supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2008). E64, m792-m793    [ doi:10.1107/S1600536808013196 ]

Poly[diaquabis([mu]2-azido-[kappa]2N1:N1)bis([mu]3-1-oxoisonicotinato-[kappa]3O:O':O'')dicadmium(II)]

Z.-X. Wang, X.-B. Li and B.-W. Sun

Abstract top

In the title compound, [Cd2(C6H4NO3)2(N3)2(H2O)2]n, one CdII atom is located on an inversion center and is coordinated by four O atoms from four bridging 1-oxoisonicotinate ligands and two N atoms of two bridging azide ligands in a slightly distorted octahedral geometry. The other CdII atom, also lying on an inversion center, is coordinated by four O atoms from two bridging 1-oxoisonicotinate ligands and two water molecules and two N atoms of two bridging azide ligands in a slightly distorted octahedral geometry. The Cd atoms are connected via the 1-oxoisonicotinate and azide ligands into a two-dimensional coordination network. The crystal structure involves O-H...N and O-H...O hydrogen bonds.

Comment top

There is currently considerable interest in the synthesis and characterization of metal–organic frameworks because of their potential applications in molecular adsorption and separation processes, gas storage, ion exchange, catalysis, sensor technology and electronics (Du et al., 2006; Dybtsev et al., 2004). The isonicotinic acid N-oxide ligand possesses a longer bridging spacer and richer coordination modes to form a fascinating structure (He et al., 2005; Zhao et al., 2007). It is well known that azide anion is an excellent bridging ligand (Bai et al., 2004). Therefore, we expect to obtain higher dimensional structures based on isonicotinic acid N-oxide and azide ligands and transition metal ions through the control of their molar ratios. We report here the synthesis and crystal structure of the title compound.

In the title compound, the Cd1 atom is located on an inversion center and is coordinated by four O atoms from four bridging isonicotinate-N-oxide ligands and two N atoms of two bridging azide ligands in a slightly distorted octahedral geometry. The Cd2 atom, also lying on an inversion center, is coordinated by four O atoms from two bridging isonicotinate-N-oxide ligands and two water molecules and two N atoms of two azide ligands in a slightly distorted octahedral geometry (Fig. 1; Table 1). The Cd atoms are connected via the isonicotinate-N-oxide and azide ligands into a two-dimensional coordination network. Furthermore, a three-dimensional supramolecular network is formed by the intermolecular O—H···N and O—H···O hydrogen bonds (Fig. 2; Table 2).

Related literature top

For general background, see: Du et al. (2006); Dybtsev et al. (2004). For related structures, see: Bai et al. (2004); He et al. (2005); Zhao et al. (2007).

Experimental top

All reagents and solvents were used as obtained without further purification. Cd(NO3)2.4H2O (0.062 g, 0.2 mmol), isonicotinic acid N-oxide (0.028 g, 0.2 mmol), NaN3 (0.013 g, 0.2 mmol) and NaOH (0.016 g, 0.4 mmol) were dissolved in distilled water (10 ml). The mixture was sealed in a Teflon-lined stainless steel vessel and held at 443 K for one week. The vessel was gradually cooled to room temperature and colorless crystals suitable for crystallographic analysis were obtained.

Refinement top

H atoms on C atoms were positioned geometrically and refined as riding atoms, with C–H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of the water molecule were located in a difference Fourier map and fixed in the refinements with Uiso(H) = 1.2Ueq(O).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, together with symmetry-related atoms to complete the coordination units. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x, -y, 1 - z; (iii) -x, 1 - y, 2 - z; (iv) x, y, -1 + z; (v) x, 1 + y, z; (vi) x, -1 + y, z.]
[Figure 2] Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.
Poly[diaquabis(µ2-azido-κ2N1:N1)bis(µ3-1- oxoisonicotinato-κ3O:O':O'')dicadmium(II)] top
Crystal data top
[Cd2(C6H4NO3)2(N3)2(H2O)2]Z = 1
Mr = 621.10F(000) = 300
Triclinic, P1Dx = 2.312 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.5409 (17) ÅCell parameters from 2159 reflections
b = 7.850 (2) Åθ = 3.1–26.8°
c = 9.410 (3) ŵ = 2.45 mm−1
α = 99.668 (6)°T = 223 K
β = 97.164 (6)°Block, colorless
γ = 107.566 (5)°0.3 × 0.2 × 0.2 mm
V = 446.1 (2) Å3
Data collection top
Rigaku Scxmini 1K CCD area-detector
diffractometer		1567 independent reflections
Radiation source: fine-focus sealed tube1438 reflections with I > 2σ(I)
graphiteRint = 0.022
Detector resolution: 8.192 pixels mm-1θmax = 25.0°, θmin = 2.8°
thin–slice ω scansh = −7→7
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −9→7
Tmin = 0.612, Tmax = 0.613l = −11→10
5082 measured reflections
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.05P)2 + 1.3747P]
where P = (Fo2 + 2Fc2)/3
1567 reflections(Δ/σ)max < 0.001
139 parametersΔρmax = 0.60 e Å−3
1 restraintΔρmin = −1.02 e Å−3
Crystal data top
[Cd2(C6H4NO3)2(N3)2(H2O)2]γ = 107.566 (5)°
Mr = 621.10V = 446.1 (2) Å3
Triclinic, P1Z = 1
a = 6.5409 (17) ÅMo Kα radiation
b = 7.850 (2) ŵ = 2.45 mm−1
c = 9.410 (3) ÅT = 223 K
α = 99.668 (6)°0.3 × 0.2 × 0.2 mm
β = 97.164 (6)°
Data collection top
Rigaku Scxmini 1K CCD area-detector
diffractometer		1567 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		1438 reflections with I > 2σ(I)
Tmin = 0.612, Tmax = 0.613Rint = 0.022
5082 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.087Δρmax = 0.60 e Å−3
S = 1.08Δρmin = −1.02 e Å−3
1567 reflectionsAbsolute structure: ?
139 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.00000.50000.50000.01556 (17)
Cd20.00000.00000.50000.01683 (17)
O10.1884 (5)0.4600 (4)0.7066 (3)0.0244 (7)
O20.0598 (6)0.1674 (4)0.7283 (3)0.0311 (8)
O30.3130 (5)0.5495 (5)1.3892 (3)0.0270 (7)
O40.3676 (5)0.1301 (5)0.4778 (4)0.0295 (8)
H4B0.43610.20550.55460.035*
H4C0.41270.09510.39450.035*
N10.1164 (6)0.7997 (5)0.6110 (4)0.0201 (8)
N20.2664 (6)0.8640 (5)0.7131 (4)0.0227 (8)
N30.4108 (8)0.9283 (6)0.8078 (6)0.0506 (14)
N40.2847 (6)0.5005 (5)1.2437 (4)0.0208 (8)
C10.3105 (6)0.6288 (6)1.1625 (5)0.0213 (9)
H1A0.35340.75291.20950.026*
C20.2752 (6)0.5808 (6)1.0126 (5)0.0171 (8)
H2A0.29540.67140.95690.021*
C30.2086 (6)0.3959 (6)0.9430 (4)0.0168 (8)
C40.1925 (7)0.2671 (6)1.0312 (5)0.0216 (9)
H4A0.15470.14230.98730.026*
C50.2314 (7)0.3216 (6)1.1804 (5)0.0240 (9)
H5A0.22110.23451.23910.029*
C60.1483 (7)0.3368 (6)0.7782 (5)0.0189 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0215 (3)0.0136 (2)0.0112 (2)0.00553 (18)0.00313 (17)0.00218 (17)
Cd20.0216 (3)0.0152 (3)0.0132 (3)0.00717 (18)0.00221 (17)0.00086 (17)
O10.0288 (16)0.0273 (17)0.0148 (15)0.0069 (14)0.0003 (12)0.0050 (13)
O20.049 (2)0.0251 (18)0.0161 (15)0.0136 (16)0.0021 (14)−0.0019 (13)
O30.0253 (16)0.0362 (19)0.0095 (15)−0.0004 (14)0.0045 (12)−0.0036 (13)
O40.0259 (17)0.0337 (19)0.0214 (17)0.0014 (15)0.0050 (14)0.0010 (14)
N10.028 (2)0.0120 (16)0.0175 (18)0.0069 (15)−0.0020 (16)0.0005 (14)
N20.027 (2)0.0149 (17)0.027 (2)0.0079 (16)0.0011 (19)0.0071 (16)
N30.054 (3)0.024 (2)0.055 (3)0.004 (2)−0.029 (3)0.003 (2)
N40.0178 (17)0.028 (2)0.0146 (17)0.0054 (15)0.0059 (14)0.0020 (15)
C10.0146 (19)0.024 (2)0.022 (2)0.0038 (17)0.0020 (17)0.0015 (18)
C20.0159 (19)0.020 (2)0.018 (2)0.0079 (16)0.0050 (16)0.0061 (16)
C30.0133 (18)0.020 (2)0.017 (2)0.0061 (16)0.0044 (16)0.0029 (16)
C40.030 (2)0.017 (2)0.020 (2)0.0099 (18)0.0079 (18)0.0047 (17)
C50.025 (2)0.028 (2)0.017 (2)0.0057 (19)0.0076 (18)0.0046 (18)
C60.017 (2)0.027 (2)0.016 (2)0.0120 (18)0.0034 (16)0.0047 (18)
Geometric parameters (Å, °) top
Cd1—N12.259 (3)O4—H4B0.8300
Cd1—N1i2.259 (3)O4—H4C0.9000
Cd1—O12.289 (3)N1—N21.201 (5)
Cd1—O1i2.289 (3)N1—Cd2vii2.284 (3)
Cd1—O3ii2.370 (3)N2—N31.137 (6)
Cd1—O3iii2.370 (3)N4—C11.347 (6)
Cd2—O22.242 (3)N4—C51.349 (6)
Cd2—O2iv2.242 (3)C1—C21.369 (6)
Cd2—N1v2.284 (3)C1—H1A0.9400
Cd2—N1i2.284 (3)C2—C31.397 (6)
Cd2—O4iv2.363 (3)C2—H2A0.9400
Cd2—O42.363 (3)C3—C41.401 (6)
O1—C61.252 (5)C3—C61.507 (6)
O2—C61.257 (5)C4—C51.365 (6)
O3—N41.332 (5)C4—H4A0.9400
O3—Cd1vi2.370 (3)C5—H5A0.9400
N1—Cd1—N1i180.000 (1)C6—O2—Cd2130.6 (3)
N1—Cd1—O185.90 (12)N4—O3—Cd1vi118.5 (2)
N1i—Cd1—O194.10 (12)Cd2—O4—H4B109.5
N1—Cd1—O1i94.10 (12)Cd2—O4—H4C120.1
N1i—Cd1—O1i85.90 (12)H4B—O4—H4C130.4
O1—Cd1—O1i180.0N2—N1—Cd1122.0 (3)
N1—Cd1—O3ii90.18 (12)N2—N1—Cd2vii117.2 (3)
N1i—Cd1—O3ii89.82 (12)Cd1—N1—Cd2vii119.53 (15)
O1—Cd1—O3ii89.01 (11)N3—N2—N1178.2 (5)
O1i—Cd1—O3ii90.99 (11)O3—N4—C1120.0 (4)
N1—Cd1—O3iii89.82 (12)O3—N4—C5118.9 (4)
N1i—Cd1—O3iii90.18 (12)C1—N4—C5121.2 (4)
O1—Cd1—O3iii90.99 (11)N4—C1—C2120.9 (4)
O1i—Cd1—O3iii89.01 (11)N4—C1—H1A119.5
O3ii—Cd1—O3iii180.0C2—C1—H1A119.5
O2—Cd2—O2iv180.0C1—C2—C3119.4 (4)
O2—Cd2—N1v85.06 (12)C1—C2—H2A120.3
O2iv—Cd2—N1v94.94 (12)C3—C2—H2A120.3
O2—Cd2—N1i94.94 (12)C2—C3—C4118.0 (4)
O2iv—Cd2—N1i85.06 (12)C2—C3—C6120.9 (4)
N1v—Cd2—N1i180.000 (1)C4—C3—C6121.1 (4)
O2—Cd2—O4iv87.87 (12)C5—C4—C3120.4 (4)
O2iv—Cd2—O4iv92.13 (12)C5—C4—H4A119.8
N1v—Cd2—O4iv94.08 (12)C3—C4—H4A119.8
N1i—Cd2—O4iv85.92 (12)N4—C5—C4119.9 (4)
O2—Cd2—O492.13 (12)N4—C5—H5A120.0
O2iv—Cd2—O487.87 (12)C4—C5—H5A120.0
N1v—Cd2—O485.92 (12)O1—C6—O2127.4 (4)
N1i—Cd2—O494.08 (12)O1—C6—C3117.1 (4)
O4iv—Cd2—O4180.0O2—C6—C3115.5 (4)
C6—O1—Cd1132.5 (3)
N1—Cd1—O1—C6141.5 (4)O3—N4—C1—C2−177.8 (4)
N1i—Cd1—O1—C6−38.5 (4)C5—N4—C1—C22.5 (6)
O3ii—Cd1—O1—C651.2 (4)N4—C1—C2—C30.8 (6)
O3iii—Cd1—O1—C6−128.8 (4)C1—C2—C3—C4−3.5 (6)
N1v—Cd2—O2—C6136.6 (4)C1—C2—C3—C6174.4 (4)
N1i—Cd2—O2—C6−43.4 (4)C2—C3—C4—C52.9 (6)
O4iv—Cd2—O2—C6−129.1 (4)C6—C3—C4—C5−174.9 (4)
O4—Cd2—O2—C650.9 (4)O3—N4—C5—C4177.2 (4)
O1—Cd1—N1—N217.4 (4)C1—N4—C5—C4−3.1 (6)
O1i—Cd1—N1—N2−162.6 (4)C3—C4—C5—N40.3 (7)
O3ii—Cd1—N1—N2106.4 (4)Cd1—O1—C6—O238.1 (7)
O3iii—Cd1—N1—N2−73.6 (4)Cd1—O1—C6—C3−140.8 (3)
O1—Cd1—N1—Cd2vii−176.10 (19)Cd2—O2—C6—O115.1 (7)
O1i—Cd1—N1—Cd2vii3.90 (19)Cd2—O2—C6—C3−166.0 (3)
O3ii—Cd1—N1—Cd2vii−87.11 (18)C2—C3—C6—O19.4 (6)
O3iii—Cd1—N1—Cd2vii92.89 (18)C4—C3—C6—O1−172.8 (4)
Cd1vi—O3—N4—C1103.7 (4)C2—C3—C6—O2−169.6 (4)
Cd1vi—O3—N4—C5−76.7 (4)C4—C3—C6—O28.1 (6)
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2; (iii) x, y, z−1; (iv) −x, −y, −z+1; (v) x, y−1, z; (vi) x, y, z+1; (vii) x, y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4C···N3viii0.902.363.239 (7)167
O4—H4B···O3ix0.832.052.716 (4)137
Symmetry codes: (viii) −x+1, −y+1, −z+1; (ix) −x+1, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Cd1—N12.259 (3)Cd2—O22.242 (3)
Cd1—O12.289 (3)Cd2—N1ii2.284 (3)
Cd1—O3i2.370 (3)Cd2—O42.363 (3)
N1—Cd1—O185.90 (12)O2—Cd2—N1ii85.06 (12)
N1iii—Cd1—O194.10 (12)O2—Cd2—O4v87.87 (12)
N1—Cd1—O3i90.18 (12)O2v—Cd2—O4v92.13 (12)
O1—Cd1—O3i89.01 (11)N1ii—Cd2—O4v94.08 (12)
N1—Cd1—O3iv89.82 (12)N1iii—Cd2—O4v85.92 (12)
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, y−1, z; (iii) −x, −y+1, −z+1; (iv) x, y, z−1; (v) −x, −y, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4C···N3vi0.902.363.239 (7)167
O4—H4B···O3vii0.832.052.716 (4)137
Symmetry codes: (vi) −x+1, −y+1, −z+1; (vii) −x+1, −y+1, −z+2.
references
References top

Bai, L.-X., Han, W., Wang, W.-Z., Liu, X., Yan, S.-P. & Liao, D.-Z. (2004). Acta Cryst. E60, m953–m954.

Du, M., Zhang, Z.-H., Zhao, X.-J. & Xu, Q. (2006). Inorg. Chem. 45, 5785–5792.

Dybtsev, D. N., Chun, H., Yoon, S. H., Kim, D. & Kim, K. (2004). J. Am. Chem. Soc. 126, 32–33.

He, Z., Gao, E. Q., Wang, Z. M., Yan, C. H. & Kurmoo, M. (2005). Inorg. Chem. 44, 862–874.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zhao, Y.-H., Xu, H.-B., Shao, K.-Z., Xing, Y., Su, Z.-M. & Ma, J.-F. (2007). Cryst. Growth Des. 7, 513–520.