Bis(5-amino­tetra­zole-1-acetato-κO)tetra­aqua­cobalt(II) and catena-poly[[cadmium(II)]-bis­(μ-5-amino­tetra­zole-1-acetato-κ³N⁴:O,O′)]

The Co^II atom in bis(5-amino­tetra­zole-1-acetato)tetra­aqua­cobalt(II), [Co(C₃H₄N₅O₂)₂(H₂O)₄], (I), is octa­hedrally coordinated by six O atoms from two 5-amino­tetra­zole-1-acetate (atza) ligands and four water mol­ecules. The mol­ecule has a crystallographic centre of symmetry located at the Co^II atom. The mol­ecules of (I) are inter­linked by hydrogen-bond inter­actions, forming a two-dimensional supra­molecular network structure in the ac plane. The Cd^II atom in catena-poly[[cadmium(II)]-bis­(μ-5-amino­tetra­zole-1-acetato], [Cd(C₃H₄N₅O₂)₂]_n, (II), lies on a twofold axis and is coordinated by two N atoms and four O atoms from four atza ligands to form a distorted octa­hedral coordination environment. The Cd^II centres are connected through tridentate atza bridging ligands to form a two-dimensional layered structure extending along the ab plane, which is further linked into a three-dimensional structure through hydrogen-bond inter­actions.

S1. Comment

Coordination compounds containing a tetrazole group have been the subject of intense research effort in recent years, owing to their unique structures and their potential applications in advanced materials (Ye et al., 2006; Xiong et al., 2002; Stagni et al., 2006; Mautner et al., 2004; Jiang et al., 2004). Among numerous organic ligands containing a tetrazole group, 5-substituted tetrazolates [e.g. 5-methyl-, 5-ethyl-, 5-(2-pyridyl)-, 5-(3-pyridyl)- and 5-(4-pyridyl)tetrazolate] and 1-substituted tetrazoles [e.g. 1-acetato-, 1-phenyl-, 1-(2-chloroethyl)-, 1-methyl- and 1-ethyltetrazole] have already been studied, and a number of complexes containing these ligands have been reported (He et al., 2005; Wu et al., 2006, 2005; Xue et al., 2002; Qu et al., 2003; Zhao et al., 2004; Wang et al., 2005; Palazzi et al., 2002). However, adducts of another class of 1,5-disubstituted tetrazoles have only been the subject of limited study with metal ions, and few coordination complexes with 1,5-disubstituted tetrazole ligands have been reported to date (Zhilin et al., 2002; Gaponik et al., 2005). Inspired by the pioneering work of Demko & Sharpless (2002, 2001), we have recently studied [2 + 3] cycloaddition reactions of dicyandiamide with NaN₃ and ZnCl₂ as Lewis acids in aqueous solution to give 5-aminotetrazole (Hatz), and 5-aminotetrazole-1-acetic acid (Hatza) was obtained by the reaction of Hatz with chloroacetic acid in methanolic potassium hydroxide solution. Of interest to us is the coordination ability of the Hatza or the atza^- ligands through the N and O electron-donating atoms, which allows it to serve as either a multidentate or a bridging ligand in supramolecular assemblies. To our knowledge, there is no synthetic and structural information on any complex of the Hatza or atza^- ligands. In this context, we carried out the reactions of Hatza with CoCl₂·6H₂O and CdCl₂·6H₂O, and isolated two new coordination complexes, [Co(atza)₂(H₂O)₄], (I), [Cd(atza)₂]_n, (II), respectively. Here, we report the crystal structures of complexes (I) and (II).

The asymmetric unit of (I) contains half of the [Co(atza)₂(H₂O)₄] molecule. As shown in Fig. 1, atom Co1 lies on an inversion centre and is coordinated by four O atoms [O1, O1ⁱ, O3 and O3ⁱ; symmetry code: (i) -x, -y + 1, -z + 2] from two atza^- ligands and two aqua ligands, located in the equatorial plane, and two O atoms (O4 and O4ⁱ) from two aqua ligands in the apical sites, thereby forming a slightly distorted CoO₆ octahedral coordination geometry. The Co—O(carboxlate) distance [2.0768 (13) Å] is close to the values observed in [CoL₂(H₂O)₄] [2.0653 (12) Å; L is 4-hydroxypyridine-2,6-dicarboxylate; Cui et al., 2006] and [CoL₂(H₂O)₄] [2.0663 (14) Å; L is 2-(methylthio)nicotinate; Miklos et al., 2006]. The Co—O(H₂O) distances [2.0828 (15) and 2.1451 (14) Å] are in the range observed in [CoL₂(H₂O)₄] [2.0764 (13)–2.1266 (13) Å; L is 4-hydroxypyridine-2,6-dicarboxylate; Cui et al., 2006] and [CoL₂(H₂O)₄] [2.086 (16)–2.1846 (15) Å; L is 2-(methylthio)nicotinate; Miklos et al., 2006]. The cisoid angles of [CoO₆] are in the range 87.52 (5)–92.18 (5)°, close to 90°. The atza^- anion in (I) acts only as a monodentate ligand via its one carboxylate O atom.

In complex (I), six intermolecular hydrogen-bond interactions exist between water molecules and carboxylate O atoms [O4—H4A···O2ⁱ and O3—H3B···O2ⁱⁱⁱ; symmetry code: (iii) x - 1, y, z], between water molecules and tetrazole N atoms [O3—H3A···N4ⁱⁱ and O4—H4B···N2^iv; symmetry codes: (ii) -x + 1, -y + 1, -z + 1; (iv) -x + 1, -y, -z + 2], between an amino group and a tetrazole N atom [N5—H5A···N3ⁱⁱⁱ], and between an amino group and a carboxylate O atom [N5—H5B···O2ⁱⁱ]. Thus, the molecules of complex (I) are interlinked by these intermolecular hydrogen bonds, forming a two-dimensional supramolecular network structure in the ac plane (Fig. 2).

The asymmetric unit of (II) contains one-half of a Cd^II atom and one atza^- ligand. As shown in Fig. 3, atom Cd1 resides on a twofold axis and is coordinated by two N atoms [N4ⁱ and N4ⁱⁱ; symmetry codes: (i) -x + 1/2, y - 1/2, -z + 1/2; (ii) x + 1/2, y - 1/2, z] and four O atoms [O1, O1ⁱⁱⁱ, O2 and O2ⁱⁱⁱ; symmetry code: (iii) -x + 1, y, -z + 1/2] from four atza^- ligands. Two carboxylate groups chelate atom Cd1, with an O1—Cd1—O2 angle of 53.51 (5)°, leading to a severely distorted octahedral coordination geometry. The Cd—N(tetrazole) bond distance [2.2300 (16) Å] is shorter than those observed in [Cd₃(OH)₂Cl₂L₂] [2.362 (12) Å; L is 5-(4-pyridyl)tetrazolate; Xue et al., 2002], [CdL(H₂O)]_n [2.3245 (18)–2.372 (2) Å; L is 4-(tetrazolyl)benzenecarboxylate; Wang et al., 2005] and [Cd(L)₄(H₂O)₂](dipicrate)·2H₂O [2.334 (3) and 2.325 (2) Å; L is 5-amino-1,2,3,4-tetrazolyl; Zhang et al., 2001]. The Cd—O(carboxlate) bond lengths [2.2692 (15) and 2.6037 (14) Å] are in the range observed in [CdL(H₂O)]_n [2.219 (2) and 2.478 (2) Å; L is 4-(tetrazolyl)benzenecarboxylate; Wang et al., 2005], {[Cd(L)₂H₂O]0.5(3pa)}_n [2.336 (8)–2.574 (7) Å; L is isonicotinate and 3pa is 1,4-di-3-pyridyl-2,3-diaza-1,3-butadiene; Granifo & Baggio, 2007] and [CdL₂(H₂O)₂]_n [2.255 (4)–2.724 (5) Å; L is nicotinate; Zhang et al., 2004].

Each atza^- ligand in (II) acts as a tridentate ligand, chelating one Cd^II atom through its carboxylate O atoms while simultaneously binding to a second Cd^II atom through its tetrazole N atom, to form a two-dimensional neutral (4,4) network extending along the ab plane (Fig. 4). The network contains a rhombus grid (28-membered rings), with a Cd^II atom at each corner and an atza^- ligand at each edge connecting two Cd^II atoms. The edge lengths are equal, with a value of 8.5977 (18) Å. The diagonal lengths of the rhombus grid are 10.625 (13) and 13.520 (4) Å, and the angles of the rhombus are 76.326 (2) and 103.67 (2)°. The rhombus grid sheets are stacked together in an offset fashion along the c direction, in an ···A–B–A–B···sequence (Fig. 5).

Within the two-dimensional layer, one hydrogen-bond interaction is formed between an amino group and a carboxylate O atom [N5—H5B···O2^v; symmetry code: (v) -x + 1/2, y + 1/2, -z + 1/2]. Adjacent two-dimensional layers are further connected by two hydrogen-bonding interactions between an amino group, a methylene group and a carboxylate O atom [N5—H5A···O1^iv and C2—H2B···O1^iv; symmetry code: (iv) -x + 1, -y + 1, -z + 1], forming a three-dimensional supramolecular structure (Fig. 5).

In conclusion, under the same experimental conditions, the reaction of atza^- with Co^II and Cd^II ions gives two compounds with distinctly different structures. In compound (I), atza^- acts as a monodentate ligand to coordinate the Co^II ion, while in (II), atza^- acts as a tridentate bridging ligand to coordinate the Cd^II ion. Further work is to be undertaken, to react atza^- with other metal ions to study its coordination modes.

Related literature

For related literature, see: Cui et al. (2006); Demko & Sharpless (2001, 2002); Gaponik et al. (2005); Granifo & Baggio (2007); He et al. (2005); Jiang et al. (2004); Mautner et al. (2004); Miklos et al. (2006); Palazzi et al. (2002); Qu et al. (2003); Stagni et al. (2006); Wang et al. (2005); Wu et al. (2005, 2006); Xiong et al. (2002); Xue et al. (2002); Ye et al. (2006); Zhang et al. (2001, 2004); Zhao et al. (2004); Zhilin et al. (2002).

S2. Experimental

The Hatza ligand (0.0143 g, 0.1 mmol) was dissolved in distilled water (3 ml). The pH of the solution was adjusted to 5.0 using KOH solution, and a solution of CoCl₂·6H₂O (Quantity?) in distilled water (2 ml) was added. The mixture was stirred at room temperature for 3 h and then filtered. Slow evaporation of the solvent gave rise to pink crystals of (I) (yield 80%). Analysis, found: C 17.48, H 3.85, N 33.67%; calculated for C₆H₁₆CoN₁₀O₈: C 17.36, H 3.88, N 33.74%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 1655 (m), 1609 (s), 1582 (s), 1485 (m), 1435 (m), 1393 (s), 1327 (m), 1296 (w), 1134 (w), 1065 (w), 1015 (w), 949 (w), 829 (s), 768 (m), 737 (w), 694 (m), 577 (w).

Compound (II) was prepared similarly to (I), except that CdCl₂·6H₂O (0.0291 g, 0.1 mmol) was used instead of CoCl₂·6H₂O (yield 78%). Analysis, found: C 18.24, H 2.05, N 35.45%; calculated for C₆H₈CdN₁₀O₄: C 18.17, H 2.03, N 35.32%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 1657 (s), 1634 (s), 1611 (s), 1591 (s), 1526 (w), 1495 (m), 1439 (m), 1404 (s), 1323 (m), 1292 (w), 1271 (w), 1134 (w), 1103 (m), 1074 (w), 1016 (w), 953 (m), 826 (m), 758 (w), 698 (m).

S3. Refinement

Carbon-bound and nitrogen-bound H atoms were positioned geometrically (C—H = 0.99 Å and N—H = 0.88 Å), and were included in the refinement in the riding-model approximation, with U_iso(H) = 1.2U_eq(C). Water H atoms were located in a difference Fourier map and were refined with a distance restraint of O—H = 0.84(s.u.?) Å.

Computing details

For both compounds, data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A view of the molecule of complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x, -y + 1, -z + 2.]
	Fig. 2. A ce l l packing diagram for (I).
	Fig. 3. The coordination environment of the Cd^II atom of complex (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) -x + 1/2, y - 1/2, -z + 1/2; (ii) x + 1/2, y - 1/2, z; (iii) -x + 1, y, -z + 1/2.]
	Fig. 4. A view of the two-dimensional network of (II).
	Fig. 5. The three-dimensional network of (II) formed by hydrogen-bonding interactions (dashed lines).

(I) tetraaquabis(5-aminotetrazole-1-acetato-κO)cobalt(II)

Crystal data

[Co(C3H4N5O2)2(H2O)4]	Z = 1
Mr = 415.22	F(000) = 213
Triclinic, P1	Dx = 1.919 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 6.0869 (9) Å	Cell parameters from 1498 reflections
b = 6.5376 (9) Å	θ = 3.3–25.3°
c = 9.4896 (15) Å	µ = 1.27 mm^−1
α = 79.302 (8)°	T = 193 K
β = 83.344 (9)°	Block, pink
γ = 76.137 (8)°	0.41 × 0.37 × 0.18 mm
V = 359.24 (9) Å^3

Data collection

Rigaku Mercury diffractometer	1296 independent reflections
Radiation source: fine-focus sealed tube	1245 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 7.31 pixels mm^-1	θmax = 25.3°, θmin = 3.3°
ω scans	h = −6→7
Absorption correction: multi-scan (Jacobson, 1998)	k = −7→7
Tmin = 0.598, Tmax = 0.804	l = −11→10
3493 measured reflections

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0402P)^2 + 0.186P] where P = (Fo^2 + 2Fc^2)/3
1296 reflections	(Δ/σ)max < 0.001
140 parameters	Δρmax = 0.36 e Å^−3
4 restraints	Δρmin = −0.47 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.0000	0.5000	1.0000	0.01211 (15)
O1	0.2683 (2)	0.2690 (2)	0.93114 (15)	0.0159 (3)
O2	0.4852 (2)	0.4694 (2)	0.79098 (14)	0.0152 (3)
O3	−0.1190 (2)	0.5946 (2)	0.79551 (15)	0.0172 (3)
H3A	−0.044 (4)	0.616 (5)	0.7198 (19)	0.045 (9)*
H3B	−0.226 (3)	0.545 (4)	0.788 (3)	0.039 (8)*
O4	−0.1938 (2)	0.2584 (2)	1.05466 (15)	0.0174 (3)
N1	0.7515 (3)	0.1282 (2)	0.68353 (17)	0.0128 (3)
N2	0.9695 (3)	0.1123 (3)	0.71483 (18)	0.0158 (4)
N3	1.0709 (3)	0.1911 (3)	0.59781 (19)	0.0174 (4)
N4	0.9293 (3)	0.2608 (3)	0.48850 (18)	0.0156 (4)
N5	0.5412 (3)	0.2520 (3)	0.4768 (2)	0.0185 (4)
H5A	0.421 (5)	0.226 (4)	0.525 (3)	0.027 (7)*
H5B	0.527 (4)	0.339 (4)	0.400 (3)	0.021 (6)*
C1	0.4323 (3)	0.2944 (3)	0.84181 (19)	0.0126 (4)
C2	0.5738 (3)	0.0898 (3)	0.7934 (2)	0.0147 (4)
H2A	0.6429	−0.0074	0.8776	0.018*
H2B	0.4729	0.0175	0.7558	0.018*
C3	0.7301 (3)	0.2188 (3)	0.5449 (2)	0.0129 (4)
H4A	−0.305 (4)	0.323 (5)	1.110 (3)	0.050 (9)*
H4B	−0.111 (5)	0.142 (4)	1.102 (3)	0.050 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0106 (2)	0.0124 (2)	0.0118 (2)	−0.00248 (14)	0.00215 (14)	−0.00009 (14)
O1	0.0140 (7)	0.0148 (7)	0.0156 (7)	−0.0019 (6)	0.0051 (6)	0.0009 (5)
O2	0.0151 (7)	0.0140 (7)	0.0145 (7)	−0.0039 (6)	0.0017 (5)	0.0020 (5)
O3	0.0167 (8)	0.0230 (8)	0.0126 (7)	−0.0090 (6)	0.0013 (6)	−0.0001 (6)
O4	0.0166 (8)	0.0179 (8)	0.0181 (8)	−0.0072 (6)	0.0022 (6)	−0.0016 (6)
N1	0.0113 (8)	0.0137 (8)	0.0121 (8)	−0.0022 (6)	0.0017 (6)	−0.0009 (6)
N2	0.0113 (8)	0.0172 (8)	0.0181 (9)	−0.0019 (7)	0.0012 (7)	−0.0040 (7)
N3	0.0140 (8)	0.0182 (9)	0.0199 (9)	−0.0044 (7)	0.0025 (7)	−0.0038 (7)
N4	0.0146 (8)	0.0161 (9)	0.0159 (9)	−0.0051 (7)	0.0023 (7)	−0.0021 (7)
N5	0.0145 (9)	0.0227 (10)	0.0156 (9)	−0.0057 (7)	−0.0010 (7)	0.0059 (8)
C1	0.0101 (9)	0.0167 (10)	0.0092 (9)	−0.0019 (7)	−0.0030 (7)	0.0021 (7)
C2	0.0148 (10)	0.0138 (9)	0.0124 (10)	−0.0033 (8)	0.0056 (8)	0.0022 (8)
C3	0.0154 (10)	0.0091 (9)	0.0126 (9)	−0.0026 (7)	0.0033 (7)	−0.0009 (7)

Geometric parameters (Å, º)

Co1—O1	2.0768 (13)	N1—C3	1.346 (3)
Co1—O1^i	2.0768 (13)	N1—N2	1.368 (2)
Co1—O3	2.0828 (15)	N1—C2	1.446 (2)
Co1—O3^i	2.0828 (15)	N2—N3	1.289 (2)
Co1—O4^i	2.1451 (14)	N3—N4	1.368 (2)
Co1—O4	2.1451 (14)	N4—C3	1.336 (2)
O1—C1	1.254 (2)	N5—C3	1.337 (3)
O2—C1	1.257 (2)	N5—H5A	0.86 (3)
O3—H3A	0.811 (10)	N5—H5B	0.83 (3)
O3—H3B	0.812 (10)	C1—C2	1.525 (3)
O4—H4A	0.881 (18)	C2—H2A	0.9900
O4—H4B	0.881 (18)	C2—H2B	0.9900
O1—Co1—O1^i	180.0	C3—N1—N2	108.43 (16)
O1—Co1—O3	92.50 (6)	C3—N1—C2	128.05 (17)
O1^i—Co1—O3	87.50 (6)	N2—N1—C2	122.49 (16)
O1—Co1—O3^i	87.50 (6)	N3—N2—N1	105.95 (16)
O1^i—Co1—O3^i	92.50 (6)	N2—N3—N4	111.95 (16)
O3—Co1—O3^i	180.0	C3—N4—N3	105.21 (16)
O1—Co1—O4^i	92.10 (6)	C3—N5—H5A	119.0 (18)
O1^i—Co1—O4^i	87.90 (6)	C3—N5—H5B	118.8 (17)
O3—Co1—O4^i	87.69 (6)	H5A—N5—H5B	118 (2)
O3^i—Co1—O4^i	92.31 (6)	O1—C1—O2	125.89 (17)
O1—Co1—O4	87.90 (6)	O1—C1—C2	114.70 (16)
O1^i—Co1—O4	92.10 (6)	O2—C1—C2	119.41 (16)
O3—Co1—O4	92.31 (6)	N1—C2—C1	112.80 (15)
O3^i—Co1—O4	87.69 (6)	N1—C2—H2A	109.0
O4^i—Co1—O4	180.0	C1—C2—H2A	109.0
C1—O1—Co1	128.40 (12)	N1—C2—H2B	109.0
Co1—O3—H3A	127 (2)	C1—C2—H2B	109.0
Co1—O3—H3B	112 (2)	H2A—C2—H2B	107.8
H3A—O3—H3B	113 (3)	N4—C3—N5	126.99 (18)
Co1—O4—H4A	100 (2)	N4—C3—N1	108.46 (17)
Co1—O4—H4B	110 (2)	N5—C3—N1	124.51 (18)
H4A—O4—H4B	112 (3)
O3—Co1—O1—C1	63.76 (16)	C3—N1—C2—C1	−71.5 (2)
O3^i—Co1—O1—C1	−116.24 (16)	N2—N1—C2—C1	95.6 (2)
O4^i—Co1—O1—C1	−24.02 (16)	O1—C1—C2—N1	176.15 (16)
O4—Co1—O1—C1	155.98 (16)	O2—C1—C2—N1	−3.5 (3)
C3—N1—N2—N3	0.0 (2)	N3—N4—C3—N5	−177.42 (18)
C2—N1—N2—N3	−169.32 (16)	N3—N4—C3—N1	0.4 (2)
N1—N2—N3—N4	0.3 (2)	N2—N1—C3—N4	−0.2 (2)
N2—N3—N4—C3	−0.5 (2)	C2—N1—C3—N4	168.27 (17)
Co1—O1—C1—O2	11.3 (3)	N2—N1—C3—N5	177.66 (18)
Co1—O1—C1—C2	−168.34 (12)	C2—N1—C3—N5	−13.8 (3)

Symmetry code: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2^i	0.88 (2)	1.86 (2)	2.704 (2)	161 (3)
N5—H5B···O2^ii	0.83 (3)	2.00 (3)	2.835 (2)	175 (2)
N5—H5A···N3^iii	0.86 (3)	2.21 (3)	3.047 (3)	166 (2)
O4—H4B···N2^iv	0.88 (2)	2.26 (2)	3.108 (2)	161 (3)
O3—H3B···O2^iii	0.81 (1)	1.93 (1)	2.731 (2)	169 (3)
O3—H3A···N4^ii	0.81 (1)	2.10 (1)	2.889 (2)	164 (3)

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

(II) catena-poly[[cadmium(II)]bis(µ-5-aminotetrazole-1-acetato-κ³N⁴:O,O')]

Crystal data

[Cd(C3H4N5O2)2]	F(000) = 776
Mr = 396.62	Dx = 2.147 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -C 2yc	Cell parameters from 2668 reflections
a = 13.520 (4) Å	θ = 3.1–25.3°
b = 10.625 (3) Å	µ = 1.82 mm^−1
c = 8.877 (3) Å	T = 193 K
β = 105.808 (5)°	Block, colourless
V = 1227.0 (6) Å^3	0.47 × 0.38 × 0.37 mm
Z = 4

Data collection

Rigaku Mercury diffractometer	1124 independent reflections
Radiation source: fine-focus sealed tube	1097 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 7.31 pixels mm^-1	θmax = 25.3°, θmin = 3.1°
ω scans	h = −16→14
Absorption correction: multi-scan (Jacobson, 1998)	k = −12→12
Tmin = 0.439, Tmax = 0.512	l = −9→10
5638 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.016	H-atom parameters constrained
wR(F^2) = 0.044	w = 1/[σ^2(Fo^2) + (0.0301P)^2 + 1.2198P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
1124 reflections	Δρmax = 0.45 e Å^−3
98 parameters	Δρmin = −0.44 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0077 (6)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cd1	0.5000	0.202071 (15)	0.2500	0.01612 (12)
O1	0.49688 (11)	0.31422 (12)	0.46619 (18)	0.0205 (3)
O2	0.35308 (10)	0.35004 (13)	0.28019 (15)	0.0198 (3)
N1	0.26063 (11)	0.46434 (14)	0.48255 (18)	0.0158 (3)
N2	0.17720 (12)	0.39380 (15)	0.4885 (2)	0.0224 (4)
N3	0.09751 (12)	0.45610 (16)	0.4179 (2)	0.0250 (4)
N4	0.12502 (11)	0.56785 (15)	0.36296 (19)	0.0187 (3)
N5	0.28777 (12)	0.66021 (15)	0.37108 (19)	0.0185 (3)
H5A	0.3551	0.6522	0.4020	0.022*
H5B	0.2600	0.7275	0.3185	0.022*
C1	0.22796 (14)	0.57057 (17)	0.4038 (2)	0.0150 (4)
C2	0.36433 (14)	0.41749 (18)	0.5428 (2)	0.0167 (4)
H2A	0.3656	0.3549	0.6260	0.020*
H2B	0.4098	0.4881	0.5909	0.020*
C3	0.40614 (13)	0.35699 (16)	0.4187 (2)	0.0146 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01032 (15)	0.01492 (15)	0.02308 (16)	0.000	0.00447 (9)	0.000
O1	0.0121 (7)	0.0213 (7)	0.0286 (8)	0.0019 (5)	0.0064 (6)	−0.0010 (5)
O2	0.0213 (7)	0.0198 (7)	0.0185 (7)	−0.0021 (5)	0.0058 (5)	−0.0015 (5)
N1	0.0118 (7)	0.0154 (8)	0.0208 (8)	0.0009 (6)	0.0055 (6)	0.0001 (6)
N2	0.0153 (8)	0.0181 (8)	0.0352 (9)	0.0001 (7)	0.0092 (7)	0.0039 (7)
N3	0.0157 (8)	0.0206 (9)	0.0394 (10)	−0.0002 (7)	0.0084 (7)	0.0053 (7)
N4	0.0112 (8)	0.0167 (8)	0.0279 (8)	0.0009 (6)	0.0051 (6)	0.0022 (7)
N5	0.0104 (7)	0.0175 (8)	0.0265 (8)	0.0006 (6)	0.0033 (6)	0.0046 (7)
C1	0.0143 (9)	0.0159 (9)	0.0151 (8)	0.0018 (7)	0.0046 (7)	−0.0036 (7)
C2	0.0127 (9)	0.0183 (9)	0.0177 (9)	0.0029 (7)	0.0018 (7)	0.0002 (7)
C3	0.0128 (9)	0.0092 (8)	0.0226 (9)	−0.0025 (6)	0.0063 (7)	0.0013 (7)

Geometric parameters (Å, º)

Cd1—N4^i	2.2300 (16)	N1—C2	1.446 (2)
Cd1—N4^ii	2.2300 (16)	N2—N3	1.274 (2)
Cd1—O1	2.2692 (15)	N3—N4	1.373 (2)
Cd1—O1^iii	2.2692 (15)	N4—C1	1.340 (2)
Cd1—O2^iii	2.6037 (14)	N4—Cd1^iv	2.2300 (15)
Cd1—O2	2.6037 (14)	N5—C1	1.332 (2)
Cd1—C3^iii	2.7561 (18)	N5—H5A	0.8800
Cd1—C3	2.7561 (18)	N5—H5B	0.8800
O1—C3	1.268 (2)	C2—C3	1.512 (3)
O2—C3	1.245 (2)	C2—H2A	0.9900
N1—C1	1.338 (2)	C2—H2B	0.9900
N1—N2	1.367 (2)
N4^i—Cd1—N4^ii	100.49 (8)	C3—O1—Cd1	98.39 (12)
N4^i—Cd1—O1	121.98 (5)	C3—O2—Cd1	83.50 (10)
N4^ii—Cd1—O1	98.16 (6)	C1—N1—N2	108.92 (14)
N4^i—Cd1—O1^iii	98.16 (6)	C1—N1—C2	129.24 (15)
N4^ii—Cd1—O1^iii	121.98 (5)	N2—N1—C2	121.60 (15)
O1—Cd1—O1^iii	116.65 (7)	N3—N2—N1	106.99 (15)
N4^i—Cd1—O2^iii	147.77 (5)	N2—N3—N4	110.44 (15)
N4^ii—Cd1—O2^iii	85.77 (5)	C1—N4—N3	106.53 (15)
O1—Cd1—O2^iii	87.73 (5)	C1—N4—Cd1^iv	135.43 (13)
O1^iii—Cd1—O2^iii	53.52 (5)	N3—N4—Cd1^iv	117.86 (11)
N4^i—Cd1—O2	85.77 (5)	C1—N5—H5A	120.0
N4^ii—Cd1—O2	147.77 (5)	C1—N5—H5B	120.0
O1—Cd1—O2	53.52 (5)	H5A—N5—H5B	120.0
O1^iii—Cd1—O2	87.73 (5)	N5—C1—N1	125.72 (17)
O2^iii—Cd1—O2	105.71 (6)	N5—C1—N4	127.17 (17)
N4^i—Cd1—C3^iii	122.85 (6)	N1—C1—N4	107.11 (16)
N4^ii—Cd1—C3^iii	102.79 (6)	N1—C2—C3	113.21 (15)
O1—Cd1—C3^iii	105.26 (5)	N1—C2—H2A	108.9
O1^iii—Cd1—C3^iii	27.07 (5)	C3—C2—H2A	108.9
O2^iii—Cd1—C3^iii	26.67 (5)	N1—C2—H2B	108.9
O2—Cd1—C3^iii	99.92 (5)	C3—C2—H2B	108.9
N4^i—Cd1—C3	102.79 (6)	H2A—C2—H2B	107.7
N4^ii—Cd1—C3	122.85 (6)	O2—C3—O1	123.53 (17)
O1—Cd1—C3	27.07 (5)	O2—C3—C2	121.02 (16)
O1^iii—Cd1—C3	105.26 (5)	O1—C3—C2	115.45 (16)
O2^iii—Cd1—C3	99.92 (5)	O2—C3—Cd1	69.82 (10)
O2—Cd1—C3	26.67 (5)	O1—C3—Cd1	54.54 (9)
C3^iii—Cd1—C3	106.66 (7)	C2—C3—Cd1	165.60 (12)
N4^i—Cd1—O1—C3	−49.60 (12)	Cd1—O2—C3—O1	9.95 (16)
N4^ii—Cd1—O1—C3	−157.44 (10)	Cd1—O2—C3—C2	−169.46 (15)
O1^iii—Cd1—O1—C3	70.44 (10)	Cd1—O1—C3—O2	−11.48 (19)
O2^iii—Cd1—O1—C3	117.16 (11)	Cd1—O1—C3—C2	167.96 (13)
O2—Cd1—O1—C3	5.66 (9)	N1—C2—C3—O2	−0.4 (2)
C3^iii—Cd1—O1—C3	96.83 (12)	N1—C2—C3—O1	−179.85 (15)
N4^i—Cd1—O2—C3	129.92 (11)	N1—C2—C3—Cd1	−136.7 (4)
N4^ii—Cd1—O2—C3	26.90 (15)	N4^i—Cd1—C3—O2	−51.66 (11)
O1—Cd1—O2—C3	−5.74 (9)	N4^ii—Cd1—C3—O2	−163.31 (9)
O1^iii—Cd1—O2—C3	−131.72 (10)	O1—Cd1—C3—O2	169.82 (17)
O2^iii—Cd1—O2—C3	−80.72 (10)	O1^iii—Cd1—C3—O2	50.63 (11)
C3^iii—Cd1—O2—C3	−107.45 (11)	O2^iii—Cd1—C3—O2	105.32 (10)
C1—N1—N2—N3	−0.8 (2)	C3^iii—Cd1—C3—O2	78.77 (10)
C2—N1—N2—N3	−175.75 (16)	N4^i—Cd1—C3—O1	138.52 (11)
N1—N2—N3—N4	0.3 (2)	N4^ii—Cd1—C3—O1	26.87 (12)
N2—N3—N4—C1	0.3 (2)	O1^iii—Cd1—C3—O1	−119.19 (11)
N2—N3—N4—Cd1^iv	−175.50 (13)	O2^iii—Cd1—C3—O1	−64.50 (11)
N2—N1—C1—N5	−177.98 (17)	O2—Cd1—C3—O1	−169.82 (17)
C2—N1—C1—N5	−3.6 (3)	C3^iii—Cd1—C3—O1	−91.05 (11)
N2—N1—C1—N4	1.01 (19)	N4^i—Cd1—C3—C2	89.3 (5)
C2—N1—C1—N4	175.40 (17)	N4^ii—Cd1—C3—C2	−22.4 (5)
N3—N4—C1—N5	178.18 (17)	O1—Cd1—C3—C2	−49.2 (5)
Cd1^iv—N4—C1—N5	−7.1 (3)	O1^iii—Cd1—C3—C2	−168.4 (5)
N3—N4—C1—N1	−0.78 (19)	O2^iii—Cd1—C3—C2	−113.7 (5)
Cd1^iv—N4—C1—N1	173.88 (13)	O2—Cd1—C3—C2	140.9 (5)
C1—N1—C2—C3	−79.0 (2)	C3^iii—Cd1—C3—C2	−140.3 (5)
N2—N1—C2—C3	94.75 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O1^v	0.88	2.06	2.889 (2)	158
N5—H5B···O2^vi	0.88	2.02	2.847 (2)	157
C2—H2B···O1^v	0.99	2.57	3.426 (2)	145

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