supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

pk2057 scheme

Acta Cryst. (2008). E64, m142    [ doi:10.1107/S1600536807057169 ]

(Dicyanamido)[2-(2-pyridylmethyliminomethyl)phenolato]copper(II) monohydrate

Q.-H. Zhao, L. Zhang, L. Du and R.-B. Fang

Abstract top

The title compound, [Cu(C13H11N2O)(C2N3)]·H2O, is a mononuclear copper(II) complex in which the CuII ion has a slightly distorted square-planar geometry and is coordinated by two N atoms and one O atom from the Schiff base ligand and by an N atom from dicyanamide. The O atoms of water molecules contribute to O-H...N, O-H...O hydrogen bonds, leading to the formation of sheets parallel to the ac plane. There are also weak interactions between inversion-related molecules.

Comment top

Transition metal compounds containing Schiff base ligands have been of great interest for many years. These compounds play an important role in the development of coordination chemistry due to their potential applications in catalysis and enzymatic reactions, magnetism and molecular architecture (You & Zhu, 2004; Li & Zhang, 2004). Here we report the structure of a complex that is formed by Cu(CH3COO)2, the Schiff base ligand 2-(pyridin-2-ylmethyliminomethyl)phenol and sodium dicyanamide.

As shown in Fig. 1, the asymmetric unit consists of a mononuclear [Cu(C13H11N2O)N(CN)2] and a H-bonded water molecule. The central CuII ion is four-coordinate and adopts a slightly distorted square-planar geometry that is defined by two N atoms and one O atom from the Schiff base ligand and another N atom from dicyanamide. The C7=N1 and C8—N1 distances of 1.293 (4) Å and 1.466 (4) Å indicate double and single bonds respectively. The bond angles around the CuII centre show some deviations from ideal square-planar geometry (You et al., 2004). Also, the closeness of the planes of inversion related molecules imply weak intramolecular interactions cross an inversion centre such that the distance between Cu1 and O1 of an inversion related phenolato is 2.814 (2) Å, which is much longer than Cu—O bond length.

The water molecule is involved in intermolecular (O1W—H1WA···N5) and intramolecular hydrogen bonds (O1W—H1WB···O1, O1W—H1WB···N3), which leads to sheets parallel to the ac plane (Fig. 2).

Related literature top

For related literature, see: You & Zhu (2004); Li & Zhang (2004); You et al. (2004); Zhang et al. (2005).

Experimental top

All chemicals used (reagent grade) were commercially available. Salicylaldehyde (0.122 g, 1 mmol) was dissolved in ethanol (5 mL) and ethanol solution (5 mL) containing 2-aminomethylpyridine (0.108 g, 1 mmol) was added slowly with stirring. The resulting yellow solution was continuously stirred for about 30 min at room temperature, and then Cu(CH3COO)2.H2O (0.200 g, 1 mmol) in aqueous solution (5 mL) was added with stirring homogeneously. Dark blue crystals suitable for X-ray ananlysis were obtained by slow evaporation at room temperature over several days (Zhang et al., 2005).

Refinement top

Water H atoms were located in a difference map and refined with distance restraints of O1W—H = 0.87 (2). Other H atoms were placed in calculated positions and allowed to ride on their attached C atoms with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A crystal packing diagram of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines.
(Dicyanamido)[2-(2-pyridylmethyliminomethyl)phenolato]copper(II) monohydrate top
Crystal data top
[Cu(C13H11N2O)(C2N3)]·H2OF000 = 732
Mr = 358.84Dx = 1.622 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3146 reflections
a = 9.8851 (12) Åθ = 3.0–27.5º
b = 7.0240 (6) ŵ = 1.50 mm−1
c = 21.398 (3) ÅT = 293 (2) K
β = 98.382 (9)ºPrism, colourless
V = 1469.9 (3) Å30.2 × 0.2 × 0.2 mm
Z = 4
Data collection top
Rigaku Mercury2 CCD
diffractometer		3487 independent reflections
Radiation source: fine-focus sealed tube2664 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.048
Detector resolution: 13.6612 pixels mm-1θmax = 27.9º
T = 293(2) Kθmin = 2.6º
ω scansh = −13→13
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −9→9
Tmin = 0.693, Tmax = 0.741l = −28→28
14839 measured reflections
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)] = 0.042H-atom parameters constrained
wR(F2) = 0.115  w = 1/[σ2(Fo2) + (0.0583P)2 + 0.2406P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3487 reflectionsΔρmax = 0.61 e Å−3
208 parametersΔρmin = −0.35 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C13H11N2O)(C2N3)]·H2OV = 1469.9 (3) Å3
Mr = 358.84Z = 4
Monoclinic, P21/cMo Kα
a = 9.8851 (12) ŵ = 1.50 mm−1
b = 7.0240 (6) ÅT = 293 (2) K
c = 21.398 (3) Å0.2 × 0.2 × 0.2 mm
β = 98.382 (9)º
Data collection top
Rigaku Mercury2 CCD
diffractometer		3487 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		2664 reflections with I > 2σ(I)
Tmin = 0.693, Tmax = 0.741Rint = 0.048
14839 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042208 parameters
wR(F2) = 0.115H-atom parameters constrained
S = 1.04Δρmax = 0.61 e Å−3
3487 reflectionsΔρmin = −0.35 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 > 2σ(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
Cu10.56134 (3)0.30788 (5)0.548195 (15)0.04185 (13)
O10.42489 (19)0.2985 (3)0.47469 (10)0.0489 (5)
N20.7131 (2)0.3036 (3)0.62161 (11)0.0411 (5)
N10.6994 (2)0.1915 (3)0.50553 (12)0.0463 (6)
C10.4349 (3)0.2127 (4)0.41987 (14)0.0439 (6)
N30.4226 (2)0.3912 (4)0.59818 (11)0.0477 (5)
O1W0.1486 (2)0.3114 (5)0.50627 (14)0.0968 (11)
H1WA0.09840.30910.46900.116*
H1WB0.23220.32660.49740.116*
C100.7040 (3)0.3557 (4)0.68161 (15)0.0508 (7)
H10A0.62190.40510.69080.061*
C70.6801 (3)0.1162 (4)0.44982 (13)0.0454 (6)
H7A0.75360.05210.43700.055*
C60.3203 (3)0.2118 (4)0.37236 (14)0.0501 (7)
H6A0.23840.26470.38050.060*
N40.2314 (2)0.4829 (5)0.65140 (12)0.0617 (7)
C140.3289 (3)0.4396 (4)0.62031 (12)0.0436 (6)
C30.5580 (3)0.0428 (4)0.34622 (14)0.0525 (7)
H3A0.6374−0.01630.33770.063*
C80.8366 (3)0.1772 (5)0.54199 (15)0.0582 (8)
H8A0.89860.26150.52420.070*
H8B0.87040.04800.54000.070*
C130.9430 (3)0.2075 (5)0.65564 (17)0.0584 (8)
H13A1.02410.15620.64600.070*
C20.5558 (3)0.1225 (4)0.40608 (13)0.0441 (6)
C110.8115 (4)0.3384 (5)0.72932 (16)0.0616 (8)
H11A0.80300.37800.77000.074*
C40.4466 (3)0.0493 (5)0.29979 (15)0.0594 (8)
H4B0.4506−0.00140.26000.071*
C90.8314 (3)0.2302 (4)0.60885 (14)0.0456 (6)
C120.9325 (3)0.2615 (5)0.71624 (18)0.0652 (9)
H12A1.00620.24640.74820.078*
C50.3281 (3)0.1335 (4)0.31392 (15)0.0549 (8)
H5A0.25140.13730.28310.066*
C150.1320 (3)0.5962 (5)0.62805 (14)0.0545 (7)
N50.0420 (3)0.6967 (5)0.61320 (16)0.0770 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03160 (19)0.0507 (2)0.0433 (2)0.00257 (13)0.00549 (13)0.00151 (14)
O10.0344 (10)0.0648 (13)0.0469 (11)0.0028 (8)0.0043 (8)−0.0062 (9)
N20.0357 (11)0.0430 (12)0.0442 (13)0.0004 (9)0.0047 (9)0.0042 (9)
N10.0312 (11)0.0562 (14)0.0521 (14)−0.0002 (9)0.0083 (10)0.0005 (11)
C10.0412 (14)0.0423 (15)0.0486 (17)−0.0065 (11)0.0073 (11)0.0018 (12)
N30.0408 (12)0.0539 (14)0.0489 (14)0.0061 (11)0.0080 (10)0.0039 (11)
O1W0.0436 (13)0.174 (3)0.0718 (18)−0.0051 (16)0.0055 (12)−0.0185 (18)
C100.0467 (16)0.0547 (16)0.0497 (17)0.0006 (13)0.0028 (13)0.0026 (13)
C70.0406 (14)0.0480 (15)0.0501 (17)0.0011 (12)0.0145 (12)0.0022 (13)
C60.0427 (15)0.0533 (17)0.0525 (18)−0.0056 (12)0.0004 (12)−0.0015 (13)
N40.0453 (14)0.096 (2)0.0449 (14)0.0191 (14)0.0118 (11)0.0100 (14)
C140.0391 (14)0.0506 (15)0.0396 (14)0.0007 (11)0.0008 (11)0.0042 (12)
C30.0577 (17)0.0534 (17)0.0491 (17)−0.0048 (13)0.0165 (14)0.0012 (13)
C80.0320 (14)0.082 (2)0.061 (2)0.0052 (14)0.0089 (13)−0.0044 (16)
C130.0336 (15)0.069 (2)0.070 (2)0.0030 (13)−0.0012 (13)−0.0001 (17)
C20.0431 (14)0.0453 (14)0.0448 (16)−0.0048 (11)0.0099 (11)0.0029 (12)
C110.065 (2)0.068 (2)0.0484 (18)−0.0034 (16)−0.0009 (15)−0.0006 (15)
C40.073 (2)0.0593 (19)0.0467 (18)−0.0120 (16)0.0101 (15)−0.0048 (14)
C90.0321 (13)0.0475 (15)0.0569 (17)−0.0037 (11)0.0056 (11)0.0026 (13)
C120.0453 (18)0.073 (2)0.071 (2)−0.0014 (16)−0.0122 (15)0.0050 (18)
C50.0582 (18)0.0539 (16)0.0496 (18)−0.0096 (14)−0.0025 (14)0.0038 (14)
C150.0403 (15)0.079 (2)0.0451 (16)0.0023 (15)0.0084 (12)−0.0045 (15)
N50.0517 (17)0.104 (3)0.074 (2)0.0257 (16)0.0057 (14)−0.0008 (17)
Geometric parameters (Å, °) top
Cu1—O11.9181 (19)C6—H6A0.9300
Cu1—N11.931 (2)N4—C141.284 (4)
Cu1—N31.948 (2)N4—C151.306 (4)
Cu1—N22.008 (2)C3—C41.372 (4)
O1—C11.335 (4)C3—C21.401 (4)
N2—C91.342 (4)C3—H3A0.9300
N2—C101.351 (4)C8—C91.487 (4)
N1—C71.293 (4)C8—H8A0.9700
N1—C81.466 (4)C8—H8B0.9700
C1—C61.407 (4)C13—C121.369 (5)
C1—C21.421 (4)C13—C91.386 (4)
N3—C141.152 (3)C13—H13A0.9300
O1W—H1WA0.8754C11—C121.377 (5)
O1W—H1WB0.8814C11—H11A0.9300
C10—C111.367 (4)C4—C51.384 (4)
C10—H10A0.9300C4—H4B0.9300
C7—C21.432 (4)C12—H12A0.9300
C7—H7A0.9300C5—H5A0.9300
C6—C51.379 (4)C15—N51.144 (4)
O1—Cu1—N193.37 (9)C4—C3—H3A119.0
O1—Cu1—N389.62 (9)C2—C3—H3A119.0
N1—Cu1—N3171.71 (10)N1—C8—C9109.6 (2)
O1—Cu1—N2175.47 (9)N1—C8—H8A109.7
N1—Cu1—N282.22 (10)C9—C8—H8A109.7
N3—Cu1—N294.61 (10)N1—C8—H8B109.7
C1—O1—Cu1127.05 (18)C9—C8—H8B109.7
C9—N2—C10118.6 (2)H8A—C8—H8B108.2
C9—N2—Cu1114.9 (2)C12—C13—C9119.3 (3)
C10—N2—Cu1126.45 (19)C12—C13—H13A120.3
C7—N1—C8117.6 (2)C9—C13—H13A120.3
C7—N1—Cu1126.15 (19)C3—C2—C1119.5 (3)
C8—N1—Cu1116.1 (2)C3—C2—C7117.3 (3)
O1—C1—C6118.8 (3)C1—C2—C7123.0 (3)
O1—C1—C2123.8 (3)C10—C11—C12119.1 (3)
C6—C1—C2117.4 (3)C10—C11—H11A120.5
C14—N3—Cu1170.9 (2)C12—C11—H11A120.5
H1WA—O1W—H1WB103.3C3—C4—C5118.1 (3)
N2—C10—C11122.3 (3)C3—C4—H4B120.9
N2—C10—H10A118.9C5—C4—H4B120.9
C11—C10—H10A118.9N2—C9—C13121.5 (3)
N1—C7—C2125.9 (3)N2—C9—C8116.4 (2)
N1—C7—H7A117.0C13—C9—C8122.1 (3)
C2—C7—H7A117.0C13—C12—C11119.3 (3)
C5—C6—C1120.8 (3)C13—C12—H12A120.4
C5—C6—H6A119.6C11—C12—H12A120.4
C1—C6—H6A119.6C6—C5—C4122.0 (3)
C14—N4—C15121.7 (3)C6—C5—H5A119.0
N3—C14—N4172.7 (3)C4—C5—H5A119.0
C4—C3—C2122.1 (3)N5—C15—N4173.6 (3)
N1—Cu1—O1—C17.4 (2)C4—C3—C2—C7−176.8 (3)
N3—Cu1—O1—C1−164.8 (2)O1—C1—C2—C3−177.5 (2)
N1—Cu1—N2—C90.57 (19)C6—C1—C2—C32.0 (4)
N3—Cu1—N2—C9172.9 (2)O1—C1—C2—C7−0.6 (4)
N1—Cu1—N2—C10−175.2 (2)C6—C1—C2—C7178.9 (3)
N3—Cu1—N2—C10−2.9 (2)N1—C7—C2—C3175.9 (3)
O1—Cu1—N1—C7−8.8 (3)N1—C7—C2—C1−1.1 (5)
N2—Cu1—N1—C7170.1 (3)N2—C10—C11—C12−1.4 (5)
O1—Cu1—N1—C8175.4 (2)C2—C3—C4—C5−1.7 (5)
N2—Cu1—N1—C8−5.6 (2)C10—N2—C9—C13−0.1 (4)
Cu1—O1—C1—C6176.29 (19)Cu1—N2—C9—C13−176.2 (2)
Cu1—O1—C1—C2−4.3 (4)C10—N2—C9—C8−179.3 (3)
C9—N2—C10—C110.8 (4)Cu1—N2—C9—C84.5 (3)
Cu1—N2—C10—C11176.5 (2)C12—C13—C9—N2−0.1 (5)
C8—N1—C7—C2−177.1 (3)C12—C13—C9—C8179.1 (3)
Cu1—N1—C7—C27.2 (4)N1—C8—C9—N2−8.7 (4)
O1—C1—C6—C5176.7 (3)N1—C8—C9—C13172.0 (3)
C2—C1—C6—C5−2.8 (4)C9—C13—C12—C11−0.4 (5)
C7—N1—C8—C9−167.0 (3)C10—C11—C12—C131.2 (5)
Cu1—N1—C8—C99.1 (3)C1—C6—C5—C41.4 (5)
C4—C3—C2—C10.2 (4)C3—C4—C5—C60.9 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···N5i0.882.082.947 (4)173
O1W—H1WB···O10.882.042.909 (3)167
O1W—H1WB···N30.882.693.157 (3)115
Symmetry codes: (i) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···N5i0.882.082.947 (4)173
O1W—H1WB···O10.882.042.909 (3)167
O1W—H1WB···N30.882.693.157 (3)115
Symmetry codes: (i) −x, −y+1, −z+1.
Acknowledgements top

This work was financially supported by the NNSFC (No. 20361004 and 20561004), the Key Project of the Chinese Ministry of Education (No. 205147), the Specialized Research Fund for the Doctoral Program of Higher Education (No. 2006673015) and the NSF of Yunnan Province (No. 2004E0008M and 2003RC13).

references
References top

Li, Z.-X. & Zhang, X.-L. (2004). Acta Cryst. E60, m1017–m1019.

Rigaku (2005). CrystalStructure. Version 1.4.0. Rigaku Americas Corporation, The Woodlands, Texas, USA.

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

Sheldrick, G. M. (1999). SHELXTL/PC. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

You, Z.-L., Chen, B., Zhu, H.-L. & Liu, W.-S. (2004). Acta Cryst. E60, m884–m886.

You, Z.-L. & Zhu, H.-L. (2004). Z. Anorg. Allg. Chem. 630, 2754–2760.

Zhang, J.-H., Xi, Y., Wang, C., Li, J., Zhang, F.-X. & Ng, S. W. (2005). Acta Cryst. E61, m2338–m2339.