supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2056-m2057    [ doi:10.1107/S160053680703173X ]

catena-Poly[[diaquacobalt(II)]-[mu]3-5-aminoisophthalato-[kappa]4O,O':O'':N]

Y. Yang, M.-H. Zeng, S.-H. Zhang and H. Liang

Abstract top

In the title compound, [Co(C8H5NO4)(H2O)2]n, the CoII atom is coordinated in a distorted octahedral fashion by three O atoms of two carboxylate groups (one in a monodentate and one in a 1,3-bidentate mode) from two 5-aminoisophthalate anions, one N atom from the third 5-aminoisophthalate anion and two aqua ligands. The complex consists of an infinite neutral railroad-like linear polymer, which is packed into a three-dimensional framework through intricate N-H...O and O-H...O hydrogen bonding.

Comment top

In recent years, a large number of metal-organic compounds have been prepared because of the fascinating structural and topological features of these compounds and their potential applications as functional materials, such as catalysts, optical materials and molecule-based magnets (Hagrman et al., 1999; Moulton & Zaworotko, 2001; Janiak, 2003). 5-aminoisophthalic acid (AIP) (Dobson et al., 1998), a polydentate organic ligand containing an amino group and two carboxyl groups, can be used as a bridging and/or terminal ligand. In this field, studies have been focused on organic-inorganic hybrid materials containing N-donor rigid heteroaromatic ligands, such as pyrazine or 4,4' –bipyridine. However, much less work has been carried out to investigate transition metal polymers containing aminobenzoic acid ligands. Using AIP, we have hydrothermally prepared the title compound, [Co(AIP) (H2O)2]n. The title complex consists of one Co(II) cation, one 5-aminoisophthalate anion and two coordinated water molecules (Fig. 1). Each AIP ligand employs its two carboxylate groups and one amino group to coordinate to three different metal centers. Each CoII center possesses a distorted six-coordinated octahedral geometry, defined by three carboxyl oxygen atoms, one from a monodentate and two from a 1,3-bidentate AIP2- ligands, one nitrogen atom from the third 5-aminoisophthalate anion and two aqua ligands. The mean Co—O (carboxyl) bond distance is 2.092 (18) Å, which is slightly shorter than that in [Co(C8NH5O4)(H2O)]n (2.109 (2) Å) (Wu et al., 2002). This difference is probably attributed to the different coordination modes of the ligands. The most interesting feature is that the AIP ligands link cobalt centers in different ways to produces two different subrings A and B, which are both 14-membered rings located on an inversion centre, with Co—Co distances of 7.917 (3) and 7.689 (3) Å, respectively. THe difference between the rings is that the A ring is closed by bidentate carboxylate groups and the B ring by monodentate carboxylate groups. Together they form an open railroad-like framework polymer, running in the c direction. Each linear polymer is connected into a three-dimensional supramolecular network by intermolecular hydrogen bonds among aqua ligands, the oxygen atoms of carboxylate groups and amino groups (Table 2).

Related literature top

For related literature, see: Dobson & Gerkin (1998); Hagrman et al. (1999); Janiak (2003); Moulton & Zaworotko (2001); Wu et al. (2002).

Experimental top

Cobalt chlorine hexahydrate (0.119 g, 0.5 mmol), and 5-aminoisophthalic acid (0.0905 g, 0.5 mmol) were dissolved in water (9 ml). The solution was placed in a 15-ml Teflon-lined, stainless-steel, Parr bomb. The bomb was heated at 433 K for 6 days. The cooled-down mixture yielded light red crystals; these were washed with water and then dried in air (yield ca 70%, based on Co).

Refinement top

The water H atoms were located on difference Fourier maps; their coordinates and isotropic displacement parameters were refined freely. All other H atoms were positioned geometrically and refined with a riding model, with C—H distances of 0.95 (aromatic) Å, N—H distances of 0.92 Å, and with Uiso(H) = 1.2Ueq(C & N).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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.

Figures top
[Figure 1]
Fig. 1. A view of (I), showing 30% probability displacement ellipsoids.

Symmetry codes:(i)-x + 1,-y + 1,-z + 2; (ii) -x + 1,-y + 1,-z + 1.
catena-Poly[[diaquacobalt(II)]-µ3-5-aminoisophthalato- κ4O,O':O'':N] top
Crystal data top
[Co(C8H5NO4)(H2O)2]Z = 2
Mr = 274.10F(000) = 278
Triclinic, P1Dx = 1.969 Mg m−3
a = 6.4168 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.0919 (4) ÅCell parameters from 3976 reflections
c = 10.1493 (7) Åθ = 3.3–27.5°
α = 113.184 (1)°µ = 1.87 mm−1
β = 99.946 (3)°T = 153 K
γ = 98.995 (2)°PRISM, green
V = 462.28 (5) Å30.15 × 0.13 × 0.10 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2110 independent reflections
Radiation source: Rotating Anode1854 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.5°, θmin = 3.3°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.767, Tmax = 0.835k = −10→10
4523 measured reflectionsl = −13→13
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.0586P)2 + 0.466P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
2110 reflectionsΔρmax = 0.55 e Å−3
162 parametersΔρmin = −0.75 e Å−3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.007 (1)
Crystal data top
[Co(C8H5NO4)(H2O)2]γ = 98.995 (2)°
Mr = 274.10V = 462.28 (5) Å3
Triclinic, P1Z = 2
a = 6.4168 (4) ÅMo Kα radiation
b = 8.0919 (4) ŵ = 1.87 mm−1
c = 10.1493 (7) ÅT = 153 K
α = 113.184 (1)°0.15 × 0.13 × 0.10 mm
β = 99.946 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2110 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)		1854 reflections with I > 2σ(I)
Tmin = 0.767, Tmax = 0.835Rint = 0.027
4523 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096Δρmax = 0.55 e Å−3
S = 1.01Δρmin = −0.75 e Å−3
2110 reflectionsAbsolute structure: ?
162 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Co0.20196 (5)0.75115 (5)0.80493 (3)0.01298 (14)
O10.6666 (3)0.2413 (3)0.9957 (2)0.0187 (4)
O20.9520 (3)0.2510 (3)0.8966 (2)0.0244 (4)
O30.8351 (3)0.2502 (3)0.4037 (2)0.0201 (4)
O40.5073 (3)0.2130 (3)0.2718 (2)0.0187 (4)
O50.2461 (3)1.0316 (3)0.9070 (2)0.0218 (4)
O6−0.1152 (3)0.7068 (3)0.8195 (2)0.0213 (4)
N0.1401 (4)0.4592 (3)0.7069 (2)0.0165 (4)
H0A0.07450.41800.76590.020*
H0B0.03890.41550.61720.020*
C10.3142 (4)0.3725 (4)0.6807 (3)0.0166 (5)
C20.4366 (4)0.3411 (4)0.7907 (3)0.0184 (5)
H20.39830.37180.88230.022*
C30.6145 (4)0.2655 (4)0.7693 (3)0.0164 (5)
C40.6708 (4)0.2196 (4)0.6345 (3)0.0171 (5)
H40.79070.16560.61820.021*
C50.5498 (4)0.2536 (4)0.5241 (3)0.0171 (5)
C60.3705 (4)0.3267 (4)0.5456 (3)0.0169 (5)
H60.28570.34560.46870.020*
C70.7566 (4)0.2477 (3)0.8947 (3)0.0168 (5)
C80.6319 (4)0.2345 (4)0.3918 (3)0.0162 (5)
H5A0.150 (7)1.097 (6)0.873 (5)0.047 (12)*
H5B0.373 (9)1.097 (7)0.930 (6)0.068 (16)*
H6A−0.227 (7)0.764 (6)0.792 (5)0.046 (11)*
H6B−0.093 (8)0.719 (6)0.910 (5)0.051 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0108 (2)0.0199 (2)0.0113 (2)0.00718 (13)0.00536 (13)0.00760 (15)
O10.0169 (9)0.0289 (10)0.0139 (9)0.0070 (8)0.0050 (7)0.0119 (8)
O20.0179 (10)0.0403 (12)0.0225 (10)0.0142 (9)0.0086 (8)0.0171 (10)
O30.0170 (9)0.0317 (11)0.0153 (9)0.0092 (8)0.0066 (7)0.0119 (9)
O40.0155 (9)0.0282 (10)0.0154 (9)0.0086 (8)0.0066 (7)0.0101 (8)
O50.0183 (10)0.0240 (10)0.0248 (10)0.0088 (8)0.0079 (8)0.0100 (9)
O60.0144 (9)0.0321 (11)0.0203 (10)0.0091 (8)0.0076 (8)0.0116 (9)
N0.0137 (10)0.0207 (11)0.0157 (10)0.0061 (8)0.0050 (8)0.0075 (9)
C10.0157 (12)0.0180 (12)0.0171 (12)0.0051 (10)0.0069 (10)0.0071 (11)
C20.0170 (12)0.0230 (12)0.0175 (12)0.0055 (10)0.0076 (10)0.0096 (11)
C30.0167 (12)0.0198 (12)0.0141 (12)0.0050 (10)0.0056 (10)0.0079 (11)
C40.0157 (12)0.0179 (12)0.0202 (13)0.0071 (10)0.0072 (10)0.0087 (11)
C50.0175 (12)0.0209 (12)0.0135 (12)0.0043 (10)0.0074 (10)0.0068 (11)
C60.0172 (12)0.0197 (12)0.0148 (12)0.0054 (10)0.0045 (10)0.0080 (11)
C70.0194 (13)0.0172 (12)0.0169 (12)0.0076 (10)0.0069 (10)0.0085 (11)
C80.0174 (12)0.0186 (12)0.0144 (12)0.0064 (10)0.0046 (10)0.0081 (11)
Geometric parameters (Å, °) top
Co—O1i2.0266 (18)O6—H6B0.86 (5)
Co—O52.037 (2)N—C11.418 (3)
Co—O62.0516 (19)N—H0A0.9200
Co—O3ii2.0848 (18)N—H0B0.9200
Co—N2.109 (2)C1—C21.382 (4)
Co—O4ii2.1631 (18)C1—C61.401 (4)
Co—C8ii2.452 (3)C2—C31.387 (4)
O1—C71.274 (3)C2—H20.9500
O1—Coi2.0266 (18)C3—C41.397 (4)
O2—C71.246 (3)C3—C71.503 (3)
O3—C81.270 (3)C4—C51.394 (4)
O3—Coii2.0848 (18)C4—H40.9500
O4—C81.267 (3)C5—C61.385 (4)
O4—Coii2.1632 (18)C5—C81.487 (3)
O5—H5A0.98 (4)C6—H60.9500
O5—H5B0.84 (6)C8—Coii2.452 (3)
O6—H6A0.97 (4)
O1i—Co—O588.76 (8)Co—N—H0A107.3
O1i—Co—O695.54 (8)C1—N—H0B107.3
O5—Co—O691.77 (8)Co—N—H0B107.3
O1i—Co—O3ii162.55 (8)H0A—N—H0B106.9
O5—Co—O3ii92.15 (8)C2—C1—C6119.4 (2)
O6—Co—O3ii101.84 (8)C2—C1—N120.4 (2)
O1i—Co—N89.82 (8)C6—C1—N120.1 (2)
O5—Co—N176.15 (8)C1—C2—C3121.0 (2)
O6—Co—N84.80 (9)C1—C2—H2119.5
O3ii—Co—N90.27 (8)C3—C2—H2119.5
O1i—Co—O4ii100.38 (7)C2—C3—C4119.7 (2)
O5—Co—O4ii90.18 (8)C2—C3—C7120.1 (2)
O6—Co—O4ii163.99 (8)C4—C3—C7120.1 (2)
O3ii—Co—O4ii62.20 (7)C5—C4—C3119.6 (2)
N—Co—O4ii93.60 (8)C5—C4—H4120.2
O1i—Co—C8ii131.37 (8)C3—C4—H4120.2
O5—Co—C8ii92.79 (8)C6—C5—C4120.3 (2)
O6—Co—C8ii132.92 (9)C6—C5—C8120.0 (2)
O3ii—Co—C8ii31.18 (8)C4—C5—C8119.2 (2)
N—Co—C8ii90.83 (8)C5—C6—C1120.0 (2)
O4ii—Co—C8ii31.08 (8)C5—C6—H6120.0
C7—O1—Coi130.14 (17)C1—C6—H6120.0
C8—O3—Coii90.60 (15)O2—C7—O1125.6 (2)
C8—O4—Coii87.15 (15)O2—C7—C3118.7 (2)
Co—O5—H5A123 (3)O1—C7—C3115.7 (2)
Co—O5—H5B117 (4)O4—C8—O3119.8 (2)
H5A—O5—H5B106 (4)O4—C8—C5121.9 (2)
Co—O6—H6A128 (3)O3—C8—C5118.2 (2)
Co—O6—H6B99 (3)O4—C8—Coii61.77 (13)
H6A—O6—H6B114 (4)O3—C8—Coii58.23 (13)
C1—N—Co120.08 (17)C5—C8—Coii171.81 (19)
C1—N—H0A107.3
O1i—Co—N—C1−74.77 (19)C2—C1—C6—C5−1.1 (4)
O6—Co—N—C1−170.35 (19)N—C1—C6—C5175.6 (2)
O3ii—Co—N—C187.78 (19)Coi—O1—C7—O23.9 (4)
O4ii—Co—N—C125.62 (19)Coi—O1—C7—C3−171.81 (17)
C8ii—Co—N—C156.61 (19)C2—C3—C7—O2−152.1 (3)
Co—N—C1—C286.4 (3)C4—C3—C7—O222.9 (4)
Co—N—C1—C6−90.3 (3)C2—C3—C7—O123.9 (4)
C6—C1—C2—C30.2 (4)C4—C3—C7—O1−161.1 (2)
N—C1—C2—C3−176.5 (2)Coii—O4—C8—O3−4.7 (2)
C1—C2—C3—C4−0.2 (4)Coii—O4—C8—C5171.5 (2)
C1—C2—C3—C7174.8 (2)Coii—O3—C8—O44.8 (3)
C2—C3—C4—C51.2 (4)Coii—O3—C8—C5−171.5 (2)
C7—C3—C4—C5−173.8 (2)C6—C5—C8—O4−27.7 (4)
C3—C4—C5—C6−2.2 (4)C4—C5—C8—O4160.3 (2)
C3—C4—C5—C8169.8 (2)C6—C5—C8—O3148.5 (3)
C4—C5—C6—C12.1 (4)C4—C5—C8—O3−23.4 (4)
C8—C5—C6—C1−169.8 (2)
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N—H0A···O2iii0.922.383.275 (3)165
N—H0B···O3iii0.922.092.991 (3)165
O5—H5B···O1iv0.84 (6)1.90 (6)2.738 (3)175 (5)
O5—H5A···O2v0.98 (4)1.89 (5)2.802 (3)154 (4)
O6—H6B···O2i0.86 (5)1.92 (5)2.755 (3)162 (4)
O6—H6A···O4vi0.97 (4)1.87 (5)2.791 (3)158 (4)
Symmetry codes: (iii) x−1, y, z; (iv) x, y+1, z; (v) x−1, y+1, z; (i) −x+1, −y+1, −z+2; (vi) −x, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Co—O1i2.0266 (18)Co—O3ii2.0848 (18)
Co—O52.037 (2)Co—N2.109 (2)
Co—O62.0516 (19)Co—O4ii2.1631 (18)
O1i—Co—O588.76 (8)O5—Co—N176.15 (8)
O1i—Co—O695.54 (8)O6—Co—N84.80 (9)
O5—Co—O691.77 (8)O3ii—Co—N90.27 (8)
O1i—Co—O3ii162.55 (8)O1i—Co—O4ii100.38 (7)
O5—Co—O3ii92.15 (8)O5—Co—O4ii90.18 (8)
O6—Co—O3ii101.84 (8)O6—Co—O4ii163.99 (8)
O1i—Co—N89.82 (8)O3ii—Co—O4ii62.20 (7)
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N—H0A···O2iii0.922.383.275 (3)165
N—H0B···O3iii0.922.092.991 (3)165
O5—H5B···O1iv0.84 (6)1.90 (6)2.738 (3)175 (5)
O5—H5A···O2v0.98 (4)1.89 (5)2.802 (3)154 (4)
O6—H6B···O2i0.86 (5)1.92 (5)2.755 (3)162 (4)
O6—H6A···O4vi0.97 (4)1.87 (5)2.791 (3)158 (4)
Symmetry codes: (iii) x−1, y, z; (iv) x, y+1, z; (v) x−1, y+1, z; (i) −x+1, −y+1, −z+2; (vi) −x, −y+1, −z+1.
Acknowledgements top

We acknowledge financial support from the NSFC (author please give this abbreviation in full) (Nos. 30460153, 20561001), and the Natural Science Foundation of Guangxi Province (No. 0447019).

references
References top

Dobson, A. J. & Gerkin, R. E. (1998). Acta Cryst. C54, 1503–1505.

Hagrman, P. J., Hagramn, D. & Zubicta, J. (1999). Angew. Chem. Int. Ed. 38, 2638–2684.

Janiak, C. (2003). Dalton Trans. pp. 2781–2804.

Moulton, B. & Zaworotko, M. J. (2001). Chem. Rev. 101, 1629–1658.

Rigaku (2004). RAPID-AUTO. Version 3.0. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Wu, C.-D., Lu, C.-Z., Yang, W.-B., Zuang, H.-H. & Huang, J.-S. (2002). J. Inorg. Chem. 41, 3302–3307.