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Acta Cryst. (2007). E63, m2523    [ doi:10.1107/S1600536807043449 ]

(2,9-Dimethyl-1,10-phenanthroline-[kappa]2N,N')bis(3-hydroxybenzoato-[kappa]O) copper(II)

P.-Z. Zhao, F.-M. Yan, X.-P. Xuan and Q.-H. Tang

Abstract top

In the title compound, [Cu(C7H5O3)2(C14H12N2)], the CuII ion is located on a twofold rotation axis and is coordinated by a 2,9-dimethyl-1,10-phenanthroline (dmphen) molecule and two 3-hydroxybenzoate anions in a distorted tetrahedral geometry. Molecules are linked into a one-dimensional framework by O-H...O hydrogen bonding. The packing is further stabilized by [pi]-[pi] stacking between parallel dmphen rings of neighboring molecules, with a face-to-face distance of 3.385 (18) Å.

Comment top

Metal-phenanthroline complexes and its derivatives have attracted much attention because of their peculiar features (Wang et al., 1996; Wall et al., 1999; Naing et al., 1995). Recently, we obtained the title mononuclear copper(II) complex (I), by reaction of 2,9-dimethyl-1,10-phenanthroline, m-hydroxybenzoic acid and Cu(NO3)2 in an ethanol/water mixture. Here we report its crystal structure.

Each CuII ion is four-coordinated by two N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand, and two O atoms from two m-hydroxybenzoic anions. The CuII ion locates on a twofold rotation axis, and CuO2N2 unit forms a distorted tetrahedral geometry (Fig. 1). The Cu1–N1 bond length is slightly longer than Cu1—O1 bond length (Table 1).

In the crystal structure, molecules are linked into a two dimensional framework by intermolecular O—H···O hydrogen bonds (Fig. 2). The crystal further stabilized by π-π interactions between the dmphen ring systems (Fig. 3). These intermolecular interactions occur between the parallel rings within offset face-to-face packing. The face-to-face distance of the parallel ring planes between the neighboring molecules related by 1 − x,2 − y,1 − z is 3.385 (18) Å.

Related literature top

For related literature, see: Wang et al. (1996); Wall et al. (1999); Naing et al. (1995).

Experimental top

An aqueous solution (10 ml) of 3-hydroxybenzoic acid (0.0698 g, 0.5 mmol), NaOH (0.0198 g, 0.5 mmol) and Cu(NO3)2.3H2O (0.1212 g, 0.5 mmol) was mixed with an ethanol solution (10 ml) of 2,9-dimethyl-1,10-phenanthroline hemihydrate (0.1088 g, 0.5 mmol). The mixture was refluxed for 4 h. After cooling to room temperature the solution was filtered. The single crystals of the title compound were obtained after 3 weeks at room temperature.

Refinement top

Methyl H and hydroxy H atoms were placed in calculated positions with C—H = 0.96 and O—H = 0.82 Å, and refined with free torsion angles to fit the electron density, Uiso(H) = 1.5Ueq(carrier). Other H atoms were placed in calculated positions with C—H = 0.93 Å and refined in the riding model approximation with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex(I),with atom labels and 30% probability displacement ellipsoids for non-H atoms. Symmetry code for the symbol 'A': −x + 1, y, −z + 3/2
[Figure 2] Fig. 2. The hydrogen-bonding motifs in the crystal structure of (I). Dashed lines indicate the hydrogen.
[Figure 3] Fig. 3. The π-π interaction between the dmphen rings of neighboring molecules in the crystal structure of (I). Symmetry code: −x + 1, y, −z + 3/2
(2,9-Dimethyl-1,10-phenanthroline-κ2N,N')bis(3-hydroxybenzoato-κO) copper(II) top
Crystal data top
[Cu(C7H5O3)2(C14H12N2)]F000 = 1124
Mr = 546.02Dx = 1.450 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1908 reflections
a = 17.623 (3) Åθ = 2.3–24.8º
b = 14.587 (2) ŵ = 0.92 mm−1
c = 9.7581 (15) ÅT = 291 (2) K
β = 94.199 (2)ºBlock, yellow
V = 2501.8 (7) Å30.44 × 0.33 × 0.24 mm
Z = 4
Data collection top
Bruker SMART CCD area detector
diffractometer		2275 independent reflections
Radiation source: fine-focus sealed tube1766 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 291(2) Kθmax = 25.5º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −21→21
Tmin = 0.690, Tmax = 0.809k = −12→17
7268 measured reflectionsl = −8→11
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)] = 0.038H-atom parameters constrained
wR(F2) = 0.105  w = 1/[σ2(Fo2) + (0.0535P)2 + 1.4781P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
2275 reflectionsΔρmax = 0.28 e Å−3
170 parametersΔρmin = −0.33 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C7H5O3)2(C14H12N2)]V = 2501.8 (7) Å3
Mr = 546.02Z = 4
Monoclinic, C2/cMo Kα
a = 17.623 (3) ŵ = 0.92 mm−1
b = 14.587 (2) ÅT = 291 (2) K
c = 9.7581 (15) Å0.44 × 0.33 × 0.24 mm
β = 94.199 (2)º
Data collection top
Bruker SMART CCD area detector
diffractometer		2275 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1766 reflections with I > 2σ(I)
Tmin = 0.690, Tmax = 0.809Rint = 0.030
7268 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038170 parameters
wR(F2) = 0.105H-atom parameters constrained
S = 1.01Δρmax = 0.28 e Å−3
2275 reflectionsΔρmin = −0.33 e Å−3
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
Cu10.50000.76339 (3)0.75000.0548 (2)
O10.48033 (10)0.67482 (13)0.89294 (19)0.0591 (5)
O20.37612 (12)0.75613 (14)0.8785 (2)0.0708 (6)
O30.22168 (12)0.6282 (2)1.2567 (3)0.0946 (9)
H30.20090.67131.21510.142*
N10.44985 (11)0.86705 (14)0.6396 (2)0.0475 (5)
C10.28890 (14)0.6092 (2)1.2022 (3)0.0569 (7)
C20.32881 (17)0.5350 (2)1.2543 (3)0.0758 (9)
H20.30980.49991.32360.091*
C30.3970 (2)0.5128 (2)1.2036 (4)0.0938 (13)
H3A0.42420.46231.23890.113*
C40.42579 (18)0.5645 (2)1.1005 (3)0.0761 (10)
H40.47250.54941.06800.091*
C50.38563 (14)0.63782 (16)1.0463 (2)0.0443 (6)
C60.31729 (14)0.66047 (19)1.0984 (3)0.0515 (6)
H60.29000.71091.06320.062*
C70.41479 (14)0.69351 (17)0.9321 (2)0.0455 (6)
C80.47227 (14)0.95027 (18)0.6924 (2)0.0480 (6)
C90.44369 (17)1.0339 (2)0.6395 (3)0.0588 (7)
C100.38814 (19)1.0287 (2)0.5295 (3)0.0714 (9)
H100.36741.08220.49080.086*
C110.36452 (17)0.9460 (3)0.4793 (3)0.0687 (9)
H110.32720.94320.40690.082*
C120.39594 (15)0.8639 (2)0.5356 (3)0.0560 (7)
C130.36969 (19)0.7725 (2)0.4826 (3)0.0752 (9)
H13A0.41300.73570.46420.113*
H13B0.33780.78040.39940.113*
H13C0.34140.74240.55010.113*
C140.47253 (19)1.1177 (2)0.6983 (3)0.0738 (9)
H140.45301.17320.66460.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0702 (3)0.0494 (3)0.0457 (3)0.0000.0106 (2)0.000
O10.0571 (11)0.0621 (12)0.0615 (12)0.0067 (9)0.0269 (9)0.0056 (9)
O20.0672 (13)0.0720 (14)0.0761 (14)0.0143 (10)0.0260 (11)0.0323 (11)
O30.0623 (13)0.139 (2)0.0871 (16)0.0299 (13)0.0399 (12)0.0534 (15)
N10.0468 (11)0.0572 (14)0.0403 (11)−0.0009 (10)0.0155 (9)0.0027 (10)
C10.0466 (14)0.0730 (19)0.0524 (16)0.0042 (13)0.0124 (12)0.0153 (14)
C20.070 (2)0.086 (2)0.074 (2)0.0079 (17)0.0206 (17)0.0384 (18)
C30.096 (3)0.082 (2)0.108 (3)0.037 (2)0.040 (2)0.055 (2)
C40.078 (2)0.073 (2)0.083 (2)0.0322 (17)0.0380 (18)0.0270 (17)
C50.0506 (14)0.0424 (14)0.0413 (13)0.0013 (11)0.0121 (11)−0.0004 (11)
C60.0513 (14)0.0554 (16)0.0489 (15)0.0092 (12)0.0111 (12)0.0128 (12)
C70.0508 (14)0.0440 (15)0.0429 (13)−0.0012 (12)0.0110 (11)−0.0038 (11)
C80.0549 (15)0.0510 (16)0.0410 (13)0.0027 (12)0.0239 (11)0.0029 (11)
C90.0705 (18)0.0584 (18)0.0513 (16)0.0077 (14)0.0311 (15)0.0102 (14)
C100.081 (2)0.077 (2)0.0592 (19)0.0209 (18)0.0271 (17)0.0202 (17)
C110.0601 (18)0.096 (3)0.0507 (17)0.0072 (17)0.0110 (14)0.0189 (17)
C120.0492 (14)0.073 (2)0.0478 (15)−0.0022 (13)0.0183 (12)0.0058 (14)
C130.0652 (19)0.096 (3)0.064 (2)−0.0180 (17)−0.0016 (16)−0.0019 (17)
C140.106 (3)0.0518 (18)0.069 (2)0.0085 (16)0.0412 (17)0.0083 (14)
Geometric parameters (Å, °) top
Cu1—O11.9509 (18)C5—C61.381 (3)
Cu1—O1i1.9509 (18)C5—C71.500 (3)
Cu1—N12.022 (2)C6—H60.9300
Cu1—N1i2.022 (2)C8—C91.403 (4)
O1—C71.272 (3)C8—C8i1.434 (5)
O2—C71.233 (3)C9—C101.400 (4)
O3—C11.362 (3)C9—C141.428 (4)
O3—H30.8200C10—C111.356 (4)
N1—C121.339 (3)C10—H100.9300
N1—C81.366 (3)C11—C121.413 (4)
C1—C21.367 (4)C11—H110.9300
C1—C61.382 (4)C12—C131.492 (4)
C2—C31.372 (4)C13—H13A0.9600
C2—H20.9300C13—H13B0.9600
C3—C41.383 (4)C13—H13C0.9600
C3—H3A0.9300C14—C14i1.346 (7)
C4—C51.367 (4)C14—H140.9300
C4—H40.9300
O1—Cu1—O1i97.05 (11)C1—C6—H6119.6
O1—Cu1—N1141.50 (8)O2—C7—O1121.2 (2)
O1i—Cu1—N1102.00 (8)O2—C7—C5120.5 (2)
O1—Cu1—N1i102.00 (8)O1—C7—C5118.3 (2)
O1i—Cu1—N1i141.50 (8)N1—C8—C9123.2 (2)
N1—Cu1—N1i83.20 (12)N1—C8—C8i117.22 (14)
C7—O1—Cu1106.58 (16)C9—C8—C8i119.62 (17)
C1—O3—H3109.5C10—C9—C8116.6 (3)
C12—N1—C8119.1 (2)C10—C9—C14124.2 (3)
C12—N1—Cu1129.51 (19)C8—C9—C14119.2 (3)
C8—N1—Cu1111.12 (16)C11—C10—C9120.2 (3)
O3—C1—C2117.1 (2)C11—C10—H10119.9
O3—C1—C6123.2 (2)C9—C10—H10119.9
C2—C1—C6119.8 (2)C10—C11—C12120.8 (3)
C1—C2—C3119.6 (3)C10—C11—H11119.6
C1—C2—H2120.2C12—C11—H11119.6
C3—C2—H2120.2N1—C12—C11120.1 (3)
C2—C3—C4120.7 (3)N1—C12—C13118.6 (3)
C2—C3—H3A119.6C11—C12—C13121.3 (3)
C4—C3—H3A119.6C12—C13—H13A109.5
C5—C4—C3120.1 (3)C12—C13—H13B109.5
C5—C4—H4120.0H13A—C13—H13B109.5
C3—C4—H4120.0C12—C13—H13C109.5
C4—C5—C6119.0 (2)H13A—C13—H13C109.5
C4—C5—C7121.0 (2)H13B—C13—H13C109.5
C6—C5—C7120.0 (2)C14i—C14—C9121.10 (18)
C5—C6—C1120.8 (2)C14i—C14—H14119.4
C5—C6—H6119.6C9—C14—H14119.4
O1i—Cu1—O1—C7−124.17 (18)C6—C5—C7—O2−4.3 (4)
N1—Cu1—O1—C7−4.7 (2)C4—C5—C7—O1−4.7 (4)
N1i—Cu1—O1—C789.48 (17)C6—C5—C7—O1175.2 (2)
O1—Cu1—N1—C12−74.0 (2)C12—N1—C8—C9−2.6 (3)
O1i—Cu1—N1—C1243.9 (2)Cu1—N1—C8—C9−177.13 (18)
N1i—Cu1—N1—C12−174.8 (2)C12—N1—C8—C8i177.4 (2)
O1—Cu1—N1—C899.75 (19)Cu1—N1—C8—C8i2.8 (3)
O1i—Cu1—N1—C8−142.29 (15)N1—C8—C9—C101.7 (4)
N1i—Cu1—N1—C8−1.00 (11)C8i—C8—C9—C10−178.3 (3)
O3—C1—C2—C3−179.8 (4)N1—C8—C9—C14−177.8 (2)
C6—C1—C2—C30.5 (5)C8i—C8—C9—C142.3 (4)
C1—C2—C3—C40.0 (6)C8—C9—C10—C110.0 (4)
C2—C3—C4—C5−1.1 (6)C14—C9—C10—C11179.4 (3)
C3—C4—C5—C61.6 (5)C9—C10—C11—C12−0.7 (4)
C3—C4—C5—C7−178.5 (3)C8—N1—C12—C111.8 (3)
C4—C5—C6—C1−1.1 (4)Cu1—N1—C12—C11175.13 (17)
C7—C5—C6—C1179.0 (2)C8—N1—C12—C13−177.5 (2)
O3—C1—C6—C5−179.6 (3)Cu1—N1—C12—C13−4.2 (3)
C2—C1—C6—C50.0 (5)C10—C11—C12—N1−0.2 (4)
Cu1—O1—C7—O21.7 (3)C10—C11—C12—C13179.1 (3)
Cu1—O1—C7—C5−177.83 (17)C10—C9—C14—C14i−178.2 (3)
C4—C5—C7—O2175.8 (3)C8—C9—C14—C14i1.2 (5)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2ii0.821.902.688 (3)160
Symmetry codes: (ii) −x+1/2, −y+3/2, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.9509 (18)Cu1—N12.022 (2)
O1—Cu1—O1i97.05 (11)O1i—Cu1—N1102.00 (8)
O1—Cu1—N1141.50 (8)N1—Cu1—N1i83.20 (12)
Symmetry codes: (i) −x+1, y, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2ii0.821.902.688 (3)160
Symmetry codes: (ii) −x+1/2, −y+3/2, −z+2.
Acknowledgements top

Financial support of this work by the Science Fund of Henan Province for Distinguished Young Scholars (No. 074100510005) is gratefully acknowledged.

references
References top

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

Wall, M., Linkletter, B., Williams, D., Lebuis, A. M., Hynes, R. C. & Chin, J. (1999). J. Am. Chem. Soc. 121, 4710–4711.

Wang, J., Cai, X., Rivas, G., Shiraishi, H., Farias, P. A. M. & Dontha, N. (1996). Anal. Chem. 68, 2629–2634.