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Acta Cryst. (2007). E63, m2488    [ doi:10.1107/S1600536807042882 ]

Bis{2,4-dibromo-6-[(naphthalen-1-ylimino)methyl]phenolato-[kappa]2N,O}(1,10-phenanthroline-[kappa]2N,N')copper(II)

Z. Liu, L. X. Jin, J. H. Xia and G. Z. Li

Abstract top

In the title compound, C46H28Br4CuN4O2 or [Cu(L)2(phen)] {L = 2,4-dibromo-6-[(naphthalen-1-ylimino)methyl]phenolate, C17H10Br2NO; phen = 1,10-phenanthroline, C12H8N2}, the central CuII, which lies on a twofold axis, binds two N and two O atoms from the two Schiff base ligands and two N atoms from 1,10-phenanthroline in a distorted octahedral arrangement. In the crystal structure, C-H...Br hydrogen bonds link the molecules into rows along c.

Comment top

Schiff bases play an important role in inorganic chemistry as they easily form stable complexes with most transition metal ions (Mostafa & Haifaa, 2007, Musie et al., 2003, Patel et al., 2006). We report herein the synthesis and crystal structure of (I), Fig 1, a mononuclear Cu(II) complex of the new Schiff base ligand 2,4-dibromo-6-((naphthalen-1-ylimino)methyl)phenolate and 1,10-phenanthroline. The copperII cation lies on a twofold axis and is coordinated by two N and two O atoms from the Schiff base and two N atoms from 1,10-phenanthroline, in a slightly distorted octahedral geometry.

In the crystal weak, non-classical C—H···Br hydrogen bonds link the molecules in rows along c, Fig 2.

Related literature top

For related complexes of Schiff bases with transition metal ions, see: Mostafa & Haifaa (2007); Musie et al. (2003); Patel et al. (2006).

For related literature, see: Mehmet et al. (2007).

Experimental top

1-naphthylamine (0.286 g, 2 mmol) and 3,5-Bibromo-2-hydroxy-benzaldehyde (0.560 g, 2 mmol) were mixed in ethanol and stirred for 30 min at room temperature to yield the Schiff base 2,4-dibromo-6-((naphthalen-1-ylimino)methyl)phenol. A mixture of this Schiff base (0.201 g, 0.5 mmol), CuSO4·5H2O2 (0.125 g, 0.5 mmol), phen (0.198 g 0.1 mmol,) and 6 drops of triethylamine in 5 ml e thanol and 5 ml acetonitrile was sealed in a 30 ml Teflon-lined stainless steel vessel, which was heated at 333 K for 7 days under autogenous pressure. On cooling to room temperature blue crystals of the title compound (I) were produced (yield: 53%, based on Cu).

Refinement top

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C).

Computing details top

Data collection: SMART (Bruker 2001); cell refinement: SAINT (Bruker 2001); data reduction: SAINT (Bruker 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 1997); software used to prepare material for publication: SHELXTL (Bruker 1997).

Figures top
[Figure 1] Fig. 1. A view of (I), showing 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. Crystal packing of (I) with H-bonds drawn as dashed lines.
Bis{2,4-dibromo-6-[(naphthalen-1-ylimino)methyl]phenolato-κ2N, O}(1,10-phenanthroline-κ2N,N')copper(II) top
Crystal data top
[Cu(C17H10Br2NO)2(C12H8N2)]F000 = 2068
Mr = 1051.90Dx = 1.750 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1985 reflections
a = 20.288 (2) Åθ = 2.8–20.6º
b = 14.5052 (18) ŵ = 4.59 mm−1
c = 15.227 (2) ÅT = 298 (2) K
β = 116.977 (2)ºBlock, blue
V = 3993.5 (9) Å30.38 × 0.19 × 0.17 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3513 independent reflections
Radiation source: fine-focus sealed tube1877 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.086
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→24
Tmin = 0.274, Tmax = 0.509k = −16→17
10067 measured reflectionsl = −17→18
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)] = 0.059H-atom parameters constrained
wR(F2) = 0.165  w = 1/[σ2(Fo2) + (0.0811P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max = 0.001
3513 reflectionsΔρmax = 0.95 e Å−3
258 parametersΔρmin = −0.73 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C17H10Br2NO)2(C12H8N2)]V = 3993.5 (9) Å3
Mr = 1051.90Z = 4
Monoclinic, C2/cMo Kα
a = 20.288 (2) ŵ = 4.59 mm−1
b = 14.5052 (18) ÅT = 298 (2) K
c = 15.227 (2) Å0.38 × 0.19 × 0.17 mm
β = 116.977 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3513 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1877 reflections with I > 2σ(I)
Tmin = 0.274, Tmax = 0.509Rint = 0.086
10067 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.059258 parameters
wR(F2) = 0.165H-atom parameters constrained
S = 0.97Δρmax = 0.95 e Å−3
3513 reflectionsΔρmin = −0.73 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
Cu10.50000.93455 (7)0.25000.0392 (4)
Br10.37169 (5)0.70105 (6)0.02414 (6)0.0636 (3)
Br20.62496 (6)0.47645 (6)0.17224 (8)0.0864 (4)
N10.6262 (3)0.9081 (4)0.2840 (4)0.0421 (15)
N20.4717 (3)1.0413 (4)0.1537 (4)0.0404 (15)
O10.4819 (3)0.8458 (3)0.1455 (3)0.0430 (12)
C10.6420 (4)0.8241 (5)0.2785 (5)0.0437 (19)
H10.69070.80640.31810.052*
C20.5920 (4)0.7527 (5)0.2168 (5)0.0398 (18)
C30.5152 (4)0.7679 (5)0.1568 (5)0.0404 (18)
C40.4749 (4)0.6892 (5)0.1040 (5)0.0435 (19)
C50.5061 (5)0.6039 (5)0.1086 (5)0.052 (2)
H50.47720.55430.07310.063*
C60.5824 (5)0.5933 (5)0.1682 (6)0.051 (2)
C70.6236 (5)0.6661 (5)0.2209 (5)0.049 (2)
H70.67410.65820.26050.058*
C80.6805 (4)0.9648 (5)0.3581 (6)0.0457 (19)
C90.7164 (5)0.9372 (5)0.4543 (6)0.061 (2)
H90.70830.87850.47190.073*
C100.7658 (6)0.9981 (7)0.5273 (7)0.085 (3)
H100.79190.97810.59210.101*
C110.7751 (5)1.0838 (7)0.5035 (8)0.087 (3)
H110.80621.12360.55280.104*
C120.7393 (5)1.1154 (5)0.4061 (8)0.066 (3)
C130.6910 (4)1.0555 (5)0.3300 (7)0.053 (2)
C140.6534 (5)1.0870 (6)0.2316 (7)0.066 (2)
H140.62281.04750.18160.079*
C150.6629 (7)1.1759 (8)0.2112 (10)0.097 (4)
H150.63731.19690.14670.116*
C160.7096 (7)1.2367 (7)0.2837 (12)0.102 (4)
H160.71581.29660.26690.122*
C170.7461 (6)1.2080 (7)0.3789 (10)0.088 (3)
H170.77601.24940.42720.105*
C180.4844 (4)1.1253 (4)0.1971 (5)0.0370 (17)
C190.4695 (4)1.2085 (5)0.1460 (6)0.049 (2)
C200.4396 (5)1.2025 (6)0.0433 (6)0.060 (2)
H200.42881.25590.00560.072*
C210.4263 (5)1.1177 (6)−0.0020 (6)0.067 (3)
H210.40631.1134−0.07020.080*
C220.4434 (4)1.0386 (5)0.0560 (5)0.050 (2)
H220.43460.98140.02510.060*
C230.4850 (5)1.2925 (5)0.2001 (6)0.067 (3)
H230.47421.34840.16640.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0522 (8)0.0356 (7)0.0274 (7)0.0000.0161 (6)0.000
Br10.0580 (6)0.0703 (6)0.0482 (5)−0.0060 (5)0.0115 (4)−0.0159 (4)
Br20.0961 (9)0.0469 (6)0.0961 (8)0.0138 (5)0.0260 (7)−0.0145 (5)
N10.044 (4)0.039 (3)0.041 (4)−0.002 (3)0.018 (3)−0.005 (3)
N20.042 (4)0.047 (4)0.032 (4)−0.001 (3)0.017 (3)0.000 (3)
O10.052 (3)0.042 (3)0.030 (3)0.003 (3)0.014 (2)−0.002 (2)
C10.046 (5)0.050 (5)0.035 (4)−0.003 (4)0.018 (4)−0.006 (3)
C20.048 (5)0.041 (4)0.030 (4)−0.006 (4)0.017 (4)−0.006 (3)
C30.058 (5)0.040 (4)0.027 (4)−0.004 (4)0.023 (4)−0.002 (3)
C40.053 (5)0.048 (4)0.030 (4)−0.002 (4)0.019 (4)−0.001 (3)
C50.078 (7)0.041 (4)0.035 (4)−0.008 (5)0.023 (5)−0.009 (3)
C60.063 (6)0.041 (4)0.047 (5)0.004 (4)0.022 (4)−0.001 (4)
C70.056 (5)0.043 (4)0.042 (5)0.003 (4)0.019 (4)0.002 (3)
C80.041 (5)0.046 (4)0.048 (5)−0.003 (4)0.017 (4)−0.007 (4)
C90.064 (6)0.056 (5)0.047 (5)0.003 (5)0.011 (4)−0.012 (4)
C100.089 (8)0.077 (6)0.044 (6)0.012 (6)−0.008 (5)−0.021 (5)
C110.059 (7)0.085 (7)0.087 (8)0.004 (6)0.008 (6)−0.048 (6)
C120.051 (6)0.045 (5)0.093 (8)0.005 (5)0.025 (6)−0.026 (5)
C130.041 (5)0.048 (5)0.074 (6)−0.001 (4)0.028 (5)−0.011 (4)
C140.061 (6)0.066 (6)0.073 (7)0.003 (5)0.034 (5)0.008 (5)
C150.098 (9)0.083 (8)0.141 (11)0.017 (7)0.083 (9)0.041 (8)
C160.093 (10)0.056 (7)0.193 (15)−0.004 (7)0.096 (11)0.016 (8)
C170.066 (7)0.060 (7)0.145 (11)−0.010 (6)0.056 (8)−0.025 (7)
C180.034 (4)0.035 (4)0.042 (4)−0.002 (3)0.017 (4)0.001 (3)
C190.048 (5)0.041 (4)0.059 (5)0.000 (4)0.026 (4)0.008 (4)
C200.074 (6)0.060 (5)0.051 (5)0.011 (5)0.032 (5)0.022 (4)
C210.091 (7)0.069 (6)0.035 (5)0.011 (5)0.024 (5)0.020 (4)
C220.064 (5)0.054 (5)0.033 (4)−0.001 (4)0.023 (4)−0.001 (3)
C230.076 (7)0.044 (4)0.081 (6)0.009 (5)0.036 (6)0.019 (4)
Geometric parameters (Å, °) top
Cu1—O11.948 (4)C9—H90.9300
Cu1—O1i1.948 (4)C10—C111.332 (13)
Cu1—N2i2.029 (5)C10—H100.9300
Cu1—N22.029 (5)C11—C121.400 (13)
Cu1—N1i2.402 (6)C11—H110.9300
Cu1—N12.402 (6)C12—C131.424 (11)
Br1—C41.893 (8)C12—C171.431 (13)
Br2—C61.890 (7)C13—C141.413 (11)
N1—C11.273 (8)C14—C151.361 (12)
N1—C81.426 (9)C14—H140.9300
N2—C221.330 (8)C15—C161.394 (16)
N2—C181.355 (8)C15—H150.9300
O1—C31.288 (8)C16—C171.360 (15)
C1—C21.455 (9)C16—H160.9300
C1—H10.9300C17—H170.9300
C2—C71.399 (9)C18—C191.393 (9)
C2—C31.421 (10)C18—C18i1.438 (13)
C3—C41.421 (9)C19—C201.401 (10)
C4—C51.377 (9)C19—C231.424 (10)
C5—C61.403 (11)C20—C211.375 (10)
C5—H50.9300C20—H200.9300
C6—C71.360 (10)C21—C221.393 (10)
C7—H70.9300C21—H210.9300
C8—C91.368 (10)C22—H220.9300
C8—C131.429 (10)C23—C23i1.357 (16)
C9—C101.417 (11)C23—H230.9300
O1—Cu1—O1i97.3 (3)C8—C9—C10120.0 (8)
O1—Cu1—N2i169.1 (2)C8—C9—H9120.0
O1i—Cu1—N2i91.5 (2)C10—C9—H9120.0
O1—Cu1—N291.5 (2)C11—C10—C9120.4 (9)
O1i—Cu1—N2169.1 (2)C11—C10—H10119.8
N2i—Cu1—N280.5 (3)C9—C10—H10119.8
O1—Cu1—N1i86.0 (2)C10—C11—C12121.6 (8)
O1i—Cu1—N1i81.9 (2)C10—C11—H11119.2
N2i—Cu1—N1i101.7 (2)C12—C11—H11119.2
N2—Cu1—N1i92.4 (2)C11—C12—C13119.8 (8)
O1—Cu1—N181.9 (2)C11—C12—C17122.8 (10)
O1i—Cu1—N186.0 (2)C13—C12—C17117.3 (10)
N2i—Cu1—N192.4 (2)C14—C13—C12120.5 (8)
N2—Cu1—N1101.7 (2)C14—C13—C8122.2 (7)
N1i—Cu1—N1161.6 (3)C12—C13—C8117.3 (8)
C1—N1—C8118.5 (6)C15—C14—C13118.9 (10)
C1—N1—Cu1114.5 (5)C15—C14—H14120.5
C8—N1—Cu1116.4 (4)C13—C14—H14120.5
C22—N2—C18117.6 (6)C14—C15—C16122.3 (12)
C22—N2—Cu1128.5 (5)C14—C15—H15118.8
C18—N2—Cu1113.9 (4)C16—C15—H15118.8
C3—O1—Cu1125.3 (4)C17—C16—C15119.7 (10)
N1—C1—C2126.9 (7)C17—C16—H16120.1
N1—C1—H1116.5C15—C16—H16120.1
C2—C1—H1116.5C16—C17—C12121.2 (10)
C7—C2—C3120.9 (6)C16—C17—H17119.4
C7—C2—C1116.0 (7)C12—C17—H17119.4
C3—C2—C1123.1 (6)N2—C18—C19124.2 (6)
O1—C3—C2125.3 (6)N2—C18—C18i115.9 (4)
O1—C3—C4119.8 (7)C19—C18—C18i120.0 (4)
C2—C3—C4114.9 (7)C18—C19—C20116.4 (7)
C5—C4—C3124.1 (7)C18—C19—C23118.9 (7)
C5—C4—Br1117.6 (6)C20—C19—C23124.7 (7)
C3—C4—Br1118.4 (5)C21—C20—C19120.2 (7)
C4—C5—C6118.5 (7)C21—C20—H20119.9
C4—C5—H5120.7C19—C20—H20119.9
C6—C5—H5120.7C20—C21—C22118.9 (7)
C7—C6—C5119.9 (7)C20—C21—H21120.5
C7—C6—Br2121.9 (6)C22—C21—H21120.5
C5—C6—Br2118.2 (6)N2—C22—C21122.8 (7)
C6—C7—C2121.7 (7)N2—C22—H22118.6
C6—C7—H7119.2C21—C22—H22118.6
C2—C7—H7119.2C23i—C23—C19121.1 (4)
C9—C8—N1121.5 (7)C23i—C23—H23119.4
C9—C8—C13120.8 (7)C19—C23—H23119.4
N1—C8—C13117.4 (7)
O1—Cu1—N1—C1−42.1 (5)Br2—C6—C7—C2179.3 (5)
O1i—Cu1—N1—C155.8 (5)C3—C2—C7—C6−0.3 (11)
N2i—Cu1—N1—C1147.2 (5)C1—C2—C7—C6178.7 (6)
N2—Cu1—N1—C1−132.0 (5)C1—N1—C8—C9−49.5 (10)
N1i—Cu1—N1—C17.1 (5)Cu1—N1—C8—C993.2 (8)
O1—Cu1—N1—C8173.7 (5)C1—N1—C8—C13136.6 (7)
O1i—Cu1—N1—C8−88.4 (5)Cu1—N1—C8—C13−80.8 (7)
N2i—Cu1—N1—C83.0 (5)N1—C8—C9—C10−175.2 (8)
N2—Cu1—N1—C883.8 (5)C13—C8—C9—C10−1.4 (12)
N1i—Cu1—N1—C8−137.1 (5)C8—C9—C10—C113.1 (15)
O1—Cu1—N2—C227.0 (6)C9—C10—C11—C12−2.7 (16)
O1i—Cu1—N2—C22−136.8 (10)C10—C11—C12—C130.6 (15)
N2i—Cu1—N2—C22179.5 (8)C10—C11—C12—C17177.6 (10)
N1i—Cu1—N2—C22−79.0 (6)C11—C12—C13—C14178.9 (8)
N1—Cu1—N2—C2289.1 (6)C17—C12—C13—C141.8 (12)
O1—Cu1—N2—C18−172.5 (5)C11—C12—C13—C81.0 (12)
O1i—Cu1—N2—C1843.7 (14)C17—C12—C13—C8−176.1 (8)
N2i—Cu1—N2—C18−0.1 (4)C9—C8—C13—C14−178.4 (8)
N1i—Cu1—N2—C18101.4 (5)N1—C8—C13—C14−4.5 (11)
N1—Cu1—N2—C18−90.5 (5)C9—C8—C13—C12−0.6 (11)
O1i—Cu1—O1—C3−35.9 (5)N1—C8—C13—C12173.4 (7)
N2i—Cu1—O1—C3107.5 (12)C12—C13—C14—C15−1.5 (13)
N2—Cu1—O1—C3150.6 (6)C8—C13—C14—C15176.3 (8)
N1i—Cu1—O1—C3−117.2 (6)C13—C14—C15—C161.5 (15)
N1—Cu1—O1—C349.0 (5)C14—C15—C16—C17−1.7 (17)
C8—N1—C1—C2172.1 (7)C15—C16—C17—C122.0 (17)
Cu1—N1—C1—C228.7 (9)C11—C12—C17—C16−179.1 (10)
N1—C1—C2—C7177.3 (7)C13—C12—C17—C16−2.1 (15)
N1—C1—C2—C3−3.7 (11)C22—N2—C18—C190.2 (11)
Cu1—O1—C3—C2−41.1 (9)Cu1—N2—C18—C19179.8 (6)
Cu1—O1—C3—C4141.3 (5)C22—N2—C18—C18i−179.4 (7)
C7—C2—C3—O1−177.1 (6)Cu1—N2—C18—C18i0.2 (10)
C1—C2—C3—O14.0 (10)N2—C18—C19—C20−0.1 (11)
C7—C2—C3—C40.6 (9)C18i—C18—C19—C20179.5 (8)
C1—C2—C3—C4−178.3 (6)N2—C18—C19—C23179.7 (7)
O1—C3—C4—C5177.7 (6)C18i—C18—C19—C23−0.7 (13)
C2—C3—C4—C5−0.1 (10)C18—C19—C20—C210.1 (12)
O1—C3—C4—Br1−3.7 (9)C23—C19—C20—C21−179.6 (9)
C2—C3—C4—Br1178.5 (5)C19—C20—C21—C22−0.3 (13)
C3—C4—C5—C6−0.7 (11)C18—N2—C22—C21−0.4 (11)
Br1—C4—C5—C6−179.3 (5)Cu1—N2—C22—C21−179.9 (6)
C4—C5—C6—C71.0 (11)C20—C21—C22—N20.4 (13)
C4—C5—C6—Br2−178.9 (5)C18—C19—C23—C23i1.3 (16)
C5—C6—C7—C2−0.6 (12)C20—C19—C23—C23i−179.0 (10)
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15···Br1ii0.932.933.773 (13)152
Symmetry codes: (ii) x+3/2, y+5/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15···Br1i0.932.933.773 (13)152
Symmetry codes: (i) x+3/2, y+5/2, z.
Acknowledgements top

We acknowledge financial support by the Soft Environment Construction Education Office of Guangxi Province (No. D203252), People's Republic of China.

references
References top

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