supplementary materials


rz5068 scheme

Acta Cryst. (2013). E69, m383    [ doi:10.1107/S1600536813015882 ]

Poly[bis{[mu]-N'-[(pyridin-4-yl)methylidene]benzohydrazidato}copper(II)]

Q. Wu, D.-C. Chen, C.-Y. Wu, C.-X. Yan and J.-Z. Liao

Abstract top

In the title complex, [Cu(C13H10N3O)2]n, the copper(II) cation is located on a crystallographic inversion centre and adopts an elongated octahedral coordination geometry with the equatorial plane provided by trans-arranged bis-N,O-chelating acylhydrazine groups from two ligands and the apices by the N atoms of two pyridine rings belonging to symmetry-related ligands. The ligand adopts a Z conformation about the C=N double bond. The dihedral angle between the pyridine and phenyl rings is 2.99 (13)°. An intraligand C-H...N hydrogen bond is observed. In the crystal, each ligand bridges two adjacent metal ions, forming a (4,4) grid layered structure. [pi]-[pi] stacking interactions [centroid-centroid distances in the range 3.569 (4)-3.584 (9) Å] involving rings of adjacent layers result in the formation of a three-dimensional supramolecular network.

Comment top

Schiff bases and their metal compounds were widely synthesized in recent years and characterized for their wide range of applications as biocides and homogeneous catalysts in industry (Schurig et al., 1980; Siddall et al., 1983; Maurya et al., 2005). In previous reports, most of the Schiff base coordination compounds were oligomers such as zero-dimensional complexes with catalytic (Cozzi, 2004) or magnetic properties (Liu, et al., 2010). In this paper, the structure of a new two-dimensional polymeric copper(II) coordination compound is reported.

The asymmetric unit of the title complex contains one copper(II) ion located on an inversion centre and one deprotonated N'-(pyridin-4-ylmethyl) benzohydrazide ligand. The metal ion adopts a significantly elongated octahedral coordination geometry provided by four ligands (Fig. 1). The equatorial plane is occupied by two trans-arranged bis-N,O-chelating acylhydrazine groups from two ligands, while the axial positions are occupied by two N atoms of pyridine rings from other two ligands. In the equatorial plane, the Cu—O and Cu—N bond lengths are 1.942 (6) Å and 2.004 (4) Å, respectively, which are similar to those reported in the literature for related compounds (Yin 2008; Uçar et al., 2004; Sommerer et al., 1998). The apical Cu—N distances (2.578 (8) Å) are slightly longer than a common stretched Cu—N distance (Moya-Hernández et al., 2003), generating an elongated octahedral coordination geometry typically attributed to the Jahn-Teller effect. The ligand is approximately planar (maximum deviation from the least square plane is 0.0473 (13) Å for atom O1) and chelates to the copper atom to form a five-numbered ring (Cu1/O1/C7/N1/N2). The dihedral angle formed by the pyridine and phenyl rings is 2.99 (13)°. An intraligand C—H···N hydrogen bond is present (Table 1). In the crystal, each ligand bridges two adjacent metal ions (Fig. 2), meanwhile each copper atom is coordinated with four ligands to form a (4, 4) grid layered structure. Adjacent layers are further connected via π···π stacking interactions between benzene rings [Cg1···Cg1i =3.584 (9) Å; Cg1 is the centroid of the C1–C6 ring; symmetry code: (i) -1/2 - x, 1/2 - y, -z] and benzene and pyridine ring [Cg1···Cg2ii = 3.569 (4) Å; Cg2 is the centroid of the N1/C9–C13 ring; symmetry code: (ii) -x, -y, -z], forming a three-dimensional supramolecular structure (Fig. 3).

Related literature top

For background to properties and applications of Schiff base–metal complexes, see: Schurig et al. (1980); Siddall et al. (1983); Maurya et al. (2005); Cozzi (2004); Liu, et al. (2010). For the structures of related compounds, see: Yin (2008); Uçar et al. (2004); Sommerer et al. (1998); Moya-Hernández et al. (2003).

Experimental top

A mixture of N'-(pyridin-4-ylmethyl)benzohydrazide (0.045 g, 0.02 mmol), Cu(CH3COO)2.4H2O (0.026 g, 0.01 mmol) in ethanol (6 mL) was stirred for 40 minutes and then heated in a 25 mL Teflon-lined autoclave at 100°C for 3 days, followed by cooling to room temperature. The resulting mixture was washed with water, and brown crystals were collected and dried in air. Yield: 40% (based on Cu).

Refinement top

All H atoms were placed in idealized positions using a riding-model approximation, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms are omitted for clarity. Symmetry codes: (i) 0.5 - x, 0.5 - y, -z; (ii) 0.5 - x, 0.5 + y, 0.5 - z; (iii) x, -y, -0.5 + z.
[Figure 2] Fig. 2. Capped sticks diagram of the two-dimensional grid in the title compound.
[Figure 3] Fig. 3. Packing diagram of the title compound, showing the π-π stacking interactions between phenyl rings (green dashed lines) or between phenyl and pyridine rings (red dashed lines). H atoms are omitted for clarity.
Poly[bis{µ-N'-[(pyridin-4-yl)methylidene]benzohydrazidato}copper(II)] top
Crystal data top
[Cu(C13H10N3O)2]Z = 4
Mr = 512.02F(000) = 1052
Monoclinic, C2/cDx = 1.586 Mg m3
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 12.288 (3) ŵ = 1.06 mm1
b = 13.349 (3) ÅT = 173 K
c = 14.244 (3) ÅBlock, brown
β = 113.39 (3)°0.40 × 0.20 × 0.12 mm
V = 2144.5 (10) Å3
Data collection top
Rigaku Mercury CCD area-detector
diffractometer
2460 independent reflections
Radiation source: fine-focus sealed tube2033 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω scanθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2007)
h = 1515
Tmin = 0.843, Tmax = 1.000k = 1717
10356 measured reflectionsl = 1818
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.038P)2 + 1.4497P]
where P = (Fo2 + 2Fc2)/3
2460 reflections(Δ/σ)max < 0.001
160 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
[Cu(C13H10N3O)2]V = 2144.5 (10) Å3
Mr = 512.02Z = 4
Monoclinic, C2/cMo Kα radiation
a = 12.288 (3) ŵ = 1.06 mm1
b = 13.349 (3) ÅT = 173 K
c = 14.244 (3) Å0.40 × 0.20 × 0.12 mm
β = 113.39 (3)°
Data collection top
Rigaku Mercury CCD area-detector
diffractometer
2460 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2007)
2033 reflections with I > 2σ(I)
Tmin = 0.843, Tmax = 1.000Rint = 0.035
10356 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.080Δρmax = 0.33 e Å3
S = 1.05Δρmin = 0.19 e Å3
2460 reflectionsAbsolute structure: ?
160 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
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
Cu10.25000.25000.00000.03006 (12)
O10.07807 (11)0.24346 (9)0.06638 (10)0.0309 (3)
N30.27033 (14)0.10391 (12)0.38950 (12)0.0319 (4)
N20.21900 (13)0.15245 (10)0.09372 (11)0.0246 (3)
N10.09996 (13)0.13652 (11)0.06875 (12)0.0278 (3)
C130.38186 (16)0.00109 (14)0.32256 (15)0.0323 (4)
H130.45760.02110.32810.039*
C100.17175 (16)0.00125 (14)0.24281 (15)0.0321 (4)
H100.09880.02420.19230.038*
C110.17304 (17)0.06719 (15)0.31632 (15)0.0346 (4)
H110.09880.08960.31430.042*
C90.27962 (16)0.03584 (13)0.24435 (14)0.0265 (4)
C70.03622 (16)0.18736 (13)0.01562 (14)0.0258 (4)
C120.37330 (17)0.06991 (15)0.39198 (15)0.0329 (4)
H120.44440.09410.44400.039*
C10.16555 (18)0.23105 (14)0.13975 (16)0.0339 (4)
H10.12960.27050.17510.041*
C60.09470 (16)0.17841 (13)0.05313 (14)0.0278 (4)
C80.29530 (15)0.10671 (13)0.17138 (14)0.0265 (4)
H80.37560.12110.18390.032*
C30.34020 (18)0.16951 (16)0.12463 (17)0.0405 (5)
H30.42410.16750.14820.049*
C40.27127 (19)0.11491 (17)0.03975 (18)0.0418 (5)
H40.30790.07430.00580.050*
C20.28764 (18)0.22705 (15)0.17542 (17)0.0389 (5)
H20.33520.26380.23470.047*
C50.14871 (17)0.11890 (15)0.00365 (16)0.0362 (4)
H50.10150.08100.05490.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02433 (17)0.0392 (2)0.02625 (18)0.00444 (14)0.00965 (13)0.01200 (14)
O10.0302 (6)0.0357 (7)0.0279 (7)0.0040 (6)0.0128 (6)0.0066 (5)
N30.0378 (9)0.0309 (8)0.0280 (9)0.0025 (7)0.0141 (7)0.0053 (6)
N20.0270 (7)0.0247 (7)0.0247 (8)0.0015 (6)0.0130 (6)0.0002 (6)
N10.0257 (7)0.0301 (8)0.0282 (8)0.0026 (6)0.0113 (6)0.0050 (6)
C130.0284 (9)0.0358 (10)0.0337 (11)0.0008 (8)0.0136 (8)0.0044 (8)
C100.0285 (9)0.0346 (9)0.0307 (10)0.0012 (8)0.0090 (8)0.0077 (8)
C110.0315 (10)0.0369 (10)0.0363 (11)0.0004 (8)0.0144 (9)0.0088 (8)
C90.0309 (9)0.0235 (8)0.0262 (9)0.0025 (7)0.0125 (8)0.0013 (7)
C70.0314 (9)0.0238 (8)0.0247 (9)0.0023 (7)0.0139 (8)0.0017 (7)
C120.0320 (9)0.0353 (10)0.0289 (10)0.0065 (8)0.0094 (8)0.0072 (8)
C10.0352 (10)0.0333 (10)0.0337 (11)0.0001 (8)0.0143 (9)0.0064 (8)
C60.0308 (9)0.0272 (9)0.0276 (10)0.0028 (7)0.0139 (8)0.0006 (7)
C80.0279 (9)0.0265 (8)0.0272 (9)0.0003 (7)0.0133 (8)0.0017 (7)
C30.0301 (10)0.0448 (12)0.0471 (13)0.0040 (9)0.0159 (9)0.0033 (9)
C40.0391 (11)0.0462 (12)0.0455 (12)0.0106 (10)0.0227 (10)0.0031 (10)
C20.0340 (10)0.0396 (11)0.0382 (12)0.0031 (9)0.0092 (9)0.0068 (8)
C50.0350 (10)0.0402 (11)0.0339 (11)0.0026 (9)0.0141 (9)0.0080 (8)
Geometric parameters (Å, º) top
Cu1—O1i1.9440 (15)C11—H110.9500
Cu1—O11.9440 (15)C9—C81.474 (2)
Cu1—N2i2.0066 (14)C7—C61.485 (2)
Cu1—N22.0066 (14)C12—H120.9500
O1—C71.282 (2)C1—C21.381 (3)
N3—C111.329 (2)C1—C61.386 (3)
N3—C121.331 (2)C1—H10.9500
N2—C81.285 (2)C6—C51.393 (3)
N2—N11.378 (2)C8—H80.9500
N1—C71.331 (2)C3—C41.377 (3)
C13—C121.384 (3)C3—C21.379 (3)
C13—C91.397 (3)C3—H30.9500
C13—H130.9500C4—C51.386 (3)
C10—C111.385 (3)C4—H40.9500
C10—C91.395 (3)C2—H20.9500
C10—H100.9500C5—H50.9500
O1i—Cu1—O1180.0N1—C7—C6116.68 (15)
O1i—Cu1—N2i80.66 (6)N3—C12—C13123.25 (18)
O1—Cu1—N2i99.34 (6)N3—C12—H12118.4
O1i—Cu1—N299.34 (6)C13—C12—H12118.4
O1—Cu1—N280.66 (6)C2—C1—C6120.98 (18)
N2i—Cu1—N2180.00 (8)C2—C1—H1119.5
C7—O1—Cu1110.72 (12)C6—C1—H1119.5
C11—N3—C12116.40 (16)C1—C6—C5118.85 (17)
C8—N2—N1119.06 (15)C1—C6—C7119.16 (16)
C8—N2—Cu1127.92 (12)C5—C6—C7121.98 (17)
N1—N2—Cu1113.01 (11)N2—C8—C9131.08 (16)
C7—N1—N2109.77 (14)N2—C8—H8114.5
C12—C13—C9120.31 (18)C9—C8—H8114.5
C12—C13—H13119.8C4—C3—C2120.16 (19)
C9—C13—H13119.8C4—C3—H3119.9
C11—C10—C9118.73 (18)C2—C3—H3119.9
C11—C10—H10120.6C3—C4—C5120.28 (19)
C9—C10—H10120.6C3—C4—H4119.9
N3—C11—C10124.95 (18)C5—C4—H4119.9
N3—C11—H11117.5C3—C2—C1119.68 (19)
C10—C11—H11117.5C3—C2—H2120.2
C10—C9—C13116.34 (17)C1—C2—H2120.2
C10—C9—C8126.20 (17)C4—C5—C6120.01 (19)
C13—C9—C8117.45 (16)C4—C5—H5120.0
O1—C7—N1125.68 (16)C6—C5—H5120.0
O1—C7—C6117.64 (16)
N2i—Cu1—O1—C7176.85 (12)C11—N3—C12—C130.8 (3)
N2—Cu1—O1—C73.15 (12)C9—C13—C12—N30.5 (3)
O1i—Cu1—N2—C82.68 (16)C2—C1—C6—C51.6 (3)
O1—Cu1—N2—C8177.32 (16)C2—C1—C6—C7178.12 (18)
O1i—Cu1—N2—N1176.46 (11)O1—C7—C6—C10.6 (3)
O1—Cu1—N2—N13.54 (11)N1—C7—C6—C1178.95 (17)
C8—N2—N1—C7177.64 (15)O1—C7—C6—C5179.64 (17)
Cu1—N2—N1—C73.13 (17)N1—C7—C6—C50.8 (3)
C12—N3—C11—C101.3 (3)N1—N2—C8—C90.2 (3)
C9—C10—C11—N30.3 (3)Cu1—N2—C8—C9178.87 (14)
C11—C10—C9—C131.0 (3)C10—C9—C8—N20.8 (3)
C11—C10—C9—C8178.68 (18)C13—C9—C8—N2179.51 (18)
C12—C13—C9—C101.4 (3)C2—C3—C4—C51.2 (3)
C12—C13—C9—C8178.30 (17)C4—C3—C2—C11.1 (3)
Cu1—O1—C7—N12.6 (2)C6—C1—C2—C30.3 (3)
Cu1—O1—C7—C6176.93 (12)C3—C4—C5—C60.1 (3)
N2—N1—C7—O10.4 (2)C1—C6—C5—C41.5 (3)
N2—N1—C7—C6179.92 (14)C7—C6—C5—C4178.24 (19)
Symmetry code: (i) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C10—H10···N10.952.322.907 (3)120

Experimental details

Crystal data
Chemical formula[Cu(C13H10N3O)2]
Mr512.02
Crystal system, space groupMonoclinic, C2/c
Temperature (K)173
a, b, c (Å)12.288 (3), 13.349 (3), 14.244 (3)
β (°) 113.39 (3)
V3)2144.5 (10)
Z4
Radiation typeMo Kα
µ (mm1)1.06
Crystal size (mm)0.40 × 0.20 × 0.12
Data collection
DiffractometerRigaku Mercury CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2007)
Tmin, Tmax0.843, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
10356, 2460, 2033
Rint0.035
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.080, 1.05
No. of reflections2460
No. of parameters160
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.33, 0.19

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C10—H10···N10.952.322.907 (3)119.7
Acknowledgements top

We thank Professor Chang-Cang Huang for his patient advice. This work was supported by the Ability Enhanced Project of Undergraduate Talent of Fuzhou University, which is supported by the National Talent Fund Projects.

references
References top

Cozzi, P. G. (2004). Chem. Soc. Rev. 33, 410–421.

Liu, C. M., Zhang, D. Q. & Zhu, D. B. (2010). Dalton Trans. 39, 1781–1785.

Maurya, M. R., Sikarwar, S. & Joseph, T. (2005). React. Funct. Polym. 63, 71–83.

Moya-Hernández, M. R., Mederos, A., Domínguez, S., Orlandini, A., Ghilardi, C. A., Cecconi, F., González-Vergara, E. & Rojas-Hernández, A. (2003). J. Inorg. Biochem. 95, 131–140.

Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Schurig, V., Koppenhoefer, B. & Buerkle, W. (1980). J. Org. Chem. 45, 538–541.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siddall, T. L., Miyaura, N. & Huffman, J. C. (1983). J. Chem. Soc. Chem. Commun. pp. 1185–1986.

Sommerer, S. O., Friebe, T. L., Jircitano, A. J., MacBeth, C. E. & Abboud, K. A. (1998). Acta Cryst. C54, 178–179.

Uçar, İ., Bulut, A., Yeşilel, O. Z., Ölmez, H. I. & Büyükgüngör, O. (2004). Acta Cryst. E60, m1945–m1948.

Yin, H. (2008). Acta Cryst. C64, m324–m326.