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Acta Cryst. (2008). E64, m118    [ doi:10.1107/S1600536807064033 ]

(1-{2-[2-(2-Ammonioethylamino)ethylamino]ethyliminomethyl}-2-naphtholato-[kappa]4O,N,N',N'')chloridocopper(II) chloride

R. Xue and M. Niu

Abstract top

In the square-pyramidal title complex, [CuCl(C17H24N4O)]Cl, the CuII atom is coordinated by three N atoms [Cu-N 1.946 (2), 2.010 (2), 2.085 (3) Å], one O atom [Cu-O 1.910 (2) Å] and one apical Cl atom [Cu-Cl 2.6437 (9) Å]. The three coordinated N and one O atom are almost coplanar, with a maximum deviation of 0.0268 Å. The tetradentate ligand forms two five-membered (N-Cu-N) and one six-membered (N-Cu-O) chelate rings with bite angles of 84.06 (10), 85.30 (10) and 91.70 (9)°, respectively. The two N-Cu-N chelate rings are non-planar.

Comment top

Schiff base complexes play an important role in coordination chemistry (Gamovski et al., 1993). In a continuation of a study of Schiff base ligands and their copper(II) complexes, we report here the title complex (Fig. 1), in which the ligand donor atoms consist of three nitrogen atoms (one imine and two amine) and one phenolic oxygen atom. Another CuII complex containing the same tetradentate ligand has been reported by Nanda et al. (2006). In the crystal structure of (I), intermolecular N—H···Cl hydrogen bonds involving all amine and the ammonium groups link the molecules into two-dimensional networks, which lie parallel to the (100) plane (Table 1, Fig. 2). The ammonium group also forms an intramolecular hydrogen bond with the phenolic O atom.

Related literature top

For the general role of Schiff bases, see: Gamovski et al. (1993). For thecrystal structures of related complexes, see: Nanda et al. (2006).

Experimental top

A solution of triethylenetetramine(1 mmol) in hot methanol (10 ml) was added dropwise to a methanol solution (5 ml) of 2-hydroxy-1-naphthaldehyde (2 mmol, 344.3 mg). The mixture was then stirred at 323 K for 2 h. An aqueous solution (2 ml) of cupric chloride dihydrate (1 mmol, 170.8 mg) was then added dropwise and the mixture stirred for another 5 h. The solution was held at room temperature for about one week, whereupon green prism-shaped crystals suitable for X-ray diffraction analysis were obtained (m.p. > 573 K).

Refinement top

All H atoms were placed in geometrically idealized positions and refined using a riding model, with C—H = 0.97 Å (methylene) or 0.93 Å (aromatic, methenyl), N—H = 0.91 Å (imine) or 0.89 Å (ammonium) and with with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(N).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. Crystal packing of the title complex showing the hydrogen bonding interactions as dashed lines.
(1-{2-[2-(2-Ammonioethylamino)ethylamino]ethyliminomethyl}-2-naphtholato- κ4O,N,N',N'')chloridocopper(II) chloride top
Crystal data top
[CuCl(C17H24N4O)]ClF000 = 900
Mr = 434.84Dx = 1.526 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
a = 12.2687 (17) ÅCell parameters from 3813 reflections
b = 13.0277 (18) Åθ = 2.5–26.7º
c = 12.7118 (18) ŵ = 1.45 mm−1
β = 111.365 (2)ºT = 298 (2) K
V = 1892.1 (5) Å3Block, green
Z = 40.48 × 0.40 × 0.37 mm
Data collection top
Bruker CCD area-detector
diffractometer		3320 independent reflections
Radiation source: fine-focus sealed tube2646 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 298(2) Kθmax = 25.0º
phi and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.543, Tmax = 0.616k = −15→12
9597 measured reflectionsl = −14→15
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)] = 0.034H-atom parameters constrained
wR(F2) = 0.099  w = 1/[σ2(Fo2) + (0.0538P)2 + 1.3872P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
3320 reflectionsΔρmax = 0.59 e Å−3
226 parametersΔρmin = −0.40 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[CuCl(C17H24N4O)]ClV = 1892.1 (5) Å3
Mr = 434.84Z = 4
Monoclinic, P21/cMo Kα
a = 12.2687 (17) ŵ = 1.45 mm−1
b = 13.0277 (18) ÅT = 298 (2) K
c = 12.7118 (18) Å0.48 × 0.40 × 0.37 mm
β = 111.365 (2)º
Data collection top
Bruker CCD area-detector
diffractometer		3320 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2646 reflections with I > 2σ(I)
Tmin = 0.543, Tmax = 0.616Rint = 0.027
9597 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034226 parameters
wR(F2) = 0.099H-atom parameters constrained
S = 1.00Δρmax = 0.59 e Å−3
3320 reflectionsΔρmin = −0.40 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
Cu10.70712 (3)0.22917 (3)0.92710 (3)0.03282 (14)
Cl10.59641 (8)0.15391 (7)0.72264 (7)0.0511 (2)
Cl20.26659 (9)0.14202 (8)0.07523 (10)0.0662 (3)
N10.8689 (2)0.22822 (18)0.9363 (2)0.0327 (6)
N20.7491 (2)0.09353 (18)1.0070 (2)0.0342 (6)
H20.72610.04260.95450.041*
N30.5626 (2)0.22573 (19)0.9765 (2)0.0377 (6)
H30.58090.26671.03850.045*
N40.4596 (3)0.4130 (2)0.8025 (3)0.0599 (8)
H4A0.44620.48030.79850.090*
H4B0.42060.38440.73580.090*
H4C0.53590.40170.82120.090*
O10.69138 (17)0.37176 (15)0.88974 (19)0.0406 (5)
C10.9272 (3)0.3033 (2)0.9185 (2)0.0328 (7)
H11.00570.29180.93080.039*
C20.8815 (2)0.4046 (2)0.8810 (2)0.0304 (6)
C30.7695 (3)0.4344 (2)0.8753 (2)0.0328 (7)
C40.7349 (3)0.5390 (2)0.8524 (3)0.0400 (7)
H40.66220.55970.85190.048*
C50.8061 (3)0.6090 (2)0.8313 (3)0.0418 (8)
H50.78160.67690.81810.050*
C60.9163 (3)0.5815 (2)0.8290 (3)0.0372 (7)
C70.9567 (3)0.4795 (2)0.8561 (2)0.0332 (7)
C81.0697 (3)0.4563 (2)0.8560 (3)0.0438 (8)
H81.09870.39000.87280.053*
C91.1367 (3)0.5298 (3)0.8319 (3)0.0502 (9)
H91.21080.51270.83330.060*
C101.0955 (3)0.6301 (3)0.8050 (3)0.0499 (9)
H101.14180.67940.78870.060*
C110.9881 (3)0.6547 (3)0.8030 (3)0.0471 (8)
H110.96050.72130.78420.057*
C120.9279 (3)0.1298 (2)0.9797 (3)0.0411 (8)
H12A1.01160.14031.01630.049*
H12B0.91450.08150.91820.049*
C130.8775 (3)0.0893 (2)1.0628 (3)0.0395 (7)
H13A0.90290.01921.08360.047*
H13B0.90290.13101.13070.047*
C140.6823 (3)0.0837 (3)1.0821 (3)0.0460 (8)
H14A0.71720.12581.14900.055*
H14B0.68200.01291.10550.055*
C150.5603 (3)0.1189 (2)1.0168 (3)0.0470 (8)
H15A0.52440.07380.95270.056*
H15B0.51400.11631.06440.056*
C160.4418 (3)0.2538 (3)0.9023 (4)0.0547 (10)
H16A0.38730.22430.93330.066*
H16B0.42550.22360.82840.066*
C170.4203 (4)0.3678 (3)0.8885 (4)0.0680 (12)
H17A0.33730.38080.86780.082*
H17B0.46090.40120.96040.082*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0285 (2)0.0288 (2)0.0378 (2)0.00173 (14)0.00819 (16)0.00456 (15)
Cl10.0517 (5)0.0531 (5)0.0416 (5)−0.0067 (4)0.0088 (4)−0.0052 (4)
Cl20.0524 (6)0.0529 (6)0.0853 (7)0.0006 (4)0.0156 (5)−0.0208 (5)
N10.0287 (13)0.0297 (13)0.0362 (14)0.0036 (10)0.0075 (11)0.0021 (11)
N20.0332 (14)0.0299 (13)0.0334 (14)−0.0002 (10)0.0048 (11)0.0015 (11)
N30.0373 (14)0.0330 (14)0.0456 (16)−0.0008 (11)0.0183 (12)0.0041 (11)
N40.0419 (17)0.0528 (19)0.077 (2)0.0075 (14)0.0127 (16)0.0175 (17)
O10.0283 (11)0.0320 (12)0.0581 (14)0.0030 (9)0.0117 (10)0.0069 (10)
C10.0287 (15)0.0347 (16)0.0330 (16)0.0019 (12)0.0087 (13)−0.0028 (13)
C20.0323 (15)0.0295 (15)0.0249 (15)−0.0011 (12)0.0050 (12)−0.0033 (12)
C30.0349 (16)0.0288 (15)0.0304 (16)−0.0018 (13)0.0066 (13)−0.0024 (12)
C40.0362 (17)0.0326 (17)0.047 (2)0.0045 (13)0.0108 (15)0.0005 (14)
C50.048 (2)0.0275 (16)0.0448 (19)0.0033 (14)0.0114 (16)0.0015 (14)
C60.0415 (18)0.0325 (16)0.0332 (17)−0.0052 (13)0.0083 (14)−0.0007 (13)
C70.0345 (16)0.0344 (16)0.0258 (15)−0.0035 (13)0.0051 (13)−0.0055 (12)
C80.0436 (19)0.0414 (19)0.047 (2)−0.0032 (15)0.0172 (16)0.0012 (15)
C90.042 (2)0.057 (2)0.054 (2)−0.0056 (16)0.0204 (17)0.0024 (17)
C100.053 (2)0.051 (2)0.047 (2)−0.0159 (17)0.0193 (18)0.0033 (16)
C110.058 (2)0.0377 (18)0.0417 (19)−0.0077 (16)0.0135 (17)0.0023 (15)
C120.0310 (17)0.0336 (17)0.054 (2)0.0074 (13)0.0098 (15)0.0043 (14)
C130.0352 (17)0.0320 (17)0.0422 (18)0.0044 (13)0.0032 (14)0.0063 (13)
C140.048 (2)0.0414 (19)0.049 (2)0.0008 (15)0.0181 (17)0.0124 (16)
C150.047 (2)0.0382 (18)0.060 (2)−0.0022 (15)0.0240 (18)0.0106 (16)
C160.0349 (19)0.059 (2)0.070 (3)0.0065 (16)0.0185 (18)0.0179 (19)
C170.061 (3)0.067 (3)0.083 (3)0.026 (2)0.035 (2)0.021 (2)
Geometric parameters (Å, °) top
Cu1—O11.910 (2)C5—H50.9300
Cu1—N11.946 (2)C6—C71.415 (4)
Cu1—N22.010 (2)C6—C111.417 (4)
Cu1—N32.085 (3)C7—C81.420 (4)
Cu1—Cl12.6437 (9)C8—C91.367 (5)
N1—C11.280 (4)C8—H80.9300
N1—C121.477 (4)C9—C101.398 (5)
N2—C141.472 (4)C9—H90.9300
N2—C131.475 (4)C10—C111.347 (5)
N2—H20.9100C10—H100.9300
N3—C161.484 (4)C11—H110.9300
N3—C151.487 (4)C12—C131.502 (5)
N3—H30.9100C12—H12A0.9700
N4—C171.470 (5)C12—H12B0.9700
N4—H4A0.8900C13—H13A0.9700
N4—H4B0.8900C13—H13B0.9700
N4—H4C0.8900C14—C151.495 (5)
O1—C31.321 (3)C14—H14A0.9700
C1—C21.445 (4)C14—H14B0.9700
C1—H10.9300C15—H15A0.9700
C2—C31.404 (4)C15—H15B0.9700
C2—C71.455 (4)C16—C171.507 (5)
C3—C41.426 (4)C16—H16A0.9700
C4—C51.355 (4)C16—H16B0.9700
C4—H40.9300C17—H17A0.9700
C5—C61.410 (4)C17—H17B0.9700
O1—Cu1—N191.70 (9)C6—C7—C2119.3 (3)
O1—Cu1—N2164.83 (10)C8—C7—C2123.6 (3)
N1—Cu1—N284.06 (10)C9—C8—C7121.2 (3)
O1—Cu1—N394.34 (9)C9—C8—H8119.4
N1—Cu1—N3160.46 (11)C7—C8—H8119.4
N2—Cu1—N385.30 (10)C8—C9—C10121.0 (3)
O1—Cu1—Cl198.46 (7)C8—C9—H9119.5
N1—Cu1—Cl1101.77 (8)C10—C9—H9119.5
N2—Cu1—Cl196.66 (7)C11—C10—C9119.5 (3)
N3—Cu1—Cl195.70 (8)C11—C10—H10120.3
C1—N1—C12120.0 (3)C9—C10—H10120.3
C1—N1—Cu1127.5 (2)C10—C11—C6121.4 (3)
C12—N1—Cu1112.23 (19)C10—C11—H11119.3
C14—N2—C13115.7 (2)C6—C11—H11119.3
C14—N2—Cu1107.68 (18)N1—C12—C13107.3 (2)
C13—N2—Cu1107.95 (18)N1—C12—H12A110.3
C14—N2—H2108.4C13—C12—H12A110.3
C13—N2—H2108.4N1—C12—H12B110.3
Cu1—N2—H2108.4C13—C12—H12B110.3
C16—N3—C15108.0 (2)H12A—C12—H12B108.5
C16—N3—Cu1124.5 (2)N2—C13—C12106.9 (2)
C15—N3—Cu1104.42 (18)N2—C13—H13A110.4
C16—N3—H3106.3C12—C13—H13A110.4
C15—N3—H3106.3N2—C13—H13B110.4
Cu1—N3—H3106.3C12—C13—H13B110.4
C17—N4—H4A109.5H13A—C13—H13B108.6
C17—N4—H4B109.5N2—C14—C15107.1 (3)
H4A—N4—H4B109.5N2—C14—H14A110.3
C17—N4—H4C109.5C15—C14—H14A110.3
H4A—N4—H4C109.5N2—C14—H14B110.3
H4B—N4—H4C109.5C15—C14—H14B110.3
C3—O1—Cu1128.49 (18)H14A—C14—H14B108.6
N1—C1—C2125.5 (3)N3—C15—C14109.7 (3)
N1—C1—H1117.2N3—C15—H15A109.7
C2—C1—H1117.2C14—C15—H15A109.7
C3—C2—C1121.6 (3)N3—C15—H15B109.7
C3—C2—C7119.3 (3)C14—C15—H15B109.7
C1—C2—C7118.9 (3)H15A—C15—H15B108.2
O1—C3—C2124.6 (3)N3—C16—C17114.1 (3)
O1—C3—C4116.2 (3)N3—C16—H16A108.7
C2—C3—C4119.2 (3)C17—C16—H16A108.7
C5—C4—C3121.2 (3)N3—C16—H16B108.7
C5—C4—H4119.4C17—C16—H16B108.7
C3—C4—H4119.4H16A—C16—H16B107.6
C4—C5—C6121.7 (3)N4—C17—C16113.0 (3)
C4—C5—H5119.1N4—C17—H17A109.0
C6—C5—H5119.1C16—C17—H17A109.0
C5—C6—C7119.1 (3)N4—C17—H17B109.0
C5—C6—C11121.1 (3)C16—C17—H17B109.0
C7—C6—C11119.8 (3)H17A—C17—H17B107.8
C6—C7—C8117.0 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl2i0.912.443.225 (3)144
N3—H3···Cl1ii0.912.503.388 (3)165
N4—H4A···Cl1iii0.892.313.204 (3)177
N4—H4B···Cl2ii0.892.253.079 (4)156
N4—H4C···O10.891.832.703 (4)167
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl2i0.912.443.225 (3)144
N3—H3···Cl1ii0.912.503.388 (3)165
N4—H4A···Cl1iii0.892.313.204 (3)177
N4—H4B···Cl2ii0.892.253.079 (4)156
N4—H4C···O10.891.832.703 (4)167
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2.
Acknowledgements top

The authors acknowledge the financial support of the Shandong Province Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University, People's Republic of China.

references
References top

Gamovski, A. D., Nivorozhkin, A. L. & Minkin, V. I. (1993). Coord. Chem. Rev. 126, 1–69.

Nanda, P. K., Bera, M., Aromi, G. & Ray, D. (2006). Polyhedron, 25, 2791–2799.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS, Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instrument Inc., Madison, Wisconsin, USA.