metal-organic compounds
Poly[diaquabis(μ2-azido-κ2N1:N1)bis(μ3-1-oxoisonicotinato-κ3O:O′:O′′)dicadmium(II)]
aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China, and bDepartment of Chemistry, Key Laboratory of Medicinal Chemistry for Natural Resources, Ministry of Education, Yunnan University, Kunming 650091, People's Republic of China
*Correspondence e-mail: chmsunbw@seu.edu.cn
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 involves O—H⋯N and O—H⋯O hydrogen bonds.
Related literature
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
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; 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.
Supporting information
10.1107/S1600536808013196/hy2123sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808013196/hy2123Isup2.hkl
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.
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).
Data collection: CrystalClear (Rigaku, 2005); cell
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).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.] | |
Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines. |
[Cd2(C6H4NO3)2(N3)2(H2O)2] | Z = 1 |
Mr = 621.10 | F(000) = 300 |
Triclinic, P1 | Dx = 2.312 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5409 (17) Å | Cell parameters from 2159 reflections |
b = 7.850 (2) Å | θ = 3.1–26.8° |
c = 9.410 (3) Å | µ = 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 |
Rigaku Scxmini 1K CCD area-detector diffractometer | 1567 independent reflections |
Radiation source: fine-focus sealed tube | 1438 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 8.192 pixels mm-1 | θmax = 25.0°, θmin = 2.8° |
thin–slice ω scans | h = −7→7 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −9→7 |
Tmin = 0.612, Tmax = 0.613 | l = −11→10 |
5082 measured reflections |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-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 parameters | Δρmax = 0.60 e Å−3 |
1 restraint | Δρmin = −1.02 e Å−3 |
[Cd2(C6H4NO3)2(N3)2(H2O)2] | γ = 107.566 (5)° |
Mr = 621.10 | V = 446.1 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.5409 (17) Å | Mo Kα radiation |
b = 7.850 (2) Å | µ = 2.45 mm−1 |
c = 9.410 (3) Å | T = 223 K |
α = 99.668 (6)° | 0.3 × 0.2 × 0.2 mm |
β = 97.164 (6)° |
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 = 0.613 | Rint = 0.022 |
5082 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 1 restraint |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.60 e Å−3 |
1567 reflections | Δρmin = −1.02 e Å−3 |
139 parameters |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.0000 | 0.5000 | 0.5000 | 0.01556 (17) | |
Cd2 | 0.0000 | 0.0000 | 0.5000 | 0.01683 (17) | |
O1 | 0.1884 (5) | 0.4600 (4) | 0.7066 (3) | 0.0244 (7) | |
O2 | 0.0598 (6) | 0.1674 (4) | 0.7283 (3) | 0.0311 (8) | |
O3 | 0.3130 (5) | 0.5495 (5) | 1.3892 (3) | 0.0270 (7) | |
O4 | 0.3676 (5) | 0.1301 (5) | 0.4778 (4) | 0.0295 (8) | |
H4B | 0.4361 | 0.2055 | 0.5546 | 0.035* | |
H4C | 0.4127 | 0.0951 | 0.3945 | 0.035* | |
N1 | 0.1164 (6) | 0.7997 (5) | 0.6110 (4) | 0.0201 (8) | |
N2 | 0.2664 (6) | 0.8640 (5) | 0.7131 (4) | 0.0227 (8) | |
N3 | 0.4108 (8) | 0.9283 (6) | 0.8078 (6) | 0.0506 (14) | |
N4 | 0.2847 (6) | 0.5005 (5) | 1.2437 (4) | 0.0208 (8) | |
C1 | 0.3105 (6) | 0.6288 (6) | 1.1625 (5) | 0.0213 (9) | |
H1A | 0.3534 | 0.7529 | 1.2095 | 0.026* | |
C2 | 0.2752 (6) | 0.5808 (6) | 1.0126 (5) | 0.0171 (8) | |
H2A | 0.2954 | 0.6714 | 0.9569 | 0.021* | |
C3 | 0.2086 (6) | 0.3959 (6) | 0.9430 (4) | 0.0168 (8) | |
C4 | 0.1925 (7) | 0.2671 (6) | 1.0312 (5) | 0.0216 (9) | |
H4A | 0.1547 | 0.1423 | 0.9873 | 0.026* | |
C5 | 0.2314 (7) | 0.3216 (6) | 1.1804 (5) | 0.0240 (9) | |
H5A | 0.2211 | 0.2345 | 1.2391 | 0.029* | |
C6 | 0.1483 (7) | 0.3368 (6) | 0.7782 (5) | 0.0189 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0215 (3) | 0.0136 (2) | 0.0112 (2) | 0.00553 (18) | 0.00313 (17) | 0.00218 (17) |
Cd2 | 0.0216 (3) | 0.0152 (3) | 0.0132 (3) | 0.00717 (18) | 0.00221 (17) | 0.00086 (17) |
O1 | 0.0288 (16) | 0.0273 (17) | 0.0148 (15) | 0.0069 (14) | 0.0003 (12) | 0.0050 (13) |
O2 | 0.049 (2) | 0.0251 (18) | 0.0161 (15) | 0.0136 (16) | 0.0021 (14) | −0.0019 (13) |
O3 | 0.0253 (16) | 0.0362 (19) | 0.0095 (15) | −0.0004 (14) | 0.0045 (12) | −0.0036 (13) |
O4 | 0.0259 (17) | 0.0337 (19) | 0.0214 (17) | 0.0014 (15) | 0.0050 (14) | 0.0010 (14) |
N1 | 0.028 (2) | 0.0120 (16) | 0.0175 (18) | 0.0069 (15) | −0.0020 (16) | 0.0005 (14) |
N2 | 0.027 (2) | 0.0149 (17) | 0.027 (2) | 0.0079 (16) | 0.0011 (19) | 0.0071 (16) |
N3 | 0.054 (3) | 0.024 (2) | 0.055 (3) | 0.004 (2) | −0.029 (3) | 0.003 (2) |
N4 | 0.0178 (17) | 0.028 (2) | 0.0146 (17) | 0.0054 (15) | 0.0059 (14) | 0.0020 (15) |
C1 | 0.0146 (19) | 0.024 (2) | 0.022 (2) | 0.0038 (17) | 0.0020 (17) | 0.0015 (18) |
C2 | 0.0159 (19) | 0.020 (2) | 0.018 (2) | 0.0079 (16) | 0.0050 (16) | 0.0061 (16) |
C3 | 0.0133 (18) | 0.020 (2) | 0.017 (2) | 0.0061 (16) | 0.0044 (16) | 0.0029 (16) |
C4 | 0.030 (2) | 0.017 (2) | 0.020 (2) | 0.0099 (18) | 0.0079 (18) | 0.0047 (17) |
C5 | 0.025 (2) | 0.028 (2) | 0.017 (2) | 0.0057 (19) | 0.0076 (18) | 0.0046 (18) |
C6 | 0.017 (2) | 0.027 (2) | 0.016 (2) | 0.0120 (18) | 0.0034 (16) | 0.0047 (18) |
Cd1—N1 | 2.259 (3) | O4—H4B | 0.8300 |
Cd1—N1i | 2.259 (3) | O4—H4C | 0.9000 |
Cd1—O1 | 2.289 (3) | N1—N2 | 1.201 (5) |
Cd1—O1i | 2.289 (3) | N1—Cd2vii | 2.284 (3) |
Cd1—O3ii | 2.370 (3) | N2—N3 | 1.137 (6) |
Cd1—O3iii | 2.370 (3) | N4—C1 | 1.347 (6) |
Cd2—O2 | 2.242 (3) | N4—C5 | 1.349 (6) |
Cd2—O2iv | 2.242 (3) | C1—C2 | 1.369 (6) |
Cd2—N1v | 2.284 (3) | C1—H1A | 0.9400 |
Cd2—N1i | 2.284 (3) | C2—C3 | 1.397 (6) |
Cd2—O4iv | 2.363 (3) | C2—H2A | 0.9400 |
Cd2—O4 | 2.363 (3) | C3—C4 | 1.401 (6) |
O1—C6 | 1.252 (5) | C3—C6 | 1.507 (6) |
O2—C6 | 1.257 (5) | C4—C5 | 1.365 (6) |
O3—N4 | 1.332 (5) | C4—H4A | 0.9400 |
O3—Cd1vi | 2.370 (3) | C5—H5A | 0.9400 |
N1—Cd1—N1i | 180.000 (1) | C6—O2—Cd2 | 130.6 (3) |
N1—Cd1—O1 | 85.90 (12) | N4—O3—Cd1vi | 118.5 (2) |
N1i—Cd1—O1 | 94.10 (12) | Cd2—O4—H4B | 109.5 |
N1—Cd1—O1i | 94.10 (12) | Cd2—O4—H4C | 120.1 |
N1i—Cd1—O1i | 85.90 (12) | H4B—O4—H4C | 130.4 |
O1—Cd1—O1i | 180.0 | N2—N1—Cd1 | 122.0 (3) |
N1—Cd1—O3ii | 90.18 (12) | N2—N1—Cd2vii | 117.2 (3) |
N1i—Cd1—O3ii | 89.82 (12) | Cd1—N1—Cd2vii | 119.53 (15) |
O1—Cd1—O3ii | 89.01 (11) | N3—N2—N1 | 178.2 (5) |
O1i—Cd1—O3ii | 90.99 (11) | O3—N4—C1 | 120.0 (4) |
N1—Cd1—O3iii | 89.82 (12) | O3—N4—C5 | 118.9 (4) |
N1i—Cd1—O3iii | 90.18 (12) | C1—N4—C5 | 121.2 (4) |
O1—Cd1—O3iii | 90.99 (11) | N4—C1—C2 | 120.9 (4) |
O1i—Cd1—O3iii | 89.01 (11) | N4—C1—H1A | 119.5 |
O3ii—Cd1—O3iii | 180.0 | C2—C1—H1A | 119.5 |
O2—Cd2—O2iv | 180.0 | C1—C2—C3 | 119.4 (4) |
O2—Cd2—N1v | 85.06 (12) | C1—C2—H2A | 120.3 |
O2iv—Cd2—N1v | 94.94 (12) | C3—C2—H2A | 120.3 |
O2—Cd2—N1i | 94.94 (12) | C2—C3—C4 | 118.0 (4) |
O2iv—Cd2—N1i | 85.06 (12) | C2—C3—C6 | 120.9 (4) |
N1v—Cd2—N1i | 180.000 (1) | C4—C3—C6 | 121.1 (4) |
O2—Cd2—O4iv | 87.87 (12) | C5—C4—C3 | 120.4 (4) |
O2iv—Cd2—O4iv | 92.13 (12) | C5—C4—H4A | 119.8 |
N1v—Cd2—O4iv | 94.08 (12) | C3—C4—H4A | 119.8 |
N1i—Cd2—O4iv | 85.92 (12) | N4—C5—C4 | 119.9 (4) |
O2—Cd2—O4 | 92.13 (12) | N4—C5—H5A | 120.0 |
O2iv—Cd2—O4 | 87.87 (12) | C4—C5—H5A | 120.0 |
N1v—Cd2—O4 | 85.92 (12) | O1—C6—O2 | 127.4 (4) |
N1i—Cd2—O4 | 94.08 (12) | O1—C6—C3 | 117.1 (4) |
O4iv—Cd2—O4 | 180.0 | O2—C6—C3 | 115.5 (4) |
C6—O1—Cd1 | 132.5 (3) | ||
N1—Cd1—O1—C6 | 141.5 (4) | O3—N4—C1—C2 | −177.8 (4) |
N1i—Cd1—O1—C6 | −38.5 (4) | C5—N4—C1—C2 | 2.5 (6) |
O3ii—Cd1—O1—C6 | 51.2 (4) | N4—C1—C2—C3 | 0.8 (6) |
O3iii—Cd1—O1—C6 | −128.8 (4) | C1—C2—C3—C4 | −3.5 (6) |
N1v—Cd2—O2—C6 | 136.6 (4) | C1—C2—C3—C6 | 174.4 (4) |
N1i—Cd2—O2—C6 | −43.4 (4) | C2—C3—C4—C5 | 2.9 (6) |
O4iv—Cd2—O2—C6 | −129.1 (4) | C6—C3—C4—C5 | −174.9 (4) |
O4—Cd2—O2—C6 | 50.9 (4) | O3—N4—C5—C4 | 177.2 (4) |
O1—Cd1—N1—N2 | 17.4 (4) | C1—N4—C5—C4 | −3.1 (6) |
O1i—Cd1—N1—N2 | −162.6 (4) | C3—C4—C5—N4 | 0.3 (7) |
O3ii—Cd1—N1—N2 | 106.4 (4) | Cd1—O1—C6—O2 | 38.1 (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—O1 | 15.1 (7) |
O1i—Cd1—N1—Cd2vii | 3.90 (19) | Cd2—O2—C6—C3 | −166.0 (3) |
O3ii—Cd1—N1—Cd2vii | −87.11 (18) | C2—C3—C6—O1 | 9.4 (6) |
O3iii—Cd1—N1—Cd2vii | 92.89 (18) | C4—C3—C6—O1 | −172.8 (4) |
Cd1vi—O3—N4—C1 | 103.7 (4) | C2—C3—C6—O2 | −169.6 (4) |
Cd1vi—O3—N4—C5 | −76.7 (4) | C4—C3—C6—O2 | 8.1 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4C···N3viii | 0.90 | 2.36 | 3.239 (7) | 167 |
O4—H4B···O3ix | 0.83 | 2.05 | 2.716 (4) | 137 |
Symmetry codes: (viii) −x+1, −y+1, −z+1; (ix) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cd2(C6H4NO3)2(N3)2(H2O)2] |
Mr | 621.10 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 223 |
a, b, c (Å) | 6.5409 (17), 7.850 (2), 9.410 (3) |
α, β, γ (°) | 99.668 (6), 97.164 (6), 107.566 (5) |
V (Å3) | 446.1 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.45 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Rigaku Scxmini 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.612, 0.613 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5082, 1567, 1438 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.087, 1.08 |
No. of reflections | 1567 |
No. of parameters | 139 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −1.02 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006) and SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cd1—N1 | 2.259 (3) | Cd2—O2 | 2.242 (3) |
Cd1—O1 | 2.289 (3) | Cd2—N1ii | 2.284 (3) |
Cd1—O3i | 2.370 (3) | Cd2—O4 | 2.363 (3) |
N1—Cd1—O1 | 85.90 (12) | O2—Cd2—N1ii | 85.06 (12) |
N1iii—Cd1—O1 | 94.10 (12) | O2—Cd2—O4v | 87.87 (12) |
N1—Cd1—O3i | 90.18 (12) | O2v—Cd2—O4v | 92.13 (12) |
O1—Cd1—O3i | 89.01 (11) | N1ii—Cd2—O4v | 94.08 (12) |
N1—Cd1—O3iv | 89.82 (12) | N1iii—Cd2—O4v | 85.92 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4C···N3vi | 0.90 | 2.36 | 3.239 (7) | 167 |
O4—H4B···O3vii | 0.83 | 2.05 | 2.716 (4) | 137 |
Symmetry codes: (vi) −x+1, −y+1, −z+1; (vii) −x+1, −y+1, −z+2. |
References
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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).