supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m1767    [ doi:10.1107/S1600536807023902 ]

Bis([mu]-azido-[kappa]2N,N)bis({2-[3-(dimethylamino)propyliminomethyl]-4-nitrophenolato-[kappa]3O,N,N'}copper(II))

H.-Y. Hou

Abstract top

The title complex, [Cu2(N3)2(C12H16N3O3)2], is an azide-bridged dinuclear copper(II) complex. There is a crystallographic inversion centre at the mid-point of the Cu...Cu vector. Each Cu atom is coordinated by one O and two N atoms of one Schiff base ligand and two bridging N atoms from two azide ligands, forming a trigonal-bipyramidal geometry. The Cu...Cu distance is 3.327 (2) Å.

Comment top

Many azide-bridged polynuclear complexes have been reported previously (Zhao et al., 2003; Cai et al., 2007; Yu et al., 2006; Zhang et al., 2006; Zhu et al., 2004; Li et al., 2007). These complexes have interesting structures. We report herein the new copper(II) complex, (I), derived from the Schiff base ligand 4-nitro-2-[(3-dimethylaminopropylimino)methyl]phenol with azide bridges.

Complex (I) is an azide-bridged dinuclear copper(II) complex (Fig. 1). There is a crystallographic inversion centre at the midpoint of the two copper atoms in the complex. Each Cu atom is coordinated by one O and two N atoms of one Schiff base ligand and two briding N atoms from two azide ligands, forming a trigonal-bipyramidal geometry. The Cu···Cu distance is 3.327 (2) Å.

Related literature top

For related literature, see: Cai et al. (2007); Li et al. (2007); Yu et al. (2006); Zhang et al. (2006); Zhao et al. (2003); Zhu et al. (2004).

Experimental top

5-Nitro-2-hydroxybenzaldehyde (0.2 mmol, 33.5 mg), N,N-dimethylpropane-1,3-diamine (0.2 mmol, 20.5 mg), NaN3 (0.2 mmol, 6.5 mg), and Cu(CH3COO)2.H2O (0.2 mmol, 40.0 mg) were mixed in a methanol solution. The mixture was stirred at 325 K for 30 min to give a transparent blue solution. Blue crystals were obtained by slow evaporation of the solution in air.

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C–H distances in the range 0.93–0.97Å and Uiso(H) set at 1.2Ueq(C) and 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with anisotropic displacement ellipsoids drawn at the 30% probability level.
Bis(µ-azido-κ2N,N)bis({2- [3-(dimethylamino)propyliminomethyl]-4-nitrophenolato- κ3O,N,N'}copper(II)) top
Crystal data top
[Cu2(N3)2(C12H16N3O3)2]F(000) = 732
Mr = 711.70Dx = 1.584 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.7410 (17) ÅCell parameters from 3793 reflections
b = 14.846 (3) Åθ = 2.2–27.3°
c = 11.775 (2) ŵ = 1.49 mm−1
β = 102.43 (3)°T = 293 K
V = 1492.2 (5) Å3Block, blue
Z = 20.40 × 0.38 × 0.35 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3239 independent reflections
Radiation source: fine-focus sealed tube2706 reflections with I > 2σ(I)
graphiteRint = 0.036
ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −11→11
Tmin = 0.588, Tmax = 0.624k = −18→18
12293 measured reflectionsl = −15→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0349P)2 + 0.1139P]
where P = (Fo2 + 2Fc2)/3
3239 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.35 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
[Cu2(N3)2(C12H16N3O3)2]V = 1492.2 (5) Å3
Mr = 711.70Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.7410 (17) ŵ = 1.49 mm−1
b = 14.846 (3) ÅT = 293 K
c = 11.775 (2) Å0.40 × 0.38 × 0.35 mm
β = 102.43 (3)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3239 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2706 reflections with I > 2σ(I)
Tmin = 0.588, Tmax = 0.624Rint = 0.036
12293 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.35 e Å−3
S = 1.04Δρmin = −0.25 e Å−3
3239 reflectionsAbsolute structure: ?
201 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Cu10.94961 (3)0.106755 (14)0.014558 (19)0.02791 (9)
O11.14184 (17)0.17565 (9)0.07071 (14)0.0480 (4)
O21.42356 (19)0.55892 (11)0.08461 (15)0.0562 (5)
O31.2338 (2)0.57421 (11)−0.06657 (16)0.0573 (4)
N10.85117 (18)0.21807 (10)−0.07976 (14)0.0312 (4)
N20.7638 (2)0.10303 (11)0.10393 (15)0.0374 (4)
N30.90672 (19)0.00703 (11)−0.10862 (15)0.0371 (4)
N40.7826 (2)−0.00746 (11)−0.17324 (15)0.0359 (4)
N50.6652 (2)−0.02203 (14)−0.23562 (18)0.0557 (6)
N61.3106 (2)0.52861 (12)0.01293 (17)0.0416 (4)
C11.1769 (2)0.25787 (13)0.05229 (17)0.0328 (4)
C21.3234 (2)0.29231 (14)0.11226 (18)0.0371 (5)
H21.39170.25420.16160.044*
C31.3673 (2)0.37865 (14)0.10029 (19)0.0388 (5)
H31.46350.39960.14170.047*
C41.2658 (2)0.43592 (13)0.02469 (18)0.0343 (5)
C51.1238 (2)0.40603 (12)−0.03678 (18)0.0333 (5)
H51.05890.4448−0.08750.040*
C61.0759 (2)0.31767 (13)−0.02370 (16)0.0295 (4)
C70.9186 (2)0.29377 (13)−0.08454 (17)0.0314 (4)
H70.86140.3379−0.13150.038*
C80.6851 (2)0.21132 (14)−0.13842 (18)0.0376 (5)
H8A0.66990.1597−0.19020.045*
H8B0.65400.2650−0.18460.045*
C90.5848 (2)0.20112 (15)−0.0484 (2)0.0428 (5)
H9A0.60610.25160.00490.051*
H9B0.47550.2048−0.08800.051*
C100.6085 (2)0.11484 (14)0.0218 (2)0.0401 (5)
H10A0.52740.11130.06640.048*
H10B0.59310.0645−0.03200.048*
C110.7889 (3)0.17461 (19)0.1933 (2)0.0604 (7)
H11A0.70170.17610.23090.091*
H11B0.79790.23180.15710.091*
H11C0.88340.16250.24990.091*
C120.7584 (3)0.01507 (18)0.1626 (2)0.0590 (7)
H12A0.85370.00650.21970.089*
H12B0.7470−0.03250.10610.089*
H12C0.67100.01420.19990.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02889 (14)0.01925 (13)0.03410 (15)−0.00229 (9)0.00353 (10)−0.00002 (9)
O10.0389 (8)0.0283 (8)0.0686 (11)−0.0054 (6)−0.0064 (7)0.0129 (7)
O20.0549 (10)0.0413 (10)0.0700 (12)−0.0213 (8)0.0078 (9)−0.0117 (8)
O30.0655 (11)0.0321 (8)0.0720 (12)−0.0070 (8)0.0100 (9)0.0082 (9)
N10.0303 (9)0.0265 (9)0.0352 (9)−0.0001 (7)0.0035 (7)0.0009 (7)
N20.0352 (9)0.0385 (10)0.0377 (10)−0.0022 (7)0.0059 (8)0.0036 (8)
N30.0367 (9)0.0283 (9)0.0412 (10)0.0004 (8)−0.0031 (8)−0.0044 (7)
N40.0454 (10)0.0247 (9)0.0349 (10)0.0028 (8)0.0028 (8)−0.0036 (7)
N50.0479 (11)0.0508 (12)0.0565 (13)0.0010 (10)−0.0150 (10)−0.0132 (10)
N60.0439 (10)0.0312 (10)0.0536 (12)−0.0073 (8)0.0188 (9)−0.0064 (9)
C10.0366 (11)0.0255 (10)0.0366 (11)−0.0018 (8)0.0086 (9)0.0002 (8)
C20.0310 (11)0.0369 (12)0.0414 (12)0.0006 (9)0.0034 (9)0.0050 (9)
C30.0310 (11)0.0420 (13)0.0428 (12)−0.0065 (9)0.0064 (9)−0.0032 (10)
C40.0380 (11)0.0272 (10)0.0407 (12)−0.0075 (9)0.0153 (9)−0.0035 (9)
C50.0376 (11)0.0267 (10)0.0365 (11)0.0007 (8)0.0099 (9)0.0016 (8)
C60.0302 (10)0.0260 (10)0.0330 (11)−0.0019 (8)0.0081 (8)−0.0006 (8)
C70.0356 (11)0.0260 (10)0.0316 (10)0.0006 (8)0.0053 (8)0.0036 (8)
C80.0338 (11)0.0327 (11)0.0421 (12)−0.0024 (9)−0.0010 (9)0.0047 (9)
C90.0306 (11)0.0411 (13)0.0546 (14)0.0049 (9)0.0042 (10)0.0054 (10)
C100.0309 (11)0.0422 (13)0.0468 (13)−0.0029 (9)0.0072 (9)0.0018 (10)
C110.0541 (15)0.0777 (19)0.0489 (15)−0.0052 (13)0.0101 (12)−0.0190 (14)
C120.0505 (14)0.0621 (17)0.0653 (17)−0.0008 (12)0.0145 (13)0.0314 (14)
Geometric parameters (Å, °) top
Cu1—O11.9567 (14)C3—C41.401 (3)
Cu1—N32.0498 (17)C3—H30.9300
Cu1—N12.0720 (16)C4—C51.369 (3)
Cu1—N22.1178 (18)C5—C61.396 (3)
Cu1—N3i2.2492 (17)C5—H50.9300
O1—C11.288 (2)C6—C71.451 (2)
O2—N61.237 (2)C7—H70.9300
O3—N61.231 (2)C8—C91.522 (3)
N1—C71.276 (2)C8—H8A0.9700
N1—C81.470 (2)C8—H8B0.9700
N2—C111.478 (3)C9—C101.514 (3)
N2—C121.483 (3)C9—H9A0.9700
N2—C101.498 (3)C9—H9B0.9700
N3—N41.203 (2)C10—H10A0.9700
N3—Cu1i2.2492 (17)C10—H10B0.9700
N4—N51.147 (2)C11—H11A0.9600
N6—C41.445 (3)C11—H11B0.9600
C1—C21.417 (3)C11—H11C0.9600
C1—C61.424 (3)C12—H12A0.9600
C2—C31.354 (3)C12—H12B0.9600
C2—H20.9300C12—H12C0.9600
O1—Cu1—N3129.02 (7)C4—C5—C6120.39 (19)
O1—Cu1—N189.52 (6)C4—C5—H5119.8
N3—Cu1—N1101.84 (7)C6—C5—H5119.8
O1—Cu1—N2122.72 (7)C5—C6—C1119.65 (18)
N3—Cu1—N2106.84 (7)C5—C6—C7116.77 (17)
N1—Cu1—N290.73 (6)C1—C6—C7123.47 (18)
O1—Cu1—N3i83.01 (6)N1—C7—C6126.24 (18)
N3—Cu1—N3i78.68 (7)N1—C7—H7116.9
N1—Cu1—N3i170.54 (6)C6—C7—H7116.9
N2—Cu1—N3i98.18 (6)N1—C8—C9109.78 (17)
C1—O1—Cu1131.04 (13)N1—C8—H8A109.7
C7—N1—C8117.25 (16)C9—C8—H8A109.7
C7—N1—Cu1125.72 (14)N1—C8—H8B109.7
C8—N1—Cu1116.84 (12)C9—C8—H8B109.7
C11—N2—C12108.4 (2)H8A—C8—H8B108.2
C11—N2—C10110.51 (17)C10—C9—C8115.64 (18)
C12—N2—C10106.79 (16)C10—C9—H9A108.4
C11—N2—Cu1108.82 (14)C8—C9—H9A108.4
C12—N2—Cu1111.05 (14)C10—C9—H9B108.4
C10—N2—Cu1111.20 (13)C8—C9—H9B108.4
N4—N3—Cu1125.42 (14)H9A—C9—H9B107.4
N4—N3—Cu1i120.61 (13)N2—C10—C9116.75 (17)
Cu1—N3—Cu1i101.32 (7)N2—C10—H10A108.1
N5—N4—N3179.1 (2)C9—C10—H10A108.1
O3—N6—O2122.90 (19)N2—C10—H10B108.1
O3—N6—C4118.82 (18)C9—C10—H10B108.1
O2—N6—C4118.27 (19)H10A—C10—H10B107.3
O1—C1—C2118.69 (18)N2—C11—H11A109.5
O1—C1—C6123.94 (18)N2—C11—H11B109.5
C2—C1—C6117.36 (18)H11A—C11—H11B109.5
C3—C2—C1122.37 (19)N2—C11—H11C109.5
C3—C2—H2118.8H11A—C11—H11C109.5
C1—C2—H2118.8H11B—C11—H11C109.5
C2—C3—C4119.07 (19)N2—C12—H12A109.5
C2—C3—H3120.5N2—C12—H12B109.5
C4—C3—H3120.5H12A—C12—H12B109.5
C5—C4—C3121.14 (19)N2—C12—H12C109.5
C5—C4—N6119.42 (19)H12A—C12—H12C109.5
C3—C4—N6119.43 (19)H12B—C12—H12C109.5
Symmetry codes: (i) −x+2, −y, −z.
Acknowledgements top

The author acknowledges Xian Polytechnic University for a research grant.

references
References top

Bruker (2000). SMART (Version 5.625), SAINT (Version 6.01). SHELXTL (Version 6.10) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.

Cai, W.-X., Su, H. & Feng, Y.-L. (2007). Acta Cryst. E63, m501–m503.

Li, J.-X., Jiang, Y.-M. & Wang, J.-G. (2007). Acta Cryst. E63, m213–m215.

Yu, M.-M., Kou, H.-Z., Ni, Z.-H., Ge, C.-H. & Cui, A.-L. (2006). Acta Cryst. E62, m2050–m2051.

Zhang, C., Ai, H.-Q., Sun, D.-Z. & Ng, S. W. (2006). Acta Cryst. E62, m2045–m2046.

Zhao, Q., Wang, X., Fang, R. & Tiekink, E. R. T. (2003). Acta Cryst. E59, m722–m723.

Zhu, X., Li, B.-Z., Zhou, J.-H., Li, B.-L. & Zhang, Y. (2004). Acta Cryst. C60, m191–m193.