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The title compound, {[Cu(C8H6NO4)2]·H2O}n, was prepared by the hydro­thermal assembly of 5-amino­isophthalic acid with copper nitrate. Single-crystal X-ray analysis shows that it has a two-dimensional layer coordination framework, in which the unique Cu atom lies on an inversion centre and adopts a square-planar geometry, coordinated to two N and two O atoms from symmetry-related ligands. The water molecule lies on a twofold axis and there are hydrogen-bonding interactions between the layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104020426/hj1020sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104020426/hj1020Isup2.hkl
Contains datablock I

CCDC reference: 254905

Comment top

Through coordination bonds and non-covalent interactions, such as hydrogen bonds and/or ππ stacking interactions, the self-assembly method has proved to be a powerful tool for the construction of supramolecular structures (Batten & Robson, 1998; Moulton & Zaworotko, 2001; Kepert & Rosseinsky, 1999; Biradha & Fujita, 2000). Multi-dimensional frameworks containing large channels of various shapes and sizes (Yaghi et al., 1996, 1997; Subramanian & Zaworotko, 1995; Harrison & Hannooman, 1997) and intercalating arrays (Vaccari, 1999) have recently been reported. Coordination of transition metals to multidentate ligands is one of the main design principles.

As a rigid multidentate ligand, 5-aminoisophthalic acid (AIP) has received considerable attention, owing to its variety of possible bridging modes (Wu Lu Yang et al., 2002; Wu Lu Zhuang et al., 2002; Xu et al., 2002; Tao et al., 2003; Yang et al., 2003; Yang & Zheng, 2003). It can engage in three types of intermolecular interactions, namely M—L bonding, hydrogen bonding and ππ stacking interactions. In order to understand its interesting chemistry, we recently studied the assembly reaction of AIP with various metal ions in solution or under hydrothermal conditions. Here, we report the synthesis and crystal structure of the title compound, (I), which has a two-dimensional layer network. \sch

Compound (I) crystallizes in the monoclinic space group C2/c. As illustrated in Fig. 1, the CuII atom, situated in the centre of a square plane, is coordinated by two O atoms and two N atoms from four different AIP ligands. The ligand uses its amino group and one of its two carboxyl groups to coordinate two CuII moieties [Cu—N 2.026 (4) Å and Cu—O 1.969 (3) Å]; the other carboxyl group is left free. This coordination pattern of AIP is similar to that in the complex [Co(C8NH6O4)2(H2O)]n (Wu Lu Zhuang et al. 2002), where the central CoII ion adopts an octahedral geometry.

The coordination around the CuII ion in (I) leads to a two-dimensional layer network and Fig. 2 shows the packing of the complex along the a axis. There is intramolecular hydrogen bonding within these two-dimensional layers [O2—O4(x, 1 − y, z − 1/2) 2.554 (6) Å].

Fig. 3 shows the unit-cell packing diagram viewed from the b direction. Interestingly, the two-dimensional networks are packed into a three-dimensional framework via interlayer hydrogen-bonding interactions [N1—O1 2.944 (6) Å]. There are also isolated water molecules between the layers, which form hydrogen bonds with the two-dimensional layers, with N1···OW 2.923 (6) and OW1···O4 3.294 (6) Å. The N1—H1B···OW angle is 127.0° and the OW1—HW1A···O4 angle is 157 (7)°.

Experimental top

A mixture of Cu(NO3)2·3H2O (2 mmol) and 5-aminoisophthalic acid (1 mmol) in water (15 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and heated to 413 K for 6 d under autogenous pressure. After slow cooling of the reaction solution to room temperature, black prism crystals of (I) suitable for X-ray analysis were obtained. Elemental analyses were performed on an EL III CHNOS Elemental Analyzer. Analysis, found: C 43.87, H 2.48, N 6.24%; calculated: C 43.50, H 3.19, N 6.34%.

Refinement top

Hydroxy and water H atoms were located from difference maps and refined freely. H atoms bonded to C or N atoms were placed in calculated positions and refined with isotropic displacement parameters using a riding model, with C—H = 0.93 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N). Please check amended text.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I), with the atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms and isolated water molecules have been omitted for clarity.
[Figure 2] Fig. 2. The extended two-dimensional lamellar structure of (I), viewed along the a direction. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
[Figure 3] Fig. 3. Unit-cell packing diagram of (I), viewed along the b direction, showing the interlayer hydrogen bonding connecting the two-dimensional layers into a three-dimensional framework. Displacement ellipsoids are drawn at the 50% probability level and hydrogen bonds are depicted by dashed lines.
Poly[[copper(II)-di-µ-5-aminoisophthalato(1-)-κ4N:O] monohydrate] top
Crystal data top
[Cu(C8H6NO4)2]·H2OF(000) = 900
Mr = 441.83Dx = 1.868 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1257 reflections
a = 13.2692 (11) Åθ = 2.7–25.0°
b = 9.1898 (8) ŵ = 1.45 mm1
c = 13.5155 (11) ÅT = 293 K
β = 107.542 (2)°Prism, black
V = 1571.5 (2) Å30.36 × 0.20 × 0.20 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer
1359 independent reflections
Radiation source: fine-focus sealed tube1117 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ϕ and ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1512
Tmin = 0.723, Tmax = 0.748k = 108
2289 measured reflectionsl = 1613
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0601P)2 + 12.8787P]
where P = (Fo2 + 2Fc2)/3
1359 reflections(Δ/σ)max = 0.002
137 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = 0.83 e Å3
Crystal data top
[Cu(C8H6NO4)2]·H2OV = 1571.5 (2) Å3
Mr = 441.83Z = 4
Monoclinic, C2/cMo Kα radiation
a = 13.2692 (11) ŵ = 1.45 mm1
b = 9.1898 (8) ÅT = 293 K
c = 13.5155 (11) Å0.36 × 0.20 × 0.20 mm
β = 107.542 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
1359 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
1117 reflections with I > 2σ(I)
Tmin = 0.723, Tmax = 0.748Rint = 0.029
2289 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.136H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0601P)2 + 12.8787P]
where P = (Fo2 + 2Fc2)/3
1359 reflectionsΔρmax = 0.68 e Å3
137 parametersΔρmin = 0.83 e Å3
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
Cu10.25000.25000.50000.0217 (3)
O40.3735 (3)0.3673 (4)0.3580 (3)0.0381 (10)
O30.2972 (3)0.1614 (4)0.3888 (3)0.0323 (9)
O20.3733 (3)0.4606 (4)0.0064 (3)0.0332 (9)
H2B0.374 (4)0.510 (6)0.044 (4)0.028 (15)*
O10.4182 (3)0.2832 (4)0.0857 (3)0.0344 (10)
OW10.00000.0963 (6)0.25000.0391 (14)
HW1A0.017 (7)0.036 (9)0.296 (6)0.09 (3)*
N10.3816 (3)0.1774 (4)0.1109 (3)0.0239 (9)
H1A0.39150.20630.05410.029*
H1B0.37410.24000.15550.029*
C10.3775 (4)0.0240 (5)0.1316 (3)0.0190 (10)
C20.3900 (4)0.0737 (5)0.0575 (4)0.0212 (10)
H2A0.40390.03960.00180.025*
C30.3817 (4)0.2221 (5)0.0724 (4)0.0203 (11)
C40.3648 (4)0.2742 (5)0.1628 (4)0.0203 (10)
H4A0.36000.37380.17280.024*
C50.3550 (4)0.1769 (5)0.2379 (4)0.0207 (10)
C60.3591 (4)0.0266 (5)0.2222 (3)0.0197 (10)
H6A0.34970.03860.27130.024*
C70.3931 (4)0.3237 (6)0.0107 (4)0.0234 (11)
C80.3412 (4)0.2400 (5)0.3357 (4)0.0219 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0340 (5)0.0175 (5)0.0184 (4)0.0047 (4)0.0148 (3)0.0037 (4)
O10.047 (2)0.038 (2)0.0279 (19)0.0065 (18)0.0259 (18)0.0053 (16)
O20.054 (3)0.022 (2)0.031 (2)0.0060 (17)0.0234 (19)0.0102 (17)
O30.053 (2)0.029 (2)0.0208 (17)0.0079 (18)0.0212 (17)0.0043 (15)
O40.058 (3)0.029 (2)0.031 (2)0.0002 (19)0.0198 (19)0.0115 (17)
OW10.057 (4)0.031 (3)0.032 (3)0.0000.017 (3)0.000
N10.036 (2)0.016 (2)0.023 (2)0.0013 (18)0.0145 (19)0.0018 (17)
C10.019 (2)0.020 (3)0.016 (2)0.0032 (19)0.0038 (18)0.0013 (19)
C20.022 (2)0.025 (3)0.020 (2)0.001 (2)0.0109 (19)0.002 (2)
C30.022 (2)0.023 (3)0.017 (2)0.0008 (19)0.0072 (19)0.0035 (19)
C40.024 (2)0.017 (3)0.021 (2)0.0025 (19)0.0070 (19)0.0007 (18)
C50.019 (2)0.021 (3)0.021 (2)0.001 (2)0.006 (2)0.001 (2)
C60.024 (2)0.018 (2)0.016 (2)0.0048 (19)0.0048 (19)0.0001 (18)
C70.023 (2)0.022 (3)0.026 (3)0.002 (2)0.009 (2)0.005 (2)
C80.024 (2)0.023 (3)0.019 (2)0.009 (2)0.0072 (19)0.001 (2)
Geometric parameters (Å, º) top
Cu1—O31.970 (3)C4—H4A0.9300
Cu1—O3i1.970 (3)C1—C21.391 (7)
Cu1—N1ii2.041 (4)C1—N11.442 (6)
Cu1—N1iii2.041 (4)C3—C21.388 (7)
O4—C81.251 (6)C3—C71.503 (6)
O3—C81.276 (6)N1—Cu1iv2.041 (4)
C8—C51.505 (6)N1—H1A0.8600
OW1—HW1A0.91 (8)N1—H1B0.8600
C5—C41.388 (7)C2—H2A0.9300
C5—C61.401 (7)C7—O11.217 (6)
C6—C11.398 (6)C7—O21.320 (7)
C6—H6A0.9300O2—H2B0.82 (6)
C4—C31.391 (7)
O3—Cu1—O3i180C2—C1—C6120.4 (4)
O3—Cu1—N1ii91.53 (16)C2—C1—N1118.2 (4)
O3i—Cu1—N1ii88.47 (16)C6—C1—N1121.4 (4)
O3—Cu1—N1iii88.47 (16)C2—C3—C4120.4 (4)
O3i—Cu1—N1iii91.53 (16)C2—C3—C7118.1 (4)
N1ii—Cu1—N1iii180C4—C3—C7121.4 (4)
C8—O3—Cu1120.0 (3)C1—N1—Cu1iv112.9 (3)
O4—C8—O3125.1 (4)C1—N1—H1A120.0
O4—C8—C5116.6 (4)Cu1iv—N1—H1A64.5
O3—C8—C5118.3 (4)C1—N1—H1B120.0
C4—C5—C6120.5 (4)Cu1iv—N1—H1B92.4
C4—C5—C8117.2 (4)H1A—N1—H1B120.0
C6—C5—C8122.3 (4)C3—C2—C1119.8 (4)
C1—C6—C5119.0 (4)C3—C2—H2A120.1
C1—C6—H6A120.5C1—C2—H2A120.1
C5—C6—H6A120.5O1—C7—O2123.8 (5)
C5—C4—C3119.7 (4)O1—C7—C3123.2 (5)
C5—C4—H4A120.1O2—C7—C3113.1 (4)
C3—C4—H4A120.1C7—O2—H2B110 (4)
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x, y, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3v0.862.242.874 (5)130
N1—H1A···O1vi0.862.532.944 (6)110
N1—H1B···OW1vii0.862.322.923 (6)127
N1—H1B···O3iv0.862.352.798 (6)113
OW1—HW1A···O4viii0.91 (8)2.44 (8)3.294 (6)157 (7)
O2—H2B···O4ix0.82 (6)1.74 (6)2.554 (5)174 (6)
Symmetry codes: (iv) x+1/2, y1/2, z+1/2; (v) x, y, z1/2; (vi) x+1, y, z; (vii) x+1/2, y1/2, z; (viii) x1/2, y1/2, z; (ix) x, y+1, z1/2.

Experimental details

Crystal data
Chemical formula[Cu(C8H6NO4)2]·H2O
Mr441.83
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)13.2692 (11), 9.1898 (8), 13.5155 (11)
β (°) 107.542 (2)
V3)1571.5 (2)
Z4
Radiation typeMo Kα
µ (mm1)1.45
Crystal size (mm)0.36 × 0.20 × 0.20
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.723, 0.748
No. of measured, independent and
observed [I > 2σ(I)] reflections
2289, 1359, 1117
Rint0.029
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.136, 1.06
No. of reflections1359
No. of parameters137
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0601P)2 + 12.8787P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.68, 0.83

Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens, 1994), XPREP in SHELXTL (Siemens, 1994), SHELXTL.

Selected geometric parameters (Å, º) top
Cu1—O31.970 (3)Cu1—N1ii2.041 (4)
Cu1—O3i1.970 (3)Cu1—N1iii2.041 (4)
O3—Cu1—N1ii91.53 (16)
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x, y, z+1/2; (iii) x+1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3iv0.862.242.874 (5)130
N1—H1A···O1v0.862.532.944 (6)110
N1—H1B···OW1vi0.862.322.923 (6)127
N1—H1B···O3vii0.862.352.798 (6)113
OW1—HW1A···O4viii0.91 (8)2.44 (8)3.294 (6)157 (7)
O2—H2B···O4ix0.82 (6)1.74 (6)2.554 (5)174 (6)
Symmetry codes: (iv) x, y, z1/2; (v) x+1, y, z; (vi) x+1/2, y1/2, z; (vii) x+1/2, y1/2, z+1/2; (viii) x1/2, y1/2, z; (ix) x, y+1, z1/2.
 

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