Diaqua­bis[5-(5-carboxy-2-pyridyl)tetra­zolato-κ² N ¹,N ⁵]cadmium(II) dihydrate

Abstract

In the title complex, [Cd(C₇H₄N₅O₂)₂(H₂O)₂]·2H₂O, the water-coordinated Cd^II atom ( symmetry) is coordinated by four N atoms from two symmetry-related 3-carboxy­pyidyl-6-tetra­zolato ligands, forming a distorted octa­hedral complex. The uncoordinated water mol­ecules connect the mononuclear units into a layer structure through O—H⋯N and O—H⋯O hydrogen bonds; similar hydrogen bonds between coordinated water mol­ecules and anionic groups result in a three-dimensional structure.

Related literature

For background, see: Xiong et al. (2002 ▶)

Experimental

Crystal data

• [Cd(C₇H₄N₅O₂)₂(H₂O)₂]·2H₂O

• M _r = 564.77

• Triclinic,

• a = 6.1018 (2) Å

• b = 7.3805 (1) Å

• c = 12.383 (2) Å

• α = 84.17 (3)°

• β = 88.91 (3)°

• γ = 65.71 (2)°

• V = 505.51 (8) ų

• Z = 1

• Mo Kα radiation

• μ = 1.15 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 = 0.773, T _max = 1.000 (expected range = 0.615–0.795)

• 3817 measured reflections

• 2286 independent reflections

• 2104 reflections with I > 2σ(I)

• R _int = 0.027

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.078

• S = 1.10

• 2286 reflections

• 171 parameters

• 5 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.70 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: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Cd1—N5	2.293 (2)
Cd1—O3	2.312 (3)
Cd1—N1	2.396 (2)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯N2	0.85 (3)	2.02 (3)	2.860 (4)	166 (4)
O4—H4A⋯O2ii	0.85 (3)	1.92 (3)	2.767 (4)	170 (4)
O1—H1⋯O4iii	0.89 (3)	1.68 (3)	2.566 (4)	170 (5)
O3—H3B⋯N4iv	0.86 (2)	1.96 (3)	2.804 (4)	168 (4)
O3—H3A⋯N3v	0.90 (2)	1.92 (2)	2.806 (4)	172 (3)

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

Hydrothermal reactions involving in situ ligand synthesis have attracted great interests (Xiong et al., 2002). In the contribution, we report the title mononuclear complex (I) based on tetrazol ligand obtained by in situ ligand synthesis.

In the structure of (I), the ligand chelates Cd(II) center through pyridyl N and tetrazol N to form a centrosymmetrical mononuclear complex. Two coordinated water molecules complete the octahedral geometry of Cd(II) center (Fig.1). Two solvent water molecules and carboxylic groups of the ligands form a synthon R₄⁴(12) which connects mononuclear unit into a two-dimensional layer structure through hydrogen bonds between solvent water and tetrazol groups (Table. 2). The hydrogen bonds between coordinated water molecules and tetrazol groups result in a three-dimensional structure (Fig.2).

Experimental

A mixture of Cd(NO₃)₂.4H₂O (77 mg, 0.25 mmol), sodium azide(33 mg, 0.5 mmol) and 6-cyanopyridine-3-carboxylic acid (74 mg, 0.5 mmol) was suspended in water (10 ml) and heated in a teflon-lined steel bomb at 160 ° C for 3 days. The colorless crystals were obtained.

Refinement

H atoms bonded to C were located geometrically (C—H = 0.95 Å) with U_iso(H) = 1.2 U_eq(C). H atoms bonded to O were located by difference maps and refined with a distance restraint of O—H = 0.87 (3) Å. The displacement factors were freely refined.

Figures

Fig. 1.

ORTEP of complex (I) with 30% thermal ellipsoids. A = 1 - x, -y, 1 - z

Fig. 2.

The packing structure viewed along a axis.

Crystal data

[Cd(C7H4N5O2)2(H2O)2]·2H2O	Z = 1
Mr = 564.77	F(000) = 282
Triclinic, P1	Dx = 1.855 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1018 (2) Å	Cell parameters from 612 reflections
b = 7.3805 (1) Å	θ = 3.0–27.5°
c = 12.383 (2) Å	µ = 1.15 mm−1
α = 84.17 (3)°	T = 293 K
β = 88.91 (3)°	Prism, colorless
γ = 65.71 (2)°	0.20 × 0.20 × 0.20 mm
V = 505.51 (8) Å3

Data collection

Rigaku Mercury CCD diffractometer	2286 independent reflections
Radiation source: fine-focus sealed tube	2104 reflections with I > 2σ(I)
graphite	Rint = 0.027
Detector resolution: 13.6612 pixels mm-1	θmax = 27.4°, θmin = 3.0°
CCD_Profile_fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	k = −7→9
Tmin = 0.773, Tmax = 1.000	l = −15→15
3817 measured reflections

Refinement

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0287P)2 + 0.1909P] where P = (Fo2 + 2Fc2)/3
2286 reflections	(Δ/σ)max = 0.001
171 parameters	Δρmax = 0.39 e Å−3
5 restraints	Δρmin = −0.70 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
Cd1	0.5000	0.0000	0.5000	0.03880 (13)
O1	−0.1058 (5)	−0.1234 (4)	0.1759 (2)	0.0614 (8)
N1	0.3050 (5)	0.1080 (4)	0.32445 (19)	0.0328 (6)
C1	−0.1196 (6)	0.0465 (5)	0.1283 (3)	0.0401 (7)
H1	−0.217 (7)	−0.160 (7)	0.152 (4)	0.098 (17)*
O2	−0.2500 (5)	0.1386 (4)	0.0504 (2)	0.0580 (7)
N2	0.5549 (5)	0.4825 (4)	0.2873 (2)	0.0404 (6)
C2	0.0443 (6)	0.1228 (4)	0.1777 (2)	0.0338 (7)
O3	0.1539 (5)	0.2229 (4)	0.5726 (2)	0.0512 (6)
N3	0.7080 (5)	0.4857 (4)	0.3617 (2)	0.0461 (7)
C3	0.0743 (6)	0.2851 (5)	0.1257 (3)	0.0425 (8)
H3	−0.0060	0.3468	0.0581	0.051*
H3A	0.195 (6)	0.321 (4)	0.587 (2)	0.031 (8)*
H3B	0.015 (5)	0.273 (5)	0.540 (3)	0.052 (11)*
O4	0.6141 (5)	0.7305 (4)	0.1064 (2)	0.0579 (7)
N4	0.7355 (5)	0.3463 (4)	0.4431 (2)	0.0450 (7)
C4	0.2210 (6)	0.3572 (5)	0.1722 (3)	0.0424 (8)
H4	0.2453	0.4676	0.1367	0.051*
H4A	0.492 (6)	0.781 (6)	0.063 (3)	0.062 (12)*
H4B	0.571 (7)	0.666 (6)	0.157 (3)	0.068 (13)*
N5	0.6029 (5)	0.2491 (4)	0.4230 (2)	0.0354 (6)
C5	0.1627 (6)	0.0381 (5)	0.2777 (2)	0.0366 (7)
H5	0.1418	−0.0732	0.3141	0.044*
C6	0.3338 (5)	0.2658 (4)	0.2722 (2)	0.0326 (6)
C7	0.4943 (6)	0.3343 (4)	0.3263 (2)	0.0340 (7)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cd1	0.0443 (2)	0.0424 (2)	0.03052 (19)	−0.02092 (16)	−0.00857 (14)	0.00836 (13)
O1	0.075 (2)	0.0752 (19)	0.0503 (16)	−0.0506 (17)	−0.0210 (14)	0.0103 (13)
N1	0.0369 (15)	0.0352 (13)	0.0274 (13)	−0.0169 (12)	0.0003 (10)	0.0014 (10)
C1	0.0366 (19)	0.054 (2)	0.0307 (16)	−0.0186 (16)	0.0024 (13)	−0.0080 (14)
O2	0.0524 (17)	0.0714 (17)	0.0467 (15)	−0.0237 (14)	−0.0215 (12)	0.0051 (12)
N2	0.0446 (17)	0.0393 (15)	0.0422 (16)	−0.0237 (13)	−0.0003 (12)	0.0031 (11)
C2	0.0324 (17)	0.0403 (16)	0.0252 (15)	−0.0118 (13)	−0.0002 (12)	−0.0016 (12)
O3	0.0495 (18)	0.0497 (15)	0.0547 (16)	−0.0199 (14)	−0.0028 (13)	−0.0076 (12)
N3	0.0491 (19)	0.0470 (16)	0.0503 (18)	−0.0276 (15)	0.0015 (14)	−0.0062 (13)
C3	0.042 (2)	0.0482 (19)	0.0329 (17)	−0.0168 (16)	−0.0089 (14)	0.0099 (14)
O4	0.0610 (19)	0.0764 (19)	0.0474 (16)	−0.0446 (16)	−0.0197 (14)	0.0201 (14)
N4	0.0446 (18)	0.0470 (16)	0.0478 (17)	−0.0231 (14)	−0.0064 (13)	−0.0032 (13)
C4	0.046 (2)	0.0419 (18)	0.0370 (18)	−0.0190 (16)	−0.0024 (14)	0.0105 (13)
N5	0.0352 (15)	0.0353 (13)	0.0381 (14)	−0.0178 (12)	−0.0034 (11)	0.0014 (11)
C5	0.0393 (19)	0.0405 (17)	0.0315 (16)	−0.0194 (15)	−0.0029 (13)	0.0032 (12)
C6	0.0321 (17)	0.0321 (15)	0.0312 (16)	−0.0114 (13)	0.0011 (12)	0.0000 (12)
C7	0.0345 (17)	0.0319 (15)	0.0336 (16)	−0.0128 (13)	0.0034 (12)	0.0017 (12)

Geometric parameters (Å, °)

Cd1—N5	2.293 (2)	C2—C5	1.398 (4)
Cd1—N5i	2.293 (2)	O3—H3A	0.90 (2)
Cd1—O3i	2.312 (3)	O3—H3B	0.86 (2)
Cd1—O3	2.312 (3)	N3—N4	1.325 (4)
Cd1—N1	2.396 (2)	C3—C4	1.374 (5)
Cd1—N1i	2.396 (2)	C3—H3	0.9500
O1—C1	1.301 (4)	O4—H4A	0.85 (3)
O1—H1	0.89 (3)	O4—H4B	0.85 (3)
N1—C5	1.342 (4)	N4—N5	1.324 (4)
N1—C6	1.348 (4)	C4—C6	1.394 (4)
C1—O2	1.215 (4)	C4—H4	0.9500
C1—C2	1.499 (4)	N5—C7	1.343 (4)
N2—N3	1.332 (4)	C5—H5	0.9500
N2—C7	1.336 (4)	C6—C7	1.472 (4)
C2—C3	1.379 (4)
N5—Cd1—N5i	180.0	C5—C2—C1	121.8 (3)
N5—Cd1—O3i	87.03 (10)	Cd1—O3—H3A	103 (2)
N5i—Cd1—O3i	92.97 (10)	Cd1—O3—H3B	124 (3)
N5—Cd1—O3	92.97 (10)	H3A—O3—H3B	109 (3)
N5i—Cd1—O3	87.03 (10)	N4—N3—N2	109.7 (3)
O3i—Cd1—O3	180.0	C4—C3—C2	119.7 (3)
N5—Cd1—N1	72.97 (9)	C4—C3—H3	120.2
N5i—Cd1—N1	107.03 (9)	C2—C3—H3	120.2
O3i—Cd1—N1	91.55 (9)	H4A—O4—H4B	103 (4)
O3—Cd1—N1	88.45 (9)	N5—N4—N3	109.3 (3)
N5—Cd1—N1i	107.03 (9)	C3—C4—C6	119.0 (3)
N5i—Cd1—N1i	72.97 (9)	C3—C4—H4	120.5
O3i—Cd1—N1i	88.45 (9)	C6—C4—H4	120.5
O3—Cd1—N1i	91.55 (9)	N4—N5—C7	105.1 (2)
N1—Cd1—N1i	180.00 (5)	N4—N5—Cd1	140.8 (2)
C1—O1—H1	113 (3)	C7—N5—Cd1	114.08 (19)
C5—N1—C6	118.3 (2)	N1—C5—C2	122.5 (3)
C5—N1—Cd1	127.62 (19)	N1—C5—H5	118.7
C6—N1—Cd1	113.95 (18)	C2—C5—H5	118.7
O2—C1—O1	124.7 (3)	N1—C6—C4	122.1 (3)
O2—C1—C2	121.4 (3)	N1—C6—C7	116.0 (2)
O1—C1—C2	113.9 (3)	C4—C6—C7	121.9 (3)
N3—N2—C7	104.7 (3)	N2—C7—N5	111.3 (3)
C3—C2—C5	118.4 (3)	N2—C7—C6	126.0 (3)
C3—C2—C1	119.8 (3)	N5—C7—C6	122.7 (3)

Symmetry codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···N2	0.85 (3)	2.02 (3)	2.860 (4)	166 (4)
O4—H4A···O2ii	0.85 (3)	1.92 (3)	2.767 (4)	170 (4)
O1—H1···O4iii	0.89 (3)	1.68 (3)	2.566 (4)	170 (5)
O3—H3B···N4iv	0.86 (2)	1.96 (3)	2.804 (4)	168 (4)
O3—H3A···N3v	0.90 (2)	1.92 (2)	2.806 (4)	172 (3)

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