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Acta Cryst. (2007). E63, m3108    [ doi:10.1107/S1600536807059077 ]

catena-Poly[[(nitrato-[kappa]O)(1,10-phenanthroline-[kappa]2N,N')copper(II)]-[mu]-acetamido-[kappa]2O:N]

T. Liu and J. Y. Zhu

Abstract top

In the crystal structure of the title compound, [Cu(NO3)(C2H4NO)(C12H8N2)]n, the CuII atoms are linked by acetamidate ligands, forming a chain. Each CuII atom is five-coordinated by two N atoms of the 1,10-phenanthroline ligand, one nitrate O atom, and one N and one O atoms of acetamidate in a trigonal-bipyramidal geometry. In the crystal structure, the chains are linked by hydrogen bonds into a polymeric ribbon structure.

Comment top

The crystal structure of catena-Poly[[(nitrato-κO) (1,10-phenanthroline-κ2N,N')nickel(II)]-µ-acetamido-κ2O:N], (II), has previously been reported (Liu & Zhu, 2007). The crystal structure determination of the title compound, (I), has been carried out in order to elucidate the molecular conformation and to compare it with that of (II). We report herein the crystal structure of (I).

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). The title compound, [Cu(NO3)(C2H4NO)(C12H8N2)]n, which are linked by acetamidate ligands to form a chain. Each CuII atom is five-coordinated by two N atoms of 1,10-phenanthroline (phen) ligand, one nitrate O atom, and one N and one O atoms of acetamidate within a bipyramidal coordination geometry (Table 1). The Cu—O and Cu—N bond are in the range [1.942 (2)–2.322 (2) Å] and [1.981 (2)–2.011 (3) Å], respectively (Table 1), as in (II).

In the crystal structure, no classic C—H···O hydrogen bonds (Fig. 2 and Table 2) seem to be effective in the stabilization of the structure, resulting in the formation of a polymeric ribbon structure, as in (II).

The both compounds, (I) and (II), are isostructural.

Related literature top

For a related structure, see: Liu & Zhu (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb, which was then sealed. Copper (II) nitrate hexahydrate (296.3 mg, 1 mmol), phen (180.2 mg, 1 mmol), acetamide (59.1 mg, 1 mmol) and distilled water (8 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 453 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small blue crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

Refinement top

The H atoms were positioned geometrically, with N—H = 0.86 Å (for NH), C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.2 for aromatic and NH H atoms and x = 1.5 for methyl H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code (A): -x + 3/2, y + 1/2, -z + 1/2].
[Figure 2] Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
catena-Poly[[(nitrato-κO)(1,10-phenanthroline- κ2N,N')copper(II)]-µ-acetamido-κ2O:N] top
Crystal data top
[Cu(NO3)(C2H4NO)(C12H8N2)]F(000) = 740
Mr = 363.82Dx = 1.820 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5781 reflections
a = 8.680 (2) Åθ = 2.3–27.0°
b = 9.190 (3) ŵ = 1.67 mm−1
c = 17.0137 (12) ÅT = 273 K
β = 101.904 (2)°Prism, blue
V = 1328.0 (6) Å30.41 × 0.23 × 0.22 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		2679 independent reflections
Radiation source: fine-focus sealed tube2285 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
φ and ω scansθmax = 26.7°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.624, Tmax = 0.695k = −11→11
8439 measured reflectionsl = −21→21
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0915P)2 + 0.5483P]
where P = (Fo2 + 2Fc2)/3
2679 reflections(Δ/σ)max = 0.001
209 parametersΔρmax = 0.80 e Å−3
0 restraintsΔρmin = −0.69 e Å−3
Crystal data top
[Cu(NO3)(C2H4NO)(C12H8N2)]V = 1328.0 (6) Å3
Mr = 363.82Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.680 (2) ŵ = 1.67 mm−1
b = 9.190 (3) ÅT = 273 K
c = 17.0137 (12) Å0.41 × 0.23 × 0.22 mm
β = 101.904 (2)°
Data collection top
Bruker APEXII area-detector
diffractometer		2679 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2285 reflections with I > 2σ(I)
Tmin = 0.624, Tmax = 0.695Rint = 0.017
8439 measured reflectionsθmax = 26.7°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.130Δρmax = 0.80 e Å−3
S = 1.08Δρmin = −0.69 e Å−3
2679 reflectionsAbsolute structure: ?
209 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
Cu10.66503 (4)0.92788 (4)0.803179 (19)0.03409 (17)
O10.5481 (3)1.0048 (3)0.70204 (13)0.0470 (6)
O20.3259 (4)0.9011 (4)0.72922 (19)0.0769 (10)
O30.3290 (3)1.0282 (4)0.62163 (17)0.0623 (7)
O40.6206 (3)0.5052 (3)0.74795 (15)0.0474 (6)
N10.6078 (3)1.0941 (3)0.86853 (16)0.0356 (5)
N20.7951 (3)0.8671 (3)0.90775 (14)0.0337 (5)
N30.6879 (3)0.7347 (2)0.75217 (13)0.0281 (5)
H3A0.74190.72390.71550.034*
N40.4025 (3)0.9775 (3)0.68377 (16)0.0403 (6)
C10.5201 (4)1.2102 (4)0.8464 (2)0.0441 (7)
H10.48131.22590.79190.053*
C20.4828 (4)1.3112 (4)0.9017 (2)0.0486 (8)
H20.42251.39300.88400.058*
C30.5364 (4)1.2873 (4)0.9812 (2)0.0474 (8)
H30.50941.35051.01890.057*
C40.6330 (4)1.1664 (4)1.00650 (19)0.0386 (6)
C50.6977 (4)1.1340 (4)1.08823 (19)0.0441 (7)
H50.67261.19231.12850.053*
C60.7960 (4)1.0188 (4)1.10835 (19)0.0443 (7)
H60.83811.00041.16220.053*
C70.8363 (4)0.9251 (3)1.04838 (18)0.0364 (6)
C80.9427 (4)0.8075 (4)1.06354 (19)0.0430 (7)
H80.99260.78561.11600.052*
C90.9725 (4)0.7261 (4)1.0016 (2)0.0450 (7)
H91.04380.64941.01150.054*
C100.8963 (4)0.7578 (3)0.92368 (19)0.0410 (7)
H100.91660.70120.88160.049*
C110.7675 (3)0.9512 (3)0.96854 (17)0.0313 (6)
C120.6653 (3)1.0726 (3)0.94749 (18)0.0319 (6)
C130.6164 (3)0.6283 (3)0.77790 (16)0.0298 (5)
C140.5453 (4)0.6522 (3)0.83151 (19)0.0384 (7)
H14A0.45210.59320.82350.058*
H14B0.51630.75310.83060.058*
H14C0.61150.62920.88250.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0402 (3)0.0328 (2)0.0277 (2)0.00245 (13)0.00354 (16)0.00106 (13)
O10.0436 (12)0.0556 (15)0.0381 (11)−0.0051 (11)−0.0004 (9)0.0129 (11)
O20.0571 (16)0.119 (3)0.0546 (17)−0.0216 (17)0.0123 (14)0.0260 (18)
O30.0540 (14)0.0697 (17)0.0541 (16)−0.0053 (13)−0.0104 (12)0.0154 (14)
O40.0456 (12)0.0372 (12)0.0596 (14)−0.0041 (10)0.0115 (11)−0.0154 (11)
N10.0387 (12)0.0327 (12)0.0354 (13)0.0003 (10)0.0078 (10)0.0046 (10)
N20.0380 (12)0.0302 (12)0.0322 (11)0.0023 (10)0.0057 (10)−0.0009 (10)
N30.0357 (11)0.0277 (11)0.0226 (10)−0.0040 (9)0.0097 (9)−0.0034 (8)
N40.0415 (13)0.0381 (13)0.0384 (13)0.0003 (11)0.0018 (11)0.0009 (12)
C10.0443 (16)0.0401 (17)0.0459 (17)0.0061 (14)0.0048 (14)0.0030 (14)
C20.0476 (17)0.0393 (17)0.059 (2)0.0113 (14)0.0112 (15)0.0014 (15)
C30.0483 (17)0.0381 (17)0.059 (2)0.0077 (14)0.0185 (15)−0.0056 (15)
C40.0392 (14)0.0383 (15)0.0408 (15)−0.0039 (12)0.0141 (13)−0.0049 (13)
C50.0510 (17)0.0488 (18)0.0362 (15)−0.0016 (15)0.0177 (14)−0.0078 (14)
C60.0494 (17)0.0536 (19)0.0303 (14)−0.0008 (15)0.0096 (13)−0.0018 (14)
C70.0408 (15)0.0374 (16)0.0311 (14)−0.0032 (12)0.0079 (12)0.0029 (11)
C80.0479 (16)0.0412 (16)0.0365 (15)0.0008 (14)0.0009 (13)0.0059 (13)
C90.0485 (17)0.0356 (16)0.0464 (17)0.0089 (13)−0.0007 (14)0.0036 (14)
C100.0475 (16)0.0332 (15)0.0406 (16)0.0062 (13)0.0050 (13)−0.0037 (12)
C110.0348 (13)0.0288 (13)0.0301 (13)−0.0028 (11)0.0061 (11)0.0005 (10)
C120.0325 (13)0.0292 (14)0.0344 (14)−0.0030 (10)0.0081 (12)0.0011 (11)
C130.0297 (12)0.0270 (12)0.0308 (13)0.0024 (10)0.0019 (11)−0.0028 (10)
C140.0509 (16)0.0299 (14)0.0446 (15)−0.0041 (12)0.0337 (14)−0.0055 (12)
Geometric parameters (Å, º) top
Cu1—O11.942 (2)C3—C41.405 (5)
Cu1—O4i2.322 (2)C3—H30.9300
Cu1—N12.011 (3)C4—C121.395 (4)
Cu1—N21.981 (2)C4—C51.420 (5)
Cu1—N32.004 (2)C5—C61.359 (5)
O1—N41.263 (4)C5—H50.9300
O2—N41.321 (4)C6—C71.432 (4)
O3—N41.210 (4)C6—H60.9300
O4—C131.244 (4)C7—C111.387 (4)
O4—Cu1ii2.322 (2)C7—C81.411 (5)
N1—C11.320 (4)C8—C91.360 (5)
N1—C121.347 (4)C8—H80.9300
N2—C101.325 (4)C9—C101.385 (5)
N2—C111.352 (4)C9—H90.9300
N3—C131.283 (4)C10—H100.9300
N3—H3A0.8600C11—C121.425 (4)
C1—C21.406 (5)C13—C141.222 (4)
C1—H10.9300C14—H14A0.9600
C2—C31.355 (5)C14—H14B0.9600
C2—H20.9300C14—H14C0.9600
O1—Cu1—O4i82.50 (9)C3—C4—C5123.8 (3)
O1—Cu1—N194.00 (11)C6—C5—C4120.8 (3)
O1—Cu1—N2174.61 (10)C6—C5—H5119.6
O1—Cu1—N391.10 (10)C4—C5—H5119.6
O4—Cu1—N1i138.52 (4)C5—C6—C7121.4 (3)
O4—Cu1—N2i125.47 (5)C5—C6—H6119.3
O4—Cu1—N3i141.73 (5)C7—C6—H6119.3
N1—Cu1—N282.97 (10)C11—C7—C8116.4 (3)
N1—Cu1—N3165.98 (10)C11—C7—C6118.4 (3)
N2—Cu1—N392.87 (10)C8—C7—C6125.2 (3)
N4—O1—Cu1117.34 (19)C9—C8—C7120.1 (3)
C13—O4—Cu1ii121.63 (19)C9—C8—H8119.9
C1—N1—C12118.4 (3)C7—C8—H8119.9
C1—N1—Cu1130.6 (2)C8—C9—C10119.8 (3)
C12—N1—Cu1110.93 (19)C8—C9—H9120.1
C10—N2—C11119.5 (3)C10—C9—H9120.1
C10—N2—Cu1128.9 (2)N2—C10—C9121.4 (3)
C11—N2—Cu1111.59 (19)N2—C10—H10119.3
C13—N3—Cu1115.46 (18)C9—C10—H10119.3
C13—N3—H3A122.3N2—C11—C7122.9 (3)
Cu1—N3—H3A122.3N2—C11—C12117.1 (3)
O3—N4—O2118.6 (3)C7—C11—C12120.1 (3)
O3—N4—O1117.3 (3)N1—C12—C4122.6 (3)
O2—N4—O1124.1 (3)N1—C12—C11116.6 (3)
N1—C1—C2122.9 (3)C4—C12—C11120.7 (3)
N1—C1—H1118.6C14—C13—O4122.1 (3)
C2—C1—H1118.6C14—C13—N3118.1 (3)
C3—C2—C1118.8 (3)O4—C13—N3119.8 (3)
C3—C2—H2120.6C13—C14—H14A109.5
C1—C2—H2120.6C13—C14—H14B109.5
C2—C3—C4119.6 (3)H14A—C14—H14B109.5
C2—C3—H3120.2C13—C14—H14C109.5
C4—C3—H3120.2H14A—C14—H14C109.5
C12—C4—C3117.7 (3)H14B—C14—H14C109.5
C12—C4—C5118.5 (3)
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O3iii0.932.503.319 (5)147
C5—H5···O2iv0.932.573.171 (5)124
Symmetry codes: (iii) −x+1/2, y+1/2, −z+3/2; (iv) −x+1, −y+2, −z+2.
Selected geometric parameters (Å, º) top
Cu1—O11.942 (2)Cu1—N21.981 (2)
Cu1—O4i2.322 (2)Cu1—N32.004 (2)
Cu1—N12.011 (3)
O1—Cu1—O4i82.50 (9)O4—Cu1—N2i125.47 (5)
O1—Cu1—N194.00 (11)O4—Cu1—N3i141.73 (5)
O1—Cu1—N2174.61 (10)N1—Cu1—N282.97 (10)
O1—Cu1—N391.10 (10)N1—Cu1—N3165.98 (10)
O4—Cu1—N1i138.52 (4)N2—Cu1—N392.87 (10)
Symmetry code: (i) −x+3/2, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O3ii0.932.503.319 (5)147
C5—H5···O2iii0.932.573.171 (5)124
Symmetry codes: (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1, −y+2, −z+2.
Acknowledgements top

We thank the Youth Program of Jinggangshan University for financial support of this work.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Liu, T. & Zhu, J.-Y. (2007). Acta Cryst. E63, m2977–m2978.

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

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

Siemens (1996). SAINT and SHELXTL. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.