metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Poly[bis­­[μ3-2-(1H-tetra­zol-1-yl)acetato]cadmium(II)]

aCollege of Sciences, Henan Agricultural University, Zhengzhou, Henan 450002, People's Republic of China
*Correspondence e-mail: toxielix@163.com

(Received 12 October 2009; accepted 16 October 2009; online 23 October 2009)

In the title compound, [Cd(C3H3N4O2)2]n, the CdII ion, located on a twofold rotation axis, is six-coordinated by two N atoms [Cd—N = 2.368 (2) Å] and four O atoms [Cd—O = 2.300 (1) and 2.260 (1) Å] from six 2-(1H-tetra­zol-1-yl)acetate (L) ligands in a distorted octa­hedral geometry. The metal centres are connected via the tridentate L ligands into a three-dimensional polymeric structure.

Related literature

For related structures, see: Du et al. (2007[Du, M., Zhang, Z. H., Tang, L. F., Wang, X. G., Zhao, X. J. & Batten, S. R. (2007). Chem. Eur. J. 13, 2578-2586.]); Lee et al. (2005[Lee, E. Y., Jang, S. Y. & Suh, M. P. (2005). J. Am. Chem. Soc. 127, 6374-6381.]); Won et al. (2007[Won, T. J., Clegg, J. K., Lindoy, L. F. & McMurtrie, J. C. (2007). Cryst. Growth Des. 7, 972-979.]); Yang et al. (2009[Yang, H. Y., Li, L. K., Wu, J., Hou, H. W., Xiao, B. & Fan, Y. T. (2009). Chem. Eur. J. 15, 4049-4056.]).

[Scheme 1]

Experimental

Crystal data
  • [Cd(C3H3N4O2)2]

  • Mr = 366.60

  • Monoclinic, C 2/c

  • a = 14.750 (3) Å

  • b = 8.857 (2) Å

  • c = 9.503 (2) Å

  • β = 118.42 (3)°

  • V = 1091.8 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.03 mm−1

  • T = 293 K

  • 0.20 × 0.20 × 0.20 mm

Data collection
  • Rigaku Mercury CCD diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2000[Rigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.666, Tmax = 0.673

  • 6805 measured reflections

  • 1452 independent reflections

  • 1441 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.017

  • wR(F2) = 0.049

  • S = 0.94

  • 1452 reflections

  • 87 parameters

  • H-atom parameters constrained

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.44 e Å−3

Data collection: CrystalClear (Rigaku, 2000[Rigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Multidentate ligands containing rich coordination sites (N and/or O donors) are often employed to produce polymeric networks with structural diversity owing to their various coordination modes (Won et al., 2007; Lee et al., 2005; Du et al., 2007). As ligands with multiple coordination site, tetrazole and its derivatives have been shown to be good organic linker in generation of structurally versatile metal-organic frameworks since it can bridge different metal centers to afford coordination polymers that exhibit extraordinary structural diversity and facile accessibility of functionalized materials (Yang et al., 2009). Here, we report the synthesis and crystal structure of the title compound, (I).

In (I) (Fig. 1), each CdII ion located on a twofold rotation axis is six–coordinated by two tetrazole nitrogen atoms (N4) and four carboxylate group oxygen atoms (O1 and O2) from six distinct ligands. The coordination bond lengths Cd—N and Cd—O are 2.368 (2), 2.300 (1) Å and 2.260 (1) Å, respectively. The coordination geometry around CdII can be described as a distorted octahedron - the CdII coordination angles are in the range 83.34 (6)° - 177.16 (7)°. Each fully deprotonated L ligand serves as a tridentate bridging ligand via one nitrogen atom at the 5-position of the tetrazole ring while the nitrogen atoms at 3,4-positions remain uncoordinated, and two carboxylate O atoms. In this way two metal atoms and two carboxylate form a 8-membered [M2C2O4] metallocyclic ring, the Cd···Cd distance is 4.793 Å. The Cd···Cd distance linked by the bridged L ligand is 8.603 Å. Thus each CdII centers are linked together by six L ligands into a three–dimensional polymeric structure (Fig. 2).

Related literature top

For related structures, see: Du et al. (2007); Lee et al. (2005); Won et al. (2007); Yang et al. (2009).

Experimental top

All solvents and chemicals were of analytical grade and were used without further purification. The compound [CdL2]n was synthesized as follows: 2-(1H–tetrazol–1–yl) acetic acid (1.0 mmol) was added to 5 cm3 water and the resulting solution was adjusted pH to 7.0 by NaOH aqueous. Then Cd(NO3)2(0.5 mmol) was added to the above solution, and the mixture was stirred for 30 min and filtered. After two days, colourless single crystals suitable for X-ray analysis were obtained. Anal. Calcd (%) for C6H6CdN8O4: C, 19.66; H, 1.65; N, 30.57. Found (%): C, 19.79; H, 1.45; N, 30.46.

Refinement top

The H atoms were included in calculated positions and treated as riding atoms: C–H = 0.93 Å for the tetrazole and 0.97 Å for the methylene H atoms, with Uiso(H) = 1.2Ueq(C).

Structure description top

Multidentate ligands containing rich coordination sites (N and/or O donors) are often employed to produce polymeric networks with structural diversity owing to their various coordination modes (Won et al., 2007; Lee et al., 2005; Du et al., 2007). As ligands with multiple coordination site, tetrazole and its derivatives have been shown to be good organic linker in generation of structurally versatile metal-organic frameworks since it can bridge different metal centers to afford coordination polymers that exhibit extraordinary structural diversity and facile accessibility of functionalized materials (Yang et al., 2009). Here, we report the synthesis and crystal structure of the title compound, (I).

In (I) (Fig. 1), each CdII ion located on a twofold rotation axis is six–coordinated by two tetrazole nitrogen atoms (N4) and four carboxylate group oxygen atoms (O1 and O2) from six distinct ligands. The coordination bond lengths Cd—N and Cd—O are 2.368 (2), 2.300 (1) Å and 2.260 (1) Å, respectively. The coordination geometry around CdII can be described as a distorted octahedron - the CdII coordination angles are in the range 83.34 (6)° - 177.16 (7)°. Each fully deprotonated L ligand serves as a tridentate bridging ligand via one nitrogen atom at the 5-position of the tetrazole ring while the nitrogen atoms at 3,4-positions remain uncoordinated, and two carboxylate O atoms. In this way two metal atoms and two carboxylate form a 8-membered [M2C2O4] metallocyclic ring, the Cd···Cd distance is 4.793 Å. The Cd···Cd distance linked by the bridged L ligand is 8.603 Å. Thus each CdII centers are linked together by six L ligands into a three–dimensional polymeric structure (Fig. 2).

For related structures, see: Du et al. (2007); Lee et al. (2005); Won et al. (2007); Yang et al. (2009).

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); 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. A portion of the crystal structure of (I) showing 30% probability displacement ellipsoids and the atomic labeling [symmetry codes: (i) - x, y, - z + 1/2; (ii) - x, - y + 1, - z; (iii) x, - y + 1, z + 1/2; (iv) x - 1/2, y + 1/2, z; (v) - x + 1/2, y + 1/2, - z + 1/2].
[Figure 2] Fig. 2. The crystal packing viewed along the b axis. H atoms omitted for clarity.
Poly[bis[µ3-2-(1H-tetrazol-1-yl)acetato]cadmium(II)] top
Crystal data top
[Cd(C3H3N4O2)2]F(000) = 712
Mr = 366.60Dx = 2.230 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2016 reflections
a = 14.750 (3) Åθ = 2.4–29.1°
b = 8.857 (2) ŵ = 2.03 mm1
c = 9.503 (2) ÅT = 293 K
β = 118.42 (3)°Prism, colourless
V = 1091.8 (4) Å30.20 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku Mercury CCD
diffractometer
1452 independent reflections
Radiation source: fine-focus sealed tube1441 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω scansθmax = 29.1°, θmin = 3.2°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)
h = 2019
Tmin = 0.666, Tmax = 0.673k = 1212
6805 measured reflectionsl = 1312
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.017Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.049H-atom parameters constrained
S = 0.94 w = 1/[σ2(Fo2) + (0.0394P)2 + 0.8P]
where P = (Fo2 + 2Fc2)/3
1452 reflections(Δ/σ)max = 0.001
87 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
[Cd(C3H3N4O2)2]V = 1091.8 (4) Å3
Mr = 366.60Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.750 (3) ŵ = 2.03 mm1
b = 8.857 (2) ÅT = 293 K
c = 9.503 (2) Å0.20 × 0.20 × 0.20 mm
β = 118.42 (3)°
Data collection top
Rigaku Mercury CCD
diffractometer
1452 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)
1441 reflections with I > 2σ(I)
Tmin = 0.666, Tmax = 0.673Rint = 0.025
6805 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0170 restraints
wR(F2) = 0.049H-atom parameters constrained
S = 0.94Δρmax = 0.38 e Å3
1452 reflectionsΔρmin = 0.44 e Å3
87 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
Cd10.00000.535583 (15)0.25000.01857 (7)
O10.03228 (9)0.34712 (15)0.06557 (14)0.0254 (2)
O20.05506 (13)0.28052 (17)0.06267 (17)0.0377 (3)
N30.25046 (14)0.05131 (19)0.0670 (2)0.0335 (4)
N40.32460 (13)0.02896 (15)0.1891 (2)0.0257 (3)
C30.27659 (12)0.1113 (2)0.24775 (19)0.0260 (3)
H3A0.30770.17810.33320.031*
N10.17630 (10)0.08377 (16)0.16511 (16)0.0205 (2)
C10.03356 (12)0.27150 (17)0.04894 (17)0.0208 (3)
C20.09014 (12)0.15137 (19)0.17684 (18)0.0222 (3)
H2A0.11550.19690.28170.027*
H2B0.04180.07260.16690.027*
N20.16106 (13)0.01883 (19)0.0519 (2)0.0329 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.01602 (10)0.02182 (10)0.01872 (10)0.0000.00896 (7)0.000
O10.0187 (5)0.0290 (6)0.0235 (5)0.0055 (4)0.0058 (4)0.0047 (4)
O20.0526 (9)0.0394 (7)0.0324 (7)0.0211 (6)0.0295 (7)0.0158 (6)
N30.0222 (8)0.0369 (8)0.0392 (9)0.0018 (6)0.0127 (7)0.0138 (6)
N40.0177 (7)0.0329 (8)0.0255 (7)0.0025 (5)0.0093 (6)0.0021 (5)
C30.0172 (7)0.0354 (8)0.0217 (7)0.0015 (6)0.0064 (6)0.0056 (6)
N10.0168 (6)0.0234 (6)0.0203 (6)0.0022 (5)0.0081 (5)0.0005 (5)
C10.0198 (7)0.0219 (6)0.0182 (6)0.0018 (5)0.0070 (5)0.0005 (5)
C20.0178 (6)0.0298 (7)0.0212 (7)0.0061 (5)0.0111 (5)0.0048 (6)
N20.0222 (8)0.0339 (8)0.0397 (10)0.0015 (6)0.0124 (7)0.0153 (7)
Geometric parameters (Å, º) top
Cd1—O2i2.2595 (14)N3—N41.356 (2)
Cd1—O2ii2.2595 (14)N4—C31.311 (2)
Cd1—O12.3000 (13)N4—Cd1vi2.3678 (17)
Cd1—O1iii2.3000 (13)C3—N11.326 (2)
Cd1—N4iv2.3678 (17)C3—H3A0.9300
Cd1—N4v2.3678 (17)N1—N21.343 (2)
O1—C11.2502 (19)N1—C21.4564 (19)
O2—C11.246 (2)C1—C21.530 (2)
O2—Cd1ii2.2595 (14)C2—H2A0.9700
N3—N21.289 (2)C2—H2B0.9700
O2i—Cd1—O2ii87.75 (8)C3—N4—Cd1vi129.09 (12)
O2i—Cd1—O1171.86 (5)N3—N4—Cd1vi124.37 (12)
O2ii—Cd1—O193.23 (6)N4—C3—N1108.77 (15)
O2i—Cd1—O1iii93.23 (6)N4—C3—H3A125.6
O2ii—Cd1—O1iii171.86 (5)N1—C3—H3A125.6
O1—Cd1—O1iii86.94 (7)C3—N1—N2108.25 (14)
O2i—Cd1—N4iv98.72 (6)C3—N1—C2130.32 (14)
O2ii—Cd1—N4iv83.34 (6)N2—N1—C2121.34 (14)
O1—Cd1—N4iv89.42 (5)O2—C1—O1126.95 (15)
O1iii—Cd1—N4iv88.52 (5)O2—C1—C2117.22 (14)
O2i—Cd1—N4v83.34 (6)O1—C1—C2115.79 (13)
O2ii—Cd1—N4v98.72 (6)N1—C2—C1113.02 (12)
O1—Cd1—N4v88.52 (5)N1—C2—H2A109.0
O1iii—Cd1—N4v89.42 (5)C1—C2—H2A109.0
N4iv—Cd1—N4v177.16 (7)N1—C2—H2B109.0
C1—O1—Cd1126.41 (11)C1—C2—H2B109.0
C1—O2—Cd1ii125.12 (11)H2A—C2—H2B107.8
N2—N3—N4110.14 (16)N3—N2—N1106.81 (15)
C3—N4—N3106.04 (15)
O2i—Cd1—O1—C112.4 (4)Cd1ii—O2—C1—O110.9 (3)
O2ii—Cd1—O1—C1109.08 (14)Cd1ii—O2—C1—C2171.73 (11)
O1iii—Cd1—O1—C179.07 (13)Cd1—O1—C1—O2108.22 (18)
N4iv—Cd1—O1—C1167.62 (14)Cd1—O1—C1—C274.34 (18)
N4v—Cd1—O1—C110.43 (14)C3—N1—C2—C1100.0 (2)
N2—N3—N4—C30.1 (2)N2—N1—C2—C176.1 (2)
N2—N3—N4—Cd1vi172.37 (14)O2—C1—C2—N111.3 (2)
N3—N4—C3—N10.2 (2)O1—C1—C2—N1171.02 (14)
Cd1vi—N4—C3—N1171.87 (11)N4—N3—N2—N10.1 (2)
N4—C3—N1—N20.1 (2)C3—N1—N2—N30.0 (2)
N4—C3—N1—C2176.36 (15)C2—N1—N2—N3176.83 (16)
Symmetry codes: (i) x, y+1, z+1/2; (ii) x, y+1, z; (iii) x, y, z+1/2; (iv) x1/2, y+1/2, z; (v) x+1/2, y+1/2, z+1/2; (vi) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formula[Cd(C3H3N4O2)2]
Mr366.60
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)14.750 (3), 8.857 (2), 9.503 (2)
β (°) 118.42 (3)
V3)1091.8 (4)
Z4
Radiation typeMo Kα
µ (mm1)2.03
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku Mercury CCD
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2000)
Tmin, Tmax0.666, 0.673
No. of measured, independent and
observed [I > 2σ(I)] reflections
6805, 1452, 1441
Rint0.025
(sin θ/λ)max1)0.685
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.017, 0.049, 0.94
No. of reflections1452
No. of parameters87
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.44

Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

This work was sponsored by the start-up fund of Henan Agricultural University (grant No. 30700061).

References

First citationDu, M., Zhang, Z. H., Tang, L. F., Wang, X. G., Zhao, X. J. & Batten, S. R. (2007). Chem. Eur. J. 13, 2578–2586.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationLee, E. Y., Jang, S. Y. & Suh, M. P. (2005). J. Am. Chem. Soc. 127, 6374–6381.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationRigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWon, T. J., Clegg, J. K., Lindoy, L. F. & McMurtrie, J. C. (2007). Cryst. Growth Des. 7, 972–979.  Web of Science CSD CrossRef CAS Google Scholar
First citationYang, H. Y., Li, L. K., Wu, J., Hou, H. W., Xiao, B. & Fan, Y. T. (2009). Chem. Eur. J. 15, 4049–4056.  Web of Science CrossRef PubMed CAS Google Scholar

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ISSN: 2056-9890
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