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Acta Cryst. (2007). E63, m2431    [ doi:10.1107/S1600536807041669 ]

Chlorido[2,4-dibromo-6-(2-pyridylmethylaminomethyl)phenolato]copper(II)

J.-C. Ma, J. Yang and J.-F. Ma

Abstract top

In the title compound, [Cu(C13H11Br2N2O)Cl], the CuII atom is four-coordinated by an N,N,O-tridentate 2,4-dibromo-6-(2-pyridylmethylaminomethyl)phenolate ligand and a chloride ion in a distorted square-planar arrangement. An N-H...O hydrogen bond helps to stabilize the struture.

Comment top

Copper(II) complexes with various organic ligands have been a subject of intense study because of their important biological properties (Solomon et al., 1996). Here, we report the synthesis and structure of the new title complex, Cu(dmp)Cl, (I), where dmp is 2,4-dibromo-6((pyridine-2-ylmethylamino)methy)phenol.

Selected bond lengths are listed in Table 1. The CuII atom is four-coordinated by one pyridine N atom, one amine N atom and one phenolate O atom from the ligand and one chloride ion in a distorted square-planar arangement (Fig. 1). The metal to ligand-atom distances in (I) are similar to the ones found in bis[2,4-dibromo-6((pyridnine-2-ylmethylamino)methy) phenolato]bis[nitratocopper(II)] (Ma et al., 2007).

An N—H···O hydrogen bond (Table 2) helps to stabilize the packing in (I).

Related literature top

For background, see: Solomon et al. (1996); Ma et al. (2007).

Experimental top

2,4-Dibromo-6-((pyridine-2-ylmethylamino)methyl)phenol (0.372 g, 1 mmol) was added to a methanol solution (20 ml) of CuCl2·2H2O (0.170 g, 1 mmol) with stirring. The resulting solution was left to stand at room temperture and blue blocks of (I) were obtained after several days.

Refinement top

All H-atoms bound to carbon were refined using a riding model [C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C)]. The amino H atom was located in a difference map and it sposition was freely refined with Uiso(H) = 1.2 Ueq(N).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for the H atoms).
Chlorido[2,4-dibromo-6-(2-pyridylmethylaminomethyl)phenolato]copper(II) top
Crystal data top
[Cu(C13H11Br2N2O)Cl]F000 = 908
Mr = 470.05Dx = 2.056 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8947 reflections
a = 13.447 (4) Åθ = 2.0–28.2º
b = 16.628 (5) ŵ = 6.87 mm−1
c = 6.881 (2) ÅT = 305 (2) K
β = 99.179 (4)ºBlock, blue
V = 1518.8 (8) Å30.32 × 0.26 × 0.20 mm
Z = 4
Data collection top
Bruker APEX CCD
diffractometer		3459 independent reflections
Radiation source: fine-focus sealed tube2044 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.073
T = 305(2) Kθmax = 28.2º
ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −17→11
Tmin = 0.133, Tmax = 0.251k = −21→20
8786 measured reflectionsl = −9→8
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.137  w = 1/[σ2(Fo2) + (0.0706P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
3459 reflectionsΔρmax = 1.04 e Å−3
184 parametersΔρmin = −0.83 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cu(C13H11Br2N2O)Cl]V = 1518.8 (8) Å3
Mr = 470.05Z = 4
Monoclinic, P21/cMo Kα
a = 13.447 (4) ŵ = 6.87 mm−1
b = 16.628 (5) ÅT = 305 (2) K
c = 6.881 (2) Å0.32 × 0.26 × 0.20 mm
β = 99.179 (4)º
Data collection top
Bruker APEX CCD
diffractometer		3459 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2044 reflections with I > 2σ(I)
Tmin = 0.133, Tmax = 0.251Rint = 0.073
8786 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0511 restraint
wR(F2) = 0.137H atoms treated by a mixture of
independent and constrained refinement
S = 0.94Δρmax = 1.04 e Å−3
3459 reflectionsΔρmin = −0.83 e Å−3
184 parameters
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 > 2sigma(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
C1−0.0249 (5)0.1997 (4)0.2698 (10)0.0567 (18)
H1−0.03480.25490.27690.068*
C2−0.1045 (5)0.1518 (5)0.1881 (12)0.071 (2)
H2−0.16670.17460.14020.085*
C3−0.0908 (5)0.0702 (4)0.1784 (10)0.064 (2)
H3−0.14360.03700.12390.077*
C40.0020 (5)0.0386 (4)0.2504 (10)0.0555 (17)
H40.0131−0.01650.24530.067*
C50.0794 (4)0.0900 (3)0.3312 (9)0.0433 (14)
C60.1807 (4)0.0582 (3)0.4151 (10)0.0517 (16)
H6A0.17750.03240.54050.062*
H6B0.20100.01800.32690.062*
C70.3373 (4)0.1065 (3)0.6124 (9)0.0423 (14)
H7A0.36420.05300.59770.051*
H7B0.30930.10740.73380.051*
C80.4210 (4)0.1665 (3)0.6255 (8)0.0376 (13)
C90.5188 (4)0.1412 (3)0.6364 (8)0.0388 (13)
H90.53260.08640.63380.047*
C100.5971 (4)0.1957 (4)0.6513 (9)0.0442 (14)
C110.5778 (4)0.2781 (4)0.6515 (9)0.0460 (15)
H110.63030.31500.65980.055*
C120.4791 (4)0.3039 (3)0.6390 (8)0.0381 (13)
C130.3969 (4)0.2501 (3)0.6281 (8)0.0358 (13)
N10.0656 (3)0.1695 (3)0.3389 (7)0.0453 (12)
N20.2557 (3)0.1231 (3)0.4435 (7)0.0372 (11)
O10.3038 (3)0.2762 (2)0.6237 (6)0.0431 (10)
Cu10.19000 (5)0.23063 (4)0.45485 (11)0.0392 (2)
Br10.45266 (5)0.41577 (3)0.63413 (9)0.0508 (2)
Br20.73138 (5)0.15965 (5)0.66154 (15)0.0798 (3)
Cl10.12562 (12)0.35288 (9)0.3686 (3)0.0528 (4)
H2N0.291 (4)0.133 (4)0.337 (8)0.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.045 (4)0.049 (4)0.073 (5)0.002 (3)−0.002 (3)−0.009 (3)
C20.043 (4)0.069 (6)0.093 (6)0.002 (3)−0.009 (4)0.003 (4)
C30.061 (4)0.055 (5)0.072 (5)−0.019 (3)−0.003 (4)0.002 (4)
C40.053 (4)0.045 (4)0.066 (5)−0.012 (3)0.002 (3)−0.005 (3)
C50.056 (4)0.032 (3)0.041 (4)−0.005 (3)0.005 (3)−0.004 (3)
C60.054 (4)0.024 (3)0.075 (5)−0.008 (3)0.004 (3)−0.005 (3)
C70.050 (3)0.027 (3)0.050 (4)0.003 (2)0.007 (3)0.002 (3)
C80.055 (3)0.022 (3)0.034 (3)0.002 (2)0.000 (3)−0.001 (2)
C90.041 (3)0.033 (3)0.038 (3)0.004 (2)−0.007 (2)−0.001 (2)
C100.046 (3)0.039 (4)0.046 (4)0.008 (3)0.000 (3)−0.001 (3)
C110.050 (4)0.042 (4)0.045 (4)−0.010 (3)0.003 (3)−0.005 (3)
C120.049 (3)0.024 (3)0.039 (3)0.001 (2)0.002 (3)0.001 (2)
C130.045 (3)0.029 (3)0.032 (3)0.002 (2)0.004 (2)−0.004 (2)
N10.046 (3)0.039 (3)0.050 (3)−0.003 (2)0.006 (2)−0.006 (2)
N20.038 (3)0.023 (2)0.049 (3)−0.0042 (19)0.002 (2)0.002 (2)
O10.045 (2)0.028 (2)0.053 (3)0.0031 (16)−0.0033 (18)−0.0094 (18)
Cu10.0457 (4)0.0235 (4)0.0461 (5)0.0024 (3)0.0001 (3)−0.0024 (3)
Br10.0744 (5)0.0233 (3)0.0519 (4)−0.0046 (3)0.0015 (3)−0.0005 (3)
Br20.0459 (4)0.0605 (5)0.1286 (8)0.0074 (3)0.0000 (4)−0.0052 (5)
Cl10.0572 (9)0.0307 (8)0.0698 (11)0.0100 (6)0.0079 (8)0.0083 (7)
Geometric parameters (Å, °) top
C1—N11.331 (7)C7—H7B0.9700
C1—C21.379 (9)C8—C91.372 (7)
C1—H10.9300C8—C131.428 (7)
C2—C31.372 (9)C9—C101.380 (8)
C2—H20.9300C9—H90.9300
C3—C41.373 (9)C10—C111.395 (8)
C3—H30.9300C10—Br21.893 (6)
C4—C51.392 (8)C11—C121.385 (8)
C4—H40.9300C11—H110.9300
C5—N11.338 (7)C12—C131.414 (8)
C5—C61.490 (8)C12—Br11.893 (5)
C6—N21.469 (7)C13—O11.321 (6)
C6—H6A0.9700N2—H2N0.94 (4)
C6—H6B0.9700Cu1—O11.923 (4)
C7—N21.492 (7)Cu1—N22.001 (4)
C7—C81.496 (7)Cu1—N12.011 (5)
C7—H7A0.9700Cu1—Cl12.2517 (16)
N1—C1—C2122.3 (6)C8—C9—H9119.5
N1—C1—H1118.9C10—C9—H9119.5
C2—C1—H1118.9C9—C10—C11120.4 (5)
C3—C2—C1119.3 (6)C9—C10—Br2120.5 (4)
C3—C2—H2120.4C11—C10—Br2119.1 (4)
C1—C2—H2120.4C12—C11—C10118.8 (5)
C2—C3—C4118.9 (6)C12—C11—H11120.6
C2—C3—H3120.6C10—C11—H11120.6
C4—C3—H3120.6C11—C12—C13122.7 (5)
C3—C4—C5119.2 (6)C11—C12—Br1118.8 (4)
C3—C4—H4120.4C13—C12—Br1118.6 (4)
C5—C4—H4120.4O1—C13—C12121.5 (5)
N1—C5—C4121.6 (6)O1—C13—C8122.4 (5)
N1—C5—C6117.4 (5)C12—C13—C8116.1 (5)
C4—C5—C6121.0 (6)C1—N1—C5118.9 (5)
N2—C6—C5110.9 (5)C1—N1—Cu1127.4 (4)
N2—C6—H6A109.5C5—N1—Cu1113.8 (4)
C5—C6—H6A109.5C6—N2—C7111.8 (4)
N2—C6—H6B109.5C6—N2—Cu1111.3 (4)
C5—C6—H6B109.5C7—N2—Cu1114.2 (3)
H6A—C6—H6B108.1C6—N2—H2N116 (4)
N2—C7—C8112.1 (5)C7—N2—H2N104 (4)
N2—C7—H7A109.2Cu1—N2—H2N99 (4)
C8—C7—H7A109.2C13—O1—Cu1123.0 (3)
N2—C7—H7B109.2O1—Cu1—N293.56 (16)
C8—C7—H7B109.2O1—Cu1—N1166.0 (2)
H7A—C7—H7B107.9N2—Cu1—N182.99 (19)
C9—C8—C13121.0 (5)O1—Cu1—Cl192.22 (12)
C9—C8—C7120.2 (5)N2—Cu1—Cl1161.76 (15)
C13—C8—C7118.8 (5)N1—Cu1—Cl195.21 (15)
C8—C9—C10121.1 (5)
N1—C1—C2—C30.5 (12)C2—C1—N1—Cu1178.1 (6)
C1—C2—C3—C40.0 (12)C4—C5—N1—C10.9 (10)
C2—C3—C4—C50.1 (11)C6—C5—N1—C1−178.3 (6)
C3—C4—C5—N1−0.5 (10)C4—C5—N1—Cu1−178.2 (5)
C3—C4—C5—C6178.6 (6)C6—C5—N1—Cu12.6 (7)
N1—C5—C6—N2−15.6 (8)C5—C6—N2—C7149.8 (5)
C4—C5—C6—N2165.2 (6)C5—C6—N2—Cu120.7 (7)
N2—C7—C8—C9−127.8 (6)C8—C7—N2—C6172.3 (5)
N2—C7—C8—C1352.8 (7)C8—C7—N2—Cu1−60.2 (5)
C13—C8—C9—C100.3 (9)C12—C13—O1—Cu1138.6 (4)
C7—C8—C9—C10−179.1 (5)C8—C13—O1—Cu1−42.4 (7)
C8—C9—C10—C11−1.3 (9)C13—O1—Cu1—N226.5 (4)
C8—C9—C10—Br2−178.9 (4)C13—O1—Cu1—N1101.6 (8)
C9—C10—C11—C120.8 (9)C13—O1—Cu1—Cl1−136.2 (4)
Br2—C10—C11—C12178.4 (4)C6—N2—Cu1—O1150.7 (4)
C10—C11—C12—C130.7 (9)C7—N2—Cu1—O122.9 (4)
C10—C11—C12—Br1−178.8 (4)C6—N2—Cu1—N1−15.7 (4)
C11—C12—C13—O1177.4 (5)C7—N2—Cu1—N1−143.5 (4)
Br1—C12—C13—O1−3.1 (7)C6—N2—Cu1—Cl1−101.1 (5)
C11—C12—C13—C8−1.6 (8)C7—N2—Cu1—Cl1131.1 (4)
Br1—C12—C13—C8177.9 (4)C1—N1—Cu1—O1112.1 (8)
C9—C8—C13—O1−177.9 (5)C5—N1—Cu1—O1−68.8 (9)
C7—C8—C13—O11.5 (8)C1—N1—Cu1—N2−171.6 (6)
C9—C8—C13—C121.1 (8)C5—N1—Cu1—N27.5 (4)
C7—C8—C13—C12−179.5 (5)C1—N1—Cu1—Cl1−9.8 (6)
C2—C1—N1—C5−0.9 (10)C5—N1—Cu1—Cl1169.3 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O1i0.94 (4)2.14 (5)2.918 (6)139 (5)
Symmetry codes: (i) x, −y+1/2, z−1/2.
Selected geometric parameters (Å) top
Cu1—O11.923 (4)Cu1—N12.011 (5)
Cu1—N22.001 (4)Cu1—Cl12.2517 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O1i0.94 (4)2.14 (5)2.918 (6)139 (5)
Symmetry codes: (i) x, −y+1/2, z−1/2.
Acknowledgements top

We thank the National Natural Science Foundation of China (No. 20471014), the program for New Century Excellent Talents in Chinese Universities (NCET-05–0320), the Fok Ying Tung Education Foundation, and the Analysis and Testing Foundation of Northeast Normal University for support.

references
References top

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Bruker (1999). SAINT. Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.

Ma, J.-C., Yang, J. & Ma, J.-F. (2007). Acta Cryst. E63, m2284–?.

Sheldrick, G. M. (1990). SHELXTL-Plus. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. Version 2.03. University of Göttingen, Germany.

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

Solomon, E. I., Sundaram, U. M. & Machokin, T. E. (1996). Chem. Rev. 96, 2563–2606.