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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m118.
Published online 2007 December 6. doi:  10.1107/S1600536807064033
PMCID: PMC2915070

(1-{2-[2-(2-Ammonio­ethyl­amino)ethyl­amino]ethyl­imino­meth­yl}-2-naphtholato-κ4 O,N,N′,N′′)chloridocopper(II) chloride

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-0m118-scheme1.jpg

Experimental

Crystal data

  • [CuCl(C17H24N4O)]Cl
  • M r = 434.84
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m118-efi1.jpg
  • a = 12.2687 (17) Å
  • b = 13.0277 (18) Å
  • c = 12.7118 (18) Å
  • β = 111.365 (2)°
  • V = 1892.1 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.45 mm−1
  • T = 298 (2) K
  • 0.48 × 0.40 × 0.37 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.543, T max = 0.616 (expected range = 0.515–0.585)
  • 9597 measured reflections
  • 3320 independent reflections
  • 2646 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.099
  • S = 1.00
  • 3320 reflections
  • 226 parameters
  • H-atom parameters constrained
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.40 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807064033/ln2007sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064033/ln2007Isup2.hkl

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

Fig. 1.
The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
Fig. 2.
Crystal packing of the title complex showing the hydrogen bonding interactions as dashed lines.

Crystal data

[CuCl(C17H24N4O)]ClF000 = 900
Mr = 434.84Dx = 1.526 Mg m3
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 mm1
β = 111.365 (2)ºT = 298 (2) K
V = 1892.1 (5) Å3Block, green
Z = 40.48 × 0.40 × 0.37 mm

Data collection

Bruker CCD area-detector diffractometer3320 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

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 Å3
226 parametersΔρmin = −0.40 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
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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LN2007).

References

  • 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.

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