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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703173X/kj2057sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680703173X/kj2057Isup2.hkl
Contains datablock I

CCDC reference: 626651

Key indicators

  • Single-crystal X-ray study
  • T = 153 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.032
  • wR factor = 0.096
  • Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.40 Ratio PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.26 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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).

Structure description 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).

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

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.027
ω scansθmax = 27.5°, θmin = 3.3°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.767, Tmax = 0.835k = 1010
4523 measured reflectionsl = 1313
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 Å3
162 parametersΔρmin = 0.75 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.096H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.55 e Å3
2110 reflectionsΔρmin = 0.75 e Å3
162 parameters
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)
O60.1152 (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)*
H6A0.227 (7)0.764 (6)0.792 (5)0.046 (11)*
H6B0.093 (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, º) 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—C174.77 (19)C2—C1—C6—C51.1 (4)
O6—Co—N—C1170.35 (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—C3171.81 (17)
C8ii—Co—N—C156.61 (19)C2—C3—C7—O2152.1 (3)
Co—N—C1—C286.4 (3)C4—C3—C7—O222.9 (4)
Co—N—C1—C690.3 (3)C2—C3—C7—O123.9 (4)
C6—C1—C2—C30.2 (4)C4—C3—C7—O1161.1 (2)
N—C1—C2—C3176.5 (2)Coii—O4—C8—O34.7 (2)
C1—C2—C3—C40.2 (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—C5171.5 (2)
C7—C3—C4—C5173.8 (2)C6—C5—C8—O427.7 (4)
C3—C4—C5—C62.2 (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—O323.4 (4)
C8—C5—C6—C1169.8 (2)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) 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: (i) x+1, y+1, z+2; (iii) x1, y, z; (iv) x, y+1, z; (v) x1, y+1, z; (vi) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Co(C8H5NO4)(H2O)2]
Mr274.10
Crystal system, space groupTriclinic, P1
Temperature (K)153
a, b, c (Å)6.4168 (4), 8.0919 (4), 10.1493 (7)
α, β, γ (°)113.184 (1), 99.946 (3), 98.995 (2)
V3)462.28 (5)
Z2
Radiation typeMo Kα
µ (mm1)1.87
Crystal size (mm)0.15 × 0.13 × 0.10
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.767, 0.835
No. of measured, independent and
observed [I > 2σ(I)] reflections
4523, 2110, 1854
Rint0.027
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.096, 1.01
No. of reflections2110
No. of parameters162
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.55, 0.75

Computer programs: RAPID-AUTO (Rigaku, 2004), RAPID-AUTO, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) 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.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H0A···O2iii0.922.383.275 (3)165.4
N—H0B···O3iii0.922.092.991 (3)164.5
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: (i) x+1, y+1, z+2; (iii) x1, y, z; (iv) x, y+1, z; (v) x1, y+1, z; (vi) x, y+1, z+1.
 

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