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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): m1118.
Published online 2008 August 6. doi:  10.1107/S1600536808024379
PMCID: PMC2960599

catena-Poly[[[diaqua­copper(II)]-{μ-4,4′-[1,4-phenyl­enebis(methyl­eneimino)]dibenzoato}] monohydrate]

Abstract

The asymmetric unit of the title polymeric compound, {[Cu(C22H18N2O4)(H2O)2]·H2O}n, contains a Cu ion situated on an inversion center, half of a centrosymmetric 4,4′-[1,4-phenyl­enebis(methyl­eneimino)]dibenzoate ligand, a coordin­ated water mol­ecule in a general position and an uncoordin­ated water mol­ecule situated on a twofold rotation axis. The distorted octa­hedral coordination geometry of the CuII ion is formed by six O atoms. The –NH– groups of the ligand are involved in intra­molecular N—H(...)O hydrogen bonds, while the water mol­ecules participate in the formation of a three-dimensional supra­molecular framework via inter­molecular O—H(...)O hydrogen bonds.

Related literature

For properties of 4,4′-(1,4-phenyl­enebis(methyl­ene))bis­(aza­nedi­yl)dibenzoic acid and its ramifications, see: Yamaguchi et al. (1991 [triangle]); Imhof & Göbel (2000 [triangle]). For supra­molecular networks in related structures, see: Jing et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1118-scheme1.jpg

Experimental

Crystal data

  • [Cu(C22H18N2O4)(H2O)2]·H2O
  • M r = 491.98
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1118-efi1.jpg
  • a = 16.127 (6) Å
  • b = 5.1535 (17) Å
  • c = 13.405 (8) Å
  • β = 92.76 (2)°
  • V = 1112.8 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.03 mm−1
  • T = 291 (2) K
  • 0.09 × 0.08 × 0.07 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.913, T max = 0.932
  • 10220 measured reflections
  • 2534 independent reflections
  • 2008 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.140
  • S = 1.03
  • 2534 reflections
  • 147 parameters
  • H-atom parameters constrained
  • Δρmax = 0.49 e Å−3
  • Δρmin = −0.49 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024379/cv2427sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024379/cv2427Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the financial support from the National Natural Science Foundation of China (grant 20771082).

supplementary crystallographic information

Comment

In recent years, 4,4'-(1,4-phenylenebis(methylene))bis(azanediyl)dibenzoic acid and its ramifications have become an area of interest owing to their various properties (Yamaguchi et al., 1991; Imhof & Göbel, 2000). They are also used for building up supramolecular networks through hydrogen bonds (Jing et al., 2006). Of special interest are the low-dimensional structural motifs related with highly anisotropic physical properties. Here we report the crystal structure of the title compound, (I).

For the title polymeric compound, (I), structure determination revealed a presence in the asymmetric unit of a half of centrosymmetric 4,4'-(1,4-phenylenebis(methylene))bis(azanediyl)dibenzoic ligand, one Cu ion lies on the inversion ctnter, one coordinated water molecule locates on the twofold axis and one lattice water molecule locates in the general positon. The Cu ion is coordinated by six oxygen atoms with four of which from 4,4'-(1,4-phenylenebis(methylene))bis(azanediyl)dibenzoic ligand and the other two from water moleculers into a distorted octahedral geometry (Table 1). The neighbouring Cu ions are linked by 4,4'-(1,4-phenylenebis(methylene))bis(azanediyl)dibenzoic ligand to form an infinite plolymeric zigzag chain (Fig. 1). The amino groups of the ligand are involved in intramolecular N—H···O hydrogen bonds, wihle water molecules participate in formation of three-dimensional supramolecular framework via intermolecular O—H···O hydrogen bonds (Table 2).

Experimental

The 10 ml aqueous solution of CuCl2.2H2O (0.855 g, 5 mmol) was droped into a 10 ml DMF soution of 4,4'-(1,4-phenylenebis(methylene))bis(azanediyl)dibenzoic acid (1.882 g, 5 mmol). The mixture was stirred for half an hour. The resultant solution was filtered, and the filtrate was allowed to stand at room temperature for one week, to generate blue block crystals.

Refinement

C-bound H atoms were geometrically positioned (C-H 0.93-0.97 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) Water H atoms were positioned geometrically with O—H = 0.85 Å and Uiso(H) = 1.2Ueq(O). The N-bound H atom was located on a difference Fourier map, but placed in idealized position (N-H 0.84 Å) and refined as ridinh with Uiso(H) = 1.5Ueq(N).

Figures

Fig. 1.
A portion of the polymeric chain in (I) with the atom numbering and 30% probalility displacement ellipsoids [symmetry codes: (A) 2-x, 1-y, 2-z; (B) 1-x, -y, 2-z]

Crystal data

[Cu(C22H18N2O4)(H2O)2]·H2OF000 = 510
Mr = 491.98Dx = 1.468 Mg m3
Monoclinic, P2/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 7833 reflections
a = 16.127 (6) Åθ = 3.1–27.5º
b = 5.1535 (17) ŵ = 1.03 mm1
c = 13.405 (8) ÅT = 291 (2) K
β = 92.76 (2)ºBlock, blue
V = 1112.8 (8) Å30.09 × 0.08 × 0.07 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer2534 independent reflections
Radiation source: fine-focus sealed tube2008 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.040
Detector resolution: 10.0 pixels mm-1θmax = 27.5º
T = 291(2) Kθmin = 3.0º
ω scansh = −20→20
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)k = −6→6
Tmin = 0.913, Tmax = 0.932l = −17→16
10220 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.140  w = 1/[σ2(Fo2) + (0.0854P)2 + 0.6974P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2534 reflectionsΔρmax = 0.49 e Å3
147 parametersΔρmin = −0.49 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
C10.63113 (17)0.1232 (5)0.8986 (2)0.0276 (6)
C20.69938 (16)0.1294 (5)0.82720 (19)0.0253 (5)
C30.69767 (18)−0.0493 (6)0.7480 (2)0.0312 (6)
H30.6542−0.16760.74190.037*
C40.7583 (2)−0.0552 (7)0.6790 (2)0.0383 (7)
H40.7554−0.17290.62640.046*
C50.82372 (19)0.1176 (7)0.6898 (2)0.0374 (7)
H50.86530.11430.64410.045*
C60.82859 (18)0.2944 (6)0.7668 (2)0.0333 (6)
H60.87330.40830.77240.040*
C70.76652 (16)0.3050 (5)0.8376 (2)0.0264 (5)
C80.83674 (18)0.6789 (5)0.9238 (2)0.0328 (6)
H8A0.81860.81260.96870.039*
H8B0.84270.75840.85900.039*
C90.92123 (18)0.5803 (6)0.9623 (2)0.0287 (6)
C100.9299 (2)0.3842 (8)1.0310 (3)0.0506 (9)
H100.88260.30311.05300.061*
C110.9926 (2)0.6965 (7)0.9314 (3)0.0484 (9)
H110.98880.83030.88480.058*
Cu10.50000.00001.00000.02769 (18)
N10.77292 (15)0.4809 (5)0.91439 (19)0.0326 (5)
H10.73050.49130.94840.049*
O10.56996 (16)−0.2511 (5)1.07956 (19)0.0517 (6)
H1A0.5868−0.37651.04470.062*
H1B0.5446−0.31361.12820.062*
O20.57429 (13)−0.0498 (4)0.88572 (16)0.0337 (5)
O30.62970 (13)0.2785 (4)0.97072 (15)0.0371 (5)
O40.50000.5811 (7)0.75000.0450 (8)
H4A0.52840.69940.77980.054*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0219 (13)0.0338 (14)0.0275 (14)0.0043 (11)0.0040 (10)0.0018 (11)
C20.0218 (13)0.0306 (14)0.0237 (13)0.0036 (10)0.0039 (10)0.0019 (10)
C30.0263 (14)0.0380 (15)0.0293 (15)0.0004 (11)0.0023 (11)−0.0025 (11)
C40.0366 (17)0.0494 (18)0.0294 (15)0.0018 (14)0.0073 (12)−0.0090 (12)
C50.0325 (16)0.0504 (18)0.0303 (15)0.0016 (14)0.0114 (12)0.0013 (13)
C60.0259 (14)0.0403 (16)0.0345 (15)−0.0032 (12)0.0080 (11)0.0032 (12)
C70.0222 (13)0.0308 (13)0.0264 (13)0.0051 (10)0.0016 (10)0.0035 (10)
C80.0263 (14)0.0307 (14)0.0410 (16)0.0006 (11)−0.0027 (11)−0.0008 (12)
C90.0269 (14)0.0273 (12)0.0318 (14)−0.0003 (11)0.0005 (11)−0.0023 (11)
C100.0249 (16)0.057 (2)0.070 (2)−0.0083 (15)0.0041 (15)0.0301 (18)
C110.0311 (16)0.053 (2)0.061 (2)−0.0044 (15)0.0001 (15)0.0326 (17)
Cu10.0237 (3)0.0304 (3)0.0297 (3)−0.00293 (19)0.00892 (18)−0.00458 (18)
N10.0225 (12)0.0392 (14)0.0365 (13)−0.0030 (10)0.0055 (10)−0.0070 (10)
O10.0498 (15)0.0521 (14)0.0537 (15)0.0052 (12)0.0086 (12)−0.0021 (11)
O20.0267 (10)0.0391 (11)0.0361 (11)−0.0065 (8)0.0102 (8)−0.0065 (8)
O30.0335 (11)0.0444 (12)0.0346 (11)−0.0045 (9)0.0133 (8)−0.0111 (9)
O40.048 (2)0.0425 (16)0.0444 (19)0.0000.0024 (15)0.000

Geometric parameters (Å, °)

C1—O31.257 (3)C9—C101.370 (4)
C1—O21.284 (4)C9—C111.379 (4)
C1—C21.493 (4)C10—C11i1.389 (5)
C2—C31.405 (4)C10—H100.9300
C2—C71.413 (4)C11—C10i1.389 (5)
C3—C41.378 (4)C11—H110.9300
C3—H30.9300Cu1—O1ii1.992 (3)
C4—C51.383 (5)Cu1—O11.992 (3)
C4—H40.9300Cu1—O22.006 (2)
C5—C61.376 (4)Cu1—O2ii2.006 (2)
C5—H50.9300Cu1—O32.582 (2)
C6—C71.413 (4)Cu1—O3ii2.582 (2)
C6—H60.9300Cu1—C1ii2.646 (3)
C7—N11.372 (4)N1—H10.8420
C8—N11.450 (4)O1—H1A0.8500
C8—C91.521 (4)O1—H1B0.8500
C8—H8A0.9700O4—H4A0.8500
C8—H8B0.9700
O3—C1—O2120.4 (3)C9—C11—C10i120.7 (3)
O3—C1—C2121.4 (3)C9—C11—H11119.7
O2—C1—C2118.2 (2)C10i—C11—H11119.7
C3—C2—C7118.8 (2)O1ii—Cu1—O1180.00 (13)
C3—C2—C1118.8 (2)O1ii—Cu1—O291.02 (10)
C7—C2—C1122.4 (2)O1—Cu1—O288.98 (10)
C4—C3—C2122.2 (3)O1ii—Cu1—O2ii88.98 (10)
C4—C3—H3118.9O1—Cu1—O2ii91.02 (10)
C2—C3—H3118.9O2—Cu1—O2ii180.000 (1)
C3—C4—C5118.5 (3)O1ii—Cu1—O389.98 (10)
C3—C4—H4120.7O1—Cu1—O390.02 (10)
C5—C4—H4120.7O2—Cu1—O355.75 (7)
C6—C5—C4121.4 (3)O2ii—Cu1—O3124.25 (7)
C6—C5—H5119.3O1ii—Cu1—O3ii90.02 (10)
C4—C5—H5119.3O1—Cu1—O3ii89.98 (10)
C5—C6—C7120.8 (3)O2—Cu1—O3ii124.25 (7)
C5—C6—H6119.6O2ii—Cu1—O3ii55.75 (7)
C7—C6—H6119.6O3—Cu1—O3ii180.0
N1—C7—C6120.0 (3)O1ii—Cu1—C1ii89.14 (10)
N1—C7—C2121.8 (2)O1—Cu1—C1ii90.86 (10)
C6—C7—C2118.3 (2)O2—Cu1—C1ii152.03 (9)
N1—C8—C9114.5 (2)O2ii—Cu1—C1ii27.97 (9)
N1—C8—H8A108.6O3—Cu1—C1ii152.22 (7)
C9—C8—H8A108.6O3ii—Cu1—C1ii27.78 (7)
N1—C8—H8B108.6C7—N1—C8123.9 (2)
C9—C8—H8B108.6C7—N1—H1114.5
H8A—C8—H8B107.6C8—N1—H1120.0
C10—C9—C11117.6 (3)Cu1—O1—H1A112.8
C10—C9—C8122.3 (3)Cu1—O1—H1B112.1
C11—C9—C8120.0 (3)H1A—O1—H1B108.2
C9—C10—C11i121.7 (3)C1—O2—Cu1104.92 (17)
C9—C10—H10119.1C1—O3—Cu178.92 (16)
C11i—C10—H10119.1

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O30.842.002.676 (3)137
O1—H1A···O3iii0.852.173.011 (3)174
O1—H1B···O4ii0.852.283.104 (3)164
O4—H4A···O2iv0.852.032.855 (3)163

Symmetry codes: (iii) x, y−1, z; (ii) −x+1, −y, −z+2; (iv) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2427).

References

  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Imhof, W. & Göbel, A. (2000). J. Organomet. Chem.610, 102–111.
  • Jing, L.-H., Zhang, H.-X. & Gu, S.-J. (2006). Acta Cryst. E62, o4583–o4584.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Yamaguchi, K., Matsumura, G., Kagechika, H., Azumaya, I., Ito, Y., Itai, A. & Shudo, K. (1991). J. Am. Chem. Soc 113, 5474–5475.

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