 301.95 | Z = 2 |
Monoclinic, P21/m | Mo Kα radiation |
a = 6.1055 (5) Å | µ = 2.58 mm−1 |
b = 7.6413 (6) Å | T = 291 K |
c = 11.6547 (9) Å | 0.18 × 0.14 × 0.12 mm |
β = 101.220 (2)° |
Bruker SMART APEX CCD diffractometer | 1133 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1034 reflections with I > 2σ(I) |
Tmin = 0.66, Tmax = 0.73 | Rint = 0.035 |
3060 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.70 e Å−3 |
1133 reflections | Δρmin = −0.61 e Å−3 |
94 parameters |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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 |
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—O3i | 1.493 (4) | Zn1—O1ii | 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—O1ii | 111.18 (13) |
O4—Cl1—O3i | 111.7 (2) | O2—Zn1—O1 | 111.18 (13) |
O5—Cl1—O3i | 113.9 (2) | O1ii—Zn1—O1 | 113.0 (2) |
O3—Cl1—O3i | 94.3 (3) | O2—Zn1—N1 | 103.6 (2) |
C1—N1—N2 | 110.1 (5) | O1ii—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2C···O3iii | 0.87 (6) | 2.33 (6) | 3.050 (4) | 140 (5) |
O1—H1A···N2iv | 0.85 (6) | 2.61 (6) | 3.202 (6) | 127 (5) |
O1—H1B···O3v | 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. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2H3N4)(H2O)3]ClO4 |
Mr | 301.95 |
Crystal system, space group | Monoclinic, P21/m |
Temperature (K) | 291 |
a, b, c (Å) | 6.1055 (5), 7.6413 (6), 11.6547 (9) |
β (°) | 101.220 (2) |
V (Å3) | 533.35 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.58 |
Crystal size (mm) | 0.18 × 0.14 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.66, 0.73 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3060, 1133, 1034 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.114, 1.10 |
No. of reflections | 1133 |
No. of parameters | 94 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.70, −0.61 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2C···O3i | 0.87 (6) | 2.33 (6) | 3.050 (4) | 140 (5) |
O1—H1A···N2ii | 0.85 (6) | 2.61 (6) | 3.202 (6) | 127 (5) |
O1—H1B···O3iii | 0.86 (7) | 2.29 (7) | 2.982 (5) | 138 (5) |
Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) x+1, y−1, z. |
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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 ZnII 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 ZnII 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.