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

Xie, L.-X.; Zheng, X.-F.; Su, H.; Jin, Q.

doi:10.1107/S160053680904255X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1414

https://doi.org/10.1107/S160053680904255X

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

Li-Xia Xie,^a ^* Xian-Fu Zheng,^a Hui Su ^a and Qiu Jin ^a

^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 Cd^II 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 ); Lee et al. (2005 ); Won et al. (2007 ); Yang et al. (2009 ).

Experimental

Crystal data

[Cd(C₃H₃N₄O₂)₂]
M_r = 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 ) T_min = 0.666, T_max = 0.673
6805 measured reflections
1452 independent reflections
1441 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.049
S = 0.94
1452 reflections
87 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: CrystalClear (Rigaku, 2000); 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 global, I. DOI: https://doi.org/10.1107/S160053680904255X/cv2629sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680904255X/cv2629Isup2.hkl

checkCIF report

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 Cd^II 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 Cd^II can be described as a distorted octahedron - the Cd^II 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 Cd^II 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.

Structure description top

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

	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].
	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
M_r = 366.60	D_x = 2.230 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2016 reflections
a = 14.750 (3) Å	θ = 2.4–29.1°
b = 8.857 (2) Å	µ = 2.03 mm⁻¹
c = 9.503 (2) Å	T = 293 K
β = 118.42 (3)°	Prism, colourless
V = 1091.8 (4) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	1452 independent reflections
Radiation source: fine-focus sealed tube	1441 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 29.1°, θ_min = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	h = −20→19
T_min = 0.666, T_max = 0.673	k = −12→12
6805 measured reflections	l = −13→12

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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.049	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0394P)² + 0.8P] where P = (F_o² + 2F_c²)/3
1452 reflections	(Δ/σ)_max = 0.001
87 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Cd(C₃H₃N₄O₂)₂]	V = 1091.8 (4) Å³
M_r = 366.60	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.750 (3) Å	µ = 2.03 mm⁻¹
b = 8.857 (2) Å	T = 293 K
c = 9.503 (2) Å	0.20 × 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)
T_min = 0.666, T_max = 0.673	R_int = 0.025
6805 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.049	H-atom parameters constrained
S = 0.94	Δρ_max = 0.38 e Å⁻³
1452 reflections	Δρ_min = −0.44 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cd1	0.0000	0.535583 (15)	0.2500	0.01857 (7)
O1	−0.03228 (9)	0.34712 (15)	0.06557 (14)	0.0254 (2)
O2	0.05506 (13)	0.28052 (17)	−0.06267 (17)	0.0377 (3)
N3	0.25046 (14)	−0.05131 (19)	0.0670 (2)	0.0335 (4)
N4	0.32460 (13)	0.02896 (15)	0.1891 (2)	0.0257 (3)
C3	0.27659 (12)	0.1113 (2)	0.24775 (19)	0.0260 (3)
H3A	0.3077	0.1781	0.3332	0.031*
N1	0.17630 (10)	0.08377 (16)	0.16511 (16)	0.0205 (2)
C1	0.03356 (12)	0.27150 (17)	0.04894 (17)	0.0208 (3)
C2	0.09014 (12)	0.15137 (19)	0.17684 (18)	0.0222 (3)
H2A	0.1155	0.1969	0.2817	0.027*
H2B	0.0418	0.0726	0.1669	0.027*
N2	0.16106 (13)	−0.01883 (19)	0.0519 (2)	0.0329 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01602 (10)	0.02182 (10)	0.01872 (10)	0.000	0.00896 (7)	0.000
O1	0.0187 (5)	0.0290 (6)	0.0235 (5)	0.0055 (4)	0.0058 (4)	−0.0047 (4)
O2	0.0526 (9)	0.0394 (7)	0.0324 (7)	0.0211 (6)	0.0295 (7)	0.0158 (6)
N3	0.0222 (8)	0.0369 (8)	0.0392 (9)	0.0018 (6)	0.0127 (7)	−0.0138 (6)
N4	0.0177 (7)	0.0329 (8)	0.0255 (7)	0.0025 (5)	0.0093 (6)	−0.0021 (5)
C3	0.0172 (7)	0.0354 (8)	0.0217 (7)	0.0015 (6)	0.0064 (6)	−0.0056 (6)
N1	0.0168 (6)	0.0234 (6)	0.0203 (6)	0.0022 (5)	0.0081 (5)	−0.0005 (5)
C1	0.0198 (7)	0.0219 (6)	0.0182 (6)	0.0018 (5)	0.0070 (5)	−0.0005 (5)
C2	0.0178 (6)	0.0298 (7)	0.0212 (7)	0.0061 (5)	0.0111 (5)	0.0048 (6)
N2	0.0222 (8)	0.0339 (8)	0.0397 (10)	−0.0015 (6)	0.0124 (7)	−0.0153 (7)

Geometric parameters (Å, º) top

Cd1—O2ⁱ	2.2595 (14)	N3—N4	1.356 (2)
Cd1—O2ⁱⁱ	2.2595 (14)	N4—C3	1.311 (2)
Cd1—O1	2.3000 (13)	N4—Cd1^vi	2.3678 (17)
Cd1—O1ⁱⁱⁱ	2.3000 (13)	C3—N1	1.326 (2)
Cd1—N4^iv	2.3678 (17)	C3—H3A	0.9300
Cd1—N4^v	2.3678 (17)	N1—N2	1.343 (2)
O1—C1	1.2502 (19)	N1—C2	1.4564 (19)
O2—C1	1.246 (2)	C1—C2	1.530 (2)
O2—Cd1ⁱⁱ	2.2595 (14)	C2—H2A	0.9700
N3—N2	1.289 (2)	C2—H2B	0.9700

O2ⁱ—Cd1—O2ⁱⁱ	87.75 (8)	C3—N4—Cd1^vi	129.09 (12)
O2ⁱ—Cd1—O1	171.86 (5)	N3—N4—Cd1^vi	124.37 (12)
O2ⁱⁱ—Cd1—O1	93.23 (6)	N4—C3—N1	108.77 (15)
O2ⁱ—Cd1—O1ⁱⁱⁱ	93.23 (6)	N4—C3—H3A	125.6
O2ⁱⁱ—Cd1—O1ⁱⁱⁱ	171.86 (5)	N1—C3—H3A	125.6
O1—Cd1—O1ⁱⁱⁱ	86.94 (7)	C3—N1—N2	108.25 (14)
O2ⁱ—Cd1—N4^iv	98.72 (6)	C3—N1—C2	130.32 (14)
O2ⁱⁱ—Cd1—N4^iv	83.34 (6)	N2—N1—C2	121.34 (14)
O1—Cd1—N4^iv	89.42 (5)	O2—C1—O1	126.95 (15)
O1ⁱⁱⁱ—Cd1—N4^iv	88.52 (5)	O2—C1—C2	117.22 (14)
O2ⁱ—Cd1—N4^v	83.34 (6)	O1—C1—C2	115.79 (13)
O2ⁱⁱ—Cd1—N4^v	98.72 (6)	N1—C2—C1	113.02 (12)
O1—Cd1—N4^v	88.52 (5)	N1—C2—H2A	109.0
O1ⁱⁱⁱ—Cd1—N4^v	89.42 (5)	C1—C2—H2A	109.0
N4^iv—Cd1—N4^v	177.16 (7)	N1—C2—H2B	109.0
C1—O1—Cd1	126.41 (11)	C1—C2—H2B	109.0
C1—O2—Cd1ⁱⁱ	125.12 (11)	H2A—C2—H2B	107.8
N2—N3—N4	110.14 (16)	N3—N2—N1	106.81 (15)
C3—N4—N3	106.04 (15)

O2ⁱ—Cd1—O1—C1	12.4 (4)	Cd1ⁱⁱ—O2—C1—O1	10.9 (3)
O2ⁱⁱ—Cd1—O1—C1	109.08 (14)	Cd1ⁱⁱ—O2—C1—C2	−171.73 (11)
O1ⁱⁱⁱ—Cd1—O1—C1	−79.07 (13)	Cd1—O1—C1—O2	−108.22 (18)
N4^iv—Cd1—O1—C1	−167.62 (14)	Cd1—O1—C1—C2	74.34 (18)
N4^v—Cd1—O1—C1	10.43 (14)	C3—N1—C2—C1	100.0 (2)
N2—N3—N4—C3	0.1 (2)	N2—N1—C2—C1	−76.1 (2)
N2—N3—N4—Cd1^vi	−172.37 (14)	O2—C1—C2—N1	11.3 (2)
N3—N4—C3—N1	−0.2 (2)	O1—C1—C2—N1	−171.02 (14)
Cd1^vi—N4—C3—N1	171.87 (11)	N4—N3—N2—N1	−0.1 (2)
N4—C3—N1—N2	0.1 (2)	C3—N1—N2—N3	0.0 (2)
N4—C3—N1—C2	−176.36 (15)	C2—N1—N2—N3	176.83 (16)

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

Experimental details

Crystal data
Chemical formula	[Cd(C₃H₃N₄O₂)₂]
M_r	366.60
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.750 (3), 8.857 (2), 9.503 (2)
β (°)	118.42 (3)
V (Å³)	1091.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.03
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2000)
T_min, T_max	0.666, 0.673
No. of measured, independent and observed [I > 2σ(I)] reflections	6805, 1452, 1441
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.049, 0.94
No. of reflections	1452
No. of parameters	87
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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