Diaqua­bis(1H-1,2,4-triazole-3-carboxyl­ato)cadmium(II)

Zhu, J.; Yin, X.-H.; Feng, Y.; Hu, F.-L.; Zhuang, Y.; Lin, C.-W.

doi:10.1107/S1600536807063994

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m119

https://doi.org/10.1107/S1600536807063994

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Diaquabis(1H-1,2,4-triazole-3-carboxylato)cadmium(II)

Jie Zhu,^a,^b Xian-Hong Yin,^a,^b ^* Yu Feng,^a Fei-Long Hu,^a Yue Zhuang ^a and Cui-Wu Lin ^b

^aCollege of Chemistry and Ecological Engineering, Guangxi University for Nationalities, Nanning 530006, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, People's Republic of China
^*Correspondence e-mail: yxhphd@163.com

(Received 10 November 2007; accepted 28 November 2007; online 6 December 2007)

In the title complex, [Cd(C₃H₂N₃O₂)₂(H₂O)₂], the Cd^II atom is coordinated by two N and two O atoms from two deprotonated 1H-1,2,4-triazole-3-carboxylic acid ligands (TRIA) and two water molecules. The Cd atom is located on an inversion centre. In the crystal structure, molecules are linked together via O—H⋯O and N—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For related literature, see: Guo & Wang (2005 ), Zhu et al. (2007 , 2008 ).

Experimental

Crystal data

[Cd(C₃H₂N₃O₂)₂(H₂O)₂]
M_r = 372.58
Monoclinic, P 2₁ /c
a = 9.2722 (16) Å
b = 8.8318 (14) Å
c = 6.9714 (17) Å
β = 92.230 (1)°
V = 570.46 (19) Å³
Z = 2
Mo Kα radiation
μ = 1.95 mm⁻¹
T = 298 (1) K
0.32 × 0.23 × 0.11 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.574, T_max = 0.814
2791 measured reflections
1002 independent reflections
843 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.077
S = 1.09
1002 reflections
88 parameters
H-atom parameters constrained
Δρ_max = 1.21 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3C⋯O2ⁱ	0.85	1.90	2.715 (3)	159
O3—H3B⋯O1ⁱⁱ	0.85	1.91	2.736 (3)	162
N3—H3⋯O2ⁱⁱⁱ	0.86	1.89	2.728 (4)	164
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807063994/om2190sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063994/om2190Isup2.hkl

checkCIF report

Comment top

Recently, although the crystal structure of methyl 1H-1,2,4-triazole-3-carboxylate has been reported (Guo & Wang, 2005), metal complexes with triazole ligands have been rarely of interest for decades despite the biological importance of the triazole group. We have reported the crystal structures of two new copper(II) complexes diaquobis(1H-1,2,4-triazole-3-carboxylato)copper(II) and (1H-1,2,4-triazole-3-carboxylato)(1,10-phen)copper(II)chloride (Zhu, et al., 2007, 2008). As a further investigation, we report in this paper the crystal structure of a new cadmium(II) complex, diaquobis(1H- 1,2,4-triazole-3-carboxylato)cadmium(II).

As shown in Fig. 1, the title compound consists of a centrosymmetric mononuclear cadmium(II) complex cation. In the cation the Cd atom is six-coordinated by two N and two O atoms from two TRIA ligands and two O atoms from two water molecules. The Cd^II atom is in a slightly distorted octahedral environment. The Cd—O distances range from 2.315 (2) to 2.321 (3) Å, and the Cd—N bond length is 2.293 (3) Å, i.e. normal values. The C1—C2 bond length is 1.495 (5) Å, being in the normal C—C ranges in cadmium carboxylate complexes. The angles around Cd^II atom are from 73.57 (9) to linear. The TRIA molecule acts as a bidentate ligand.

In the title compound, the water molecules contribute to the formation of intermolecular hydrogen bonds involving carboxylate O atoms. Additional hydrogen bonds exist between the N—H groups of the triazole and carboxylate O atoms.

Related literature top

For related literature, see: Guo & Wang (2005), Zhu et al. (2007a,b).

Experimental top

1H-1,2,4-triazole-3-carboxylic acid and CdCl₂.2.5H₂O were available commercially and were used without further purification. 1H-1,2,4-triazole-3-carboxylic acid (1 mmol, 113 mg) was dissolved in distilled water (15 ml) and CdCl₂.2.5H₂O (0.5 mmol, 114.2 mg) was added in distilled water (5 ml) with stirring at 323 K. The resulting colorless solution was allowed to react for 5 h and was then filtered. Colorless crystals suitable for X-ray analysis were obtained by slow evaporation of a water solution over a period of one month (yield 75%). Anal. Calcd (%) for C₆H₈CdN₆O₆ (Mr = 372.58): C, 19.34; H, 2.16; N, 22.56. Found (%): C, 19.28; H, 2.22; N, 22.49.

Structure description top

For related literature, see: Guo & Wang (2005), Zhu et al. (2007a,b).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme. Symmetry code: (i) -x, -y, -z.

Diaquabis(1H-1,2,4-triazole-3-carboxylato)cadmium(II) top

Crystal data top

[Cd(C₃H₂N₃O₂)₂(H₂O)₂]	F(000) = 364
M_r = 372.58	D_x = 2.169 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2042 reflections
a = 9.2722 (16) Å	θ = 2.2–28.2°
b = 8.8318 (14) Å	µ = 1.95 mm⁻¹
c = 6.9714 (17) Å	T = 298 K
β = 92.230 (1)°	Prism, colorless
V = 570.46 (19) Å³	0.32 × 0.23 × 0.11 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	1002 independent reflections
Radiation source: fine-focus sealed tube	843 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→11
T_min = 0.574, T_max = 0.814	k = −10→10
2791 measured reflections	l = −8→7

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0445P)² + 0.5043P] where P = (F_o² + 2F_c²)/3
1002 reflections	(Δ/σ)_max < 0.001
88 parameters	Δρ_max = 1.21 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

[Cd(C₃H₂N₃O₂)₂(H₂O)₂]	V = 570.46 (19) Å³
M_r = 372.58	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.2722 (16) Å	µ = 1.95 mm⁻¹
b = 8.8318 (14) Å	T = 298 K
c = 6.9714 (17) Å	0.32 × 0.23 × 0.11 mm
β = 92.230 (1)°

Data collection top

Bruker SMART CCD diffractometer	1002 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	843 reflections with I > 2σ(I)
T_min = 0.574, T_max = 0.814	R_int = 0.023
2791 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.09	Δρ_max = 1.21 e Å⁻³
1002 reflections	Δρ_min = −0.60 e Å⁻³
88 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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	0.0000	0.0000	0.02817 (18)
N1	0.2289 (4)	−0.0228 (3)	0.1335 (5)	0.0311 (8)
N2	0.4348 (3)	0.1039 (3)	0.2024 (4)	0.0311 (7)
N3	0.4480 (3)	−0.0451 (4)	0.2456 (5)	0.0323 (7)
H3	0.5255	−0.0865	0.2927	0.039*
O1	0.1027 (2)	0.2387 (2)	−0.0103 (3)	0.0293 (6)
O2	0.2867 (2)	0.3785 (2)	0.1013 (4)	0.0313 (6)
O3	−0.0921 (3)	0.0865 (3)	0.2849 (4)	0.0409 (7)
H3B	−0.0262	0.1228	0.3596	0.049*
H3C	−0.1369	0.0171	0.3426	0.049*
C1	0.2259 (3)	0.2549 (4)	0.0702 (5)	0.0242 (7)
C2	0.2995 (4)	0.1123 (4)	0.1356 (5)	0.0253 (7)
C3	0.3259 (4)	−0.1186 (4)	0.2057 (6)	0.0364 (9)
H3A	0.3110	−0.2215	0.2255	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0187 (2)	0.0234 (2)	0.0416 (3)	−0.00318 (12)	−0.00840 (16)	−0.00195 (14)
N1	0.0245 (18)	0.0259 (16)	0.042 (2)	0.0022 (12)	−0.0097 (14)	−0.0001 (13)
N2	0.0212 (15)	0.0333 (16)	0.0384 (17)	0.0024 (13)	−0.0050 (13)	−0.0017 (14)
N3	0.0253 (17)	0.0296 (15)	0.0415 (19)	0.0079 (14)	−0.0077 (14)	0.0029 (14)
O1	0.0226 (12)	0.0230 (12)	0.0414 (15)	−0.0009 (9)	−0.0103 (10)	0.0046 (10)
O2	0.0237 (13)	0.0225 (12)	0.0474 (15)	−0.0025 (10)	−0.0034 (11)	0.0009 (10)
O3	0.0377 (15)	0.0390 (15)	0.0458 (16)	−0.0120 (12)	−0.0014 (12)	−0.0053 (12)
C1	0.0204 (17)	0.0246 (17)	0.0275 (18)	−0.0005 (14)	0.0001 (13)	−0.0012 (14)
C2	0.0225 (18)	0.0259 (17)	0.0274 (18)	−0.0006 (14)	−0.0006 (13)	−0.0017 (14)
C3	0.032 (2)	0.0286 (19)	0.048 (2)	0.0017 (17)	−0.0058 (17)	0.0011 (17)

Geometric parameters (Å, º) top

Cd1—N1	2.293 (3)	N2—N3	1.355 (4)
Cd1—N1ⁱ	2.293 (3)	N3—C3	1.325 (5)
Cd1—O1ⁱ	2.315 (2)	N3—H3	0.8600
Cd1—O1	2.315 (2)	O1—C1	1.261 (4)
Cd1—O3ⁱ	2.321 (3)	O2—C1	1.244 (4)
Cd1—O3	2.321 (3)	O3—H3B	0.8500
N1—C3	1.321 (5)	O3—H3C	0.8500
N1—C2	1.361 (4)	C1—C2	1.495 (5)
N2—C2	1.323 (4)	C3—H3A	0.9300

N1—Cd1—N1ⁱ	180.00 (17)	C2—N2—N3	102.0 (3)
N1—Cd1—O1ⁱ	106.43 (9)	C3—N3—N2	111.2 (3)
N1ⁱ—Cd1—O1ⁱ	73.57 (9)	C3—N3—H3	124.4
N1—Cd1—O1	73.57 (9)	N2—N3—H3	124.4
N1ⁱ—Cd1—O1	106.43 (9)	C1—O1—Cd1	117.1 (2)
O1ⁱ—Cd1—O1	180.0	Cd1—O3—H3B	111.7
N1—Cd1—O3ⁱ	87.30 (11)	Cd1—O3—H3C	111.8
N1ⁱ—Cd1—O3ⁱ	92.70 (11)	H3B—O3—H3C	109.5
O1ⁱ—Cd1—O3ⁱ	83.82 (9)	O2—C1—O1	125.0 (3)
O1—Cd1—O3ⁱ	96.18 (9)	O2—C1—C2	119.2 (3)
N1—Cd1—O3	92.70 (11)	O1—C1—C2	115.8 (3)
N1ⁱ—Cd1—O3	87.30 (11)	N2—C2—N1	113.8 (3)
O1ⁱ—Cd1—O3	96.18 (9)	N2—C2—C1	124.7 (3)
O1—Cd1—O3	83.82 (9)	N1—C2—C1	121.4 (3)
O3ⁱ—Cd1—O3	180.00 (12)	N1—C3—N3	109.2 (3)
C3—N1—C2	103.7 (3)	N1—C3—H3A	125.4
C3—N1—Cd1	144.8 (3)	N3—C3—H3A	125.4
C2—N1—Cd1	111.4 (2)

O1ⁱ—Cd1—N1—C3	4.2 (5)	Cd1—O1—C1—C2	9.1 (4)
O1—Cd1—N1—C3	−175.8 (5)	N3—N2—C2—N1	−0.5 (4)
O3ⁱ—Cd1—N1—C3	−78.6 (5)	N3—N2—C2—C1	178.4 (3)
O3—Cd1—N1—C3	101.4 (5)	C3—N1—C2—N2	0.9 (5)
O1ⁱ—Cd1—N1—C2	−179.7 (2)	Cd1—N1—C2—N2	−176.8 (2)
O1—Cd1—N1—C2	0.3 (2)	C3—N1—C2—C1	−178.1 (3)
O3ⁱ—Cd1—N1—C2	97.5 (3)	Cd1—N1—C2—C1	4.2 (4)
O3—Cd1—N1—C2	−82.5 (3)	O2—C1—C2—N2	−9.7 (5)
C2—N2—N3—C3	−0.1 (4)	O1—C1—C2—N2	171.8 (3)
N1—Cd1—O1—C1	−5.4 (2)	O2—C1—C2—N1	169.2 (3)
N1ⁱ—Cd1—O1—C1	174.6 (2)	O1—C1—C2—N1	−9.3 (5)
O3ⁱ—Cd1—O1—C1	−90.8 (2)	C2—N1—C3—N3	−0.9 (5)
O3—Cd1—O1—C1	89.2 (2)	Cd1—N1—C3—N3	175.3 (3)
Cd1—O1—C1—O2	−169.3 (3)	N2—N3—C3—N1	0.7 (5)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3C···O2ⁱⁱ	0.85	1.90	2.715 (3)	159
O3—H3B···O1ⁱⁱⁱ	0.85	1.91	2.736 (3)	162
N3—H3···O2^iv	0.86	1.89	2.728 (4)	164

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

Experimental details

Crystal data
Chemical formula	[Cd(C₃H₂N₃O₂)₂(H₂O)₂]
M_r	372.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.2722 (16), 8.8318 (14), 6.9714 (17)
β (°)	92.230 (1)
V (Å³)	570.46 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.95
Crystal size (mm)	0.32 × 0.23 × 0.11

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.574, 0.814
No. of measured, independent and observed [I > 2σ(I)] reflections	2791, 1002, 843
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.077, 1.09
No. of reflections	1002
No. of parameters	88
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.21, −0.60

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3C···O2ⁱ	0.85	1.90	2.715 (3)	159.2
O3—H3B···O1ⁱⁱ	0.85	1.91	2.736 (3)	162.2
N3—H3···O2ⁱⁱⁱ	0.86	1.89	2.728 (4)	164.1

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

Acknowledgements

The authors thank the National Natural Science Foundation of China (20761002) for support. This research was sponsored by the Fund of the Talent Highland Research Program of Guangxi University (205121), the Science Foundation of the State Ethnic Affairs Commission (07GX05), the Development Foundation of Guangxi Research Institute of Chemical Industry and the Science Foundation of Guangxi University for Nationalities (0409032, 0409012, 0509ZD047).

References

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