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Acta Cryst. (2007). E63, m2284    [ doi:10.1107/S1600536807037695 ]

Bis[[mu]-2,4-dibromo-6-(2-pyridylmethylaminomethyl)phenolato]bis[nitratocopper(II)]

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

Abstract top

In the centrosymmetric binuclear title compound, [Cu2(C13H11Br2N2O)2(NO3)2], each CuII atom is five-coordinated by two phenolate O atoms, one nitrate O atom, one pyridine N atom and one amine N atom in a distorted trigonal-bipyramidal CuO3N2 environment. The Cu...Cu separation is 3.207 (4) Å.

Comment top

The synthesis and characterization of binuclear copper(II) compounds have received increasing interest in bio-inorganic chemistry (Solomon et al., 1996) and catalysis (Collman, Zhong, Zhang & Costanzo, 2001; Collman, Zhong, Zeng & Costanzo, 2001). It is well known that the phenolate anion is a good bridging ligand for the construction of binuclear transition metal compounds (Gavrilova & Bosnich 2004; Yang et al., 2006). Modification of the phenolate anion in its ortho position can lead to the formation of stable binuclear compounds through chelation (Xu, et al., 2005). The structure of a new binuclear complex [Cu2(dmp)2(NO3)2], (I), where dmp is 2,4-dibromo-6-((pyridine-2-ylmethylamino)methyl)phenol, is presented here.

As shown in Fig. 1, the title compound, [Cu2(C13H11Br2N2O)(NO3)2], contains a binuclear copper(II) unit bridged by two phenolate O atoms with a Cu···Cu distance of 3.207 (4) Å. Each CuII atom is chelated by one dmp ligand and is also coordinated by a nitrate O atom. Finally, the trigonal-bipyramidal coordination environment is completed by bond to the phenolate O atom from another dmp ligand. The axial positions of the trigonal-bipyramid are occupied by one phenolate O atom and one pyridine N atom with the O—Cu—N angle being 171.25 (10)°.

Related literature top

For related literature, see: Solomon et al. (1996); Collman, Zhong, Zhang & Costanzo (2001); Collman, Zhong, Zeng & Costanzo (2001); Xu et al. (2005).

For related literature, see: Gavrilova & Bosnich (2004); Yang et al. (2006).

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 Cu(NO3)2·3H2O (0.241 g, 1 mmol) with stirring. The resulting solution was left to stand at room temperature and green crystals of (I) were obtained after several days.

Refinement top

All H atoms on C atoms were poisitioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso = 1.2Ueq (C). The H atom bonded to N atom was located in a difference Fourier map and refined freely.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; 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.

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). Symmetry code: (i) 2 − x, −y, 1 − z.
Bis[µ-2,4-dibromo-6-(2-pyridylmethylaminomethyl)phenolato]\ bis[nitratocopper(II)] top
Crystal data top
[Cu2(C13H11Br2N2O)2(NO3)2]F000 = 964
Mr = 993.22Dx = 2.075 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 11121 reflections
a = 10.385 (5) Åθ = 3.0–27.5º
b = 11.252 (5) ŵ = 6.42 mm−1
c = 14.074 (5) ÅT = 290 (2) K
β = 104.810 (5)ºBlock, green
V = 1589.9 (12) Å30.24 × 0.16 × 0.13 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3629 independent reflections
Radiation source: rotating anode2707 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.054
Detector resolution: 10.0 pixels mm-1θmax = 27.5º
T = 290(2) Kθmin = 3º
ω scansh = −13→13
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −14→14
Tmin = 0.30, Tmax = 0.43l = −15→18
14979 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.071  w = 1/[σ2(Fo2) + (0.0224P)2 + 0.8145P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.007
3629 reflectionsΔρmax = 0.48 e Å−3
212 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2(C13H11Br2N2O)2(NO3)2]V = 1589.9 (12) Å3
Mr = 993.22Z = 2
Monoclinic, P21/nMo Kα
a = 10.385 (5) ŵ = 6.42 mm−1
b = 11.252 (5) ÅT = 290 (2) K
c = 14.074 (5) Å0.24 × 0.16 × 0.13 mm
β = 104.810 (5)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3629 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2707 reflections with I > 2σ(I)
Tmin = 0.30, Tmax = 0.43Rint = 0.054
14979 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035212 parameters
wR(F2) = 0.071H atoms treated by a mixture of
independent and constrained refinement
S = 1.05Δρmax = 0.48 e Å−3
3629 reflectionsΔρmin = −0.49 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
Cu10.93487 (4)0.01290 (3)0.38420 (3)0.03277 (11)
C10.9741 (4)0.2204 (3)0.2616 (3)0.0414 (8)
H10.92140.26360.29360.050*
C21.0259 (4)0.2770 (3)0.1930 (3)0.0461 (9)
H21.00850.35700.17890.055*
C31.1040 (4)0.2130 (3)0.1454 (3)0.0444 (9)
H31.13980.24920.09860.053*
C41.1286 (4)0.0938 (3)0.1685 (3)0.0432 (9)
H41.18060.04890.13700.052*
C51.0746 (3)0.0432 (3)0.2387 (2)0.0340 (7)
C61.1035 (4)−0.0829 (3)0.2745 (3)0.0416 (8)
H6A1.1081−0.13360.21980.050*
H6B1.1891−0.08580.32250.050*
C71.0454 (3)−0.2280 (3)0.3883 (2)0.0352 (8)
H7A1.1168−0.20200.44320.042*
H7B1.0793−0.29150.35470.042*
C80.9315 (3)−0.2731 (3)0.4252 (2)0.0314 (7)
C90.8915 (4)−0.3920 (3)0.4112 (2)0.0374 (8)
H90.9362−0.44390.37940.045*
C100.7862 (4)−0.4316 (3)0.4448 (2)0.0377 (8)
C110.7165 (4)−0.3581 (3)0.4914 (3)0.0394 (8)
H110.6448−0.38650.51310.047*
C120.7563 (3)−0.2396 (3)0.5055 (2)0.0344 (7)
C130.8643 (3)−0.1944 (3)0.4740 (2)0.0314 (7)
N10.9972 (3)0.1047 (2)0.2840 (2)0.0343 (6)
N21.0003 (3)−0.1265 (2)0.3190 (2)0.0326 (6)
N30.6808 (3)0.0902 (3)0.3379 (2)0.0450 (7)
O10.9028 (2)−0.08086 (17)0.49007 (15)0.0322 (5)
O20.7906 (3)0.13349 (19)0.38969 (19)0.0425 (6)
O30.5783 (3)0.1497 (3)0.3244 (2)0.0759 (9)
O40.6836 (3)−0.0106 (2)0.3020 (2)0.0554 (7)
Br10.65460 (4)−0.13772 (4)0.56476 (3)0.05240 (12)
Br20.73308 (4)−0.59426 (3)0.42370 (3)0.04830 (12)
H120.925 (4)−0.148 (3)0.276 (3)0.063 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0386 (2)0.02697 (19)0.0346 (2)0.00306 (17)0.01283 (18)−0.00048 (15)
C10.045 (2)0.0328 (17)0.046 (2)0.0052 (17)0.0120 (17)0.0002 (15)
C20.050 (2)0.0345 (18)0.053 (2)−0.0009 (17)0.0119 (19)0.0097 (16)
C30.046 (2)0.0450 (19)0.045 (2)−0.0064 (18)0.0167 (18)0.0034 (16)
C40.048 (2)0.0435 (19)0.042 (2)−0.0010 (18)0.0188 (18)−0.0030 (15)
C50.0352 (19)0.0360 (17)0.0312 (19)−0.0010 (15)0.0090 (15)−0.0030 (13)
C60.045 (2)0.0329 (17)0.051 (2)0.0065 (16)0.0208 (18)0.0013 (15)
C70.041 (2)0.0278 (15)0.036 (2)0.0064 (15)0.0079 (15)0.0016 (13)
C80.0329 (18)0.0285 (15)0.0303 (18)0.0021 (14)0.0034 (14)0.0039 (12)
C90.043 (2)0.0276 (16)0.039 (2)0.0022 (16)0.0068 (16)−0.0019 (14)
C100.047 (2)0.0260 (15)0.0346 (19)−0.0049 (16)0.0008 (16)0.0031 (13)
C110.040 (2)0.0364 (18)0.038 (2)−0.0081 (16)0.0044 (16)0.0049 (14)
C120.0349 (19)0.0359 (17)0.0319 (19)0.0042 (15)0.0074 (15)−0.0014 (13)
C130.0328 (18)0.0306 (16)0.0273 (18)0.0009 (14)0.0015 (14)0.0005 (12)
N10.0351 (16)0.0331 (14)0.0340 (16)0.0030 (13)0.0073 (12)−0.0016 (11)
N20.0336 (16)0.0290 (13)0.0352 (17)0.0028 (13)0.0090 (13)−0.0009 (11)
N30.048 (2)0.0483 (18)0.0425 (19)0.0085 (17)0.0188 (16)0.0103 (14)
O10.0383 (13)0.0278 (10)0.0305 (12)−0.0039 (10)0.0091 (10)−0.0040 (9)
O20.0408 (14)0.0330 (12)0.0528 (17)0.0040 (11)0.0107 (12)−0.0054 (10)
O30.0446 (17)0.101 (2)0.086 (2)0.0342 (18)0.0253 (17)0.0162 (18)
O40.0572 (18)0.0503 (15)0.0514 (17)−0.0076 (14)0.0007 (14)0.0011 (12)
Br10.0483 (2)0.0566 (2)0.0579 (3)−0.00440 (19)0.02369 (19)−0.01596 (18)
Br20.0671 (3)0.02887 (17)0.0439 (2)−0.00976 (17)0.00495 (19)0.00350 (14)
Geometric parameters (Å, °) top
Cu1—O11.923 (2)C7—C81.497 (4)
Cu1—N11.985 (3)C7—H7A0.9700
Cu1—N22.021 (3)C7—H7B0.9700
Cu1—O22.038 (2)C8—C91.399 (4)
Cu1—O1i2.243 (2)C8—C131.410 (4)
C1—N11.347 (4)C9—C101.371 (5)
C1—C21.375 (5)C9—H90.9300
C1—H10.9300C10—C111.372 (5)
C2—C31.379 (5)C10—Br21.913 (3)
C2—H20.9300C11—C121.396 (4)
C3—C41.387 (5)C11—H110.9300
C3—H30.9300C12—C131.402 (4)
C4—C51.378 (5)C12—Br11.891 (3)
C4—H40.9300C13—O11.341 (3)
C5—N11.339 (4)N2—H120.90 (4)
C5—C61.509 (4)N3—O31.230 (4)
C6—N21.457 (4)N3—O41.245 (4)
C6—H6A0.9700N3—O21.282 (4)
C6—H6B0.9700O1—Cu1i2.243 (2)
C7—N21.497 (4)
O1—Cu1—N1171.25 (10)H7A—C7—H7B108.2
O1—Cu1—N294.09 (10)C9—C8—C13120.2 (3)
N1—Cu1—N282.67 (11)C9—C8—C7120.5 (3)
O1—Cu1—O293.51 (10)C13—C8—C7119.3 (3)
N1—Cu1—O293.27 (11)C10—C9—C8119.7 (3)
N2—Cu1—O2150.47 (12)C10—C9—H9120.1
O1—Cu1—O1i79.63 (9)C8—C9—H9120.1
N1—Cu1—O1i93.86 (10)C9—C10—C11122.3 (3)
N2—Cu1—O1i110.53 (11)C9—C10—Br2118.8 (3)
O2—Cu1—O1i98.90 (9)C11—C10—Br2119.0 (3)
N1—C1—C2122.3 (3)C10—C11—C12118.1 (3)
N1—C1—H1118.9C10—C11—H11121.0
C2—C1—H1118.9C12—C11—H11121.0
C1—C2—C3118.9 (3)C11—C12—C13122.2 (3)
C1—C2—H2120.6C11—C12—Br1117.6 (3)
C3—C2—H2120.6C13—C12—Br1120.1 (2)
C2—C3—C4119.1 (3)O1—C13—C12121.4 (3)
C2—C3—H3120.4O1—C13—C8121.1 (3)
C4—C3—H3120.4C12—C13—C8117.5 (3)
C5—C4—C3118.9 (3)C5—N1—C1118.7 (3)
C5—C4—H4120.6C5—N1—Cu1114.4 (2)
C3—C4—H4120.6C1—N1—Cu1126.8 (2)
N1—C5—C4122.1 (3)C6—N2—C7113.3 (3)
N1—C5—C6114.8 (3)C6—N2—Cu1107.64 (19)
C4—C5—C6123.1 (3)C7—N2—Cu1112.4 (2)
N2—C6—C5110.8 (3)C6—N2—H12114 (3)
N2—C6—H6A109.5C7—N2—H12108 (3)
C5—C6—H6A109.5Cu1—N2—H12100 (2)
N2—C6—H6B109.5O3—N3—O4122.8 (4)
C5—C6—H6B109.5O3—N3—O2119.3 (3)
H6A—C6—H6B108.1O4—N3—O2117.9 (3)
N2—C7—C8110.0 (3)C13—O1—Cu1119.73 (19)
N2—C7—H7A109.7C13—O1—Cu1i126.11 (18)
C8—C7—H7A109.7Cu1—O1—Cu1i100.37 (9)
N2—C7—H7B109.7N3—O2—Cu1106.3 (2)
C8—C7—H7B109.7
N1—C1—C2—C30.0 (6)O1i—Cu1—N1—C596.5 (2)
C1—C2—C3—C4−0.3 (6)N2—Cu1—N1—C1169.3 (3)
C2—C3—C4—C5−0.4 (5)O2—Cu1—N1—C118.7 (3)
C3—C4—C5—N11.3 (5)O1i—Cu1—N1—C1−80.5 (3)
C3—C4—C5—C6−175.3 (3)C5—C6—N2—C7−158.1 (3)
N1—C5—C6—N224.0 (4)C5—C6—N2—Cu1−33.1 (3)
C4—C5—C6—N2−159.2 (3)C8—C7—N2—C6−176.0 (3)
N2—C7—C8—C9122.3 (3)C8—C7—N2—Cu161.6 (3)
N2—C7—C8—C13−57.5 (4)O1—Cu1—N2—C6−146.0 (2)
C13—C8—C9—C100.4 (5)N1—Cu1—N2—C625.8 (2)
C7—C8—C9—C10−179.4 (3)O2—Cu1—N2—C6109.5 (3)
C8—C9—C10—C110.6 (5)O1i—Cu1—N2—C6−65.6 (2)
C8—C9—C10—Br2179.5 (2)O1—Cu1—N2—C7−20.5 (2)
C9—C10—C11—C12−0.6 (5)N1—Cu1—N2—C7151.3 (2)
Br2—C10—C11—C12−179.6 (2)O2—Cu1—N2—C7−125.1 (2)
C10—C11—C12—C13−0.3 (5)O1i—Cu1—N2—C759.9 (2)
C10—C11—C12—Br1177.3 (3)C12—C13—O1—Cu1−132.0 (3)
C11—C12—C13—O1−178.5 (3)C8—C13—O1—Cu148.3 (4)
Br1—C12—C13—O13.9 (4)C12—C13—O1—Cu1i95.7 (3)
C11—C12—C13—C81.2 (5)C8—C13—O1—Cu1i−84.0 (3)
Br1—C12—C13—C8−176.4 (2)N2—Cu1—O1—C13−32.5 (2)
C9—C8—C13—O1178.5 (3)O2—Cu1—O1—C13119.0 (2)
C7—C8—C13—O1−1.7 (4)O1i—Cu1—O1—C13−142.6 (3)
C9—C8—C13—C12−1.2 (5)N2—Cu1—O1—Cu1i110.14 (11)
C7—C8—C13—C12178.6 (3)O2—Cu1—O1—Cu1i−98.42 (10)
C4—C5—N1—C1−1.5 (5)O1i—Cu1—O1—Cu1i0.0
C6—C5—N1—C1175.3 (3)O3—N3—O2—Cu1−175.6 (3)
C4—C5—N1—Cu1−178.7 (3)O4—N3—O2—Cu13.1 (3)
C6—C5—N1—Cu1−1.9 (4)O1—Cu1—O2—N3−84.6 (2)
C2—C1—N1—C50.9 (5)N1—Cu1—O2—N3101.0 (2)
C2—C1—N1—Cu1177.7 (3)N2—Cu1—O2—N320.1 (3)
N2—Cu1—N1—C5−13.7 (2)O1i—Cu1—O2—N3−164.6 (2)
O2—Cu1—N1—C5−164.4 (2)
Symmetry codes: (i) −x+2, −y, −z+1.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.923 (2)Cu1—O22.038 (2)
Cu1—N11.985 (3)Cu1—O1i2.243 (2)
Cu1—N22.021 (3)
Symmetry codes: (i) −x+2, −y, −z+1.
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
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