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Acta Cryst. (2007). E63, m2268    [ doi:10.1107/S1600536807037154 ]

Redetermination of catena-poly[[nitrato(1,10-phenanthroline)copper(II)]-[mu]-nitrato]

X.-C. Zhou and Y.-Q. Liu

Abstract top

The structure of the title copper coordination polymer, [Cu(NO3)3(C10H8N2)]n, previously reported by McFadden & McPhail [J. Chem. Soc. Dalton Trans. (1975), pp. 1993-1998], has been redetermined, leading to a more precise result. The crystal structure consists of a zigzag chain formed by the polymer [Cu(NO3)3(phen)]n (phen is 1,10-phenanthroline). The CuII atom has a slightly distorted square-pyramidal coordination environment consisting of two N atoms of the phen ligand, two O atoms of different nitrate ligands, and one O atom of a nitrate anion. The compound forms a one-dimensional chain using nitrate as an end-to-end bridging ligand.

Comment top

Each CuIIion is five-coordinated and possess a slightly distorted square-pyramidal coordination geometry, defined by two N atoms from one 1,10-phenanthroline ligand, two O atoms of two different bridging nitrate acid anion, and one O atom of a symetry related mono-dentate nitrate anion (Fig. 1). The compound forms a one-dimensional chain using nitrate anion as an end-to-end bridging ligand. The Cu—N bond lengths is almost equal, with Cu1—N1 being 1.998 (2) Å and Cu1—N2 being 2.004 (2) Å, respectively. The bond length between Cu1 and O atoms which set at the peak of the square-pyramidal are longer than between the O atoms which locates at the plane of square-pyramidal, the shorter bond lengths of Cu1—O1 and Cu1—O6 being 1.9556 (17) Å and 1.9979 (18) Å, the longer Cu—O bond length is 2.3410 (18) Å for Cu1—O4.

The packing is further stabilized by π_π stacking interactions involving the phenanthroline ring systems, the distance between the closest centroids being 3.66\%A with an interplanar distance of 3.60\%A.

Related literature top

For related literature, see: McFadden & McPhail (1975).

Experimental top

Cu(NO3)2.3H2O (0.0242 g, 0.1 mmol) was dissolved in a small test tube (5 ml e thanol),then 1,10-phenanthroline (0.0199 g, 1 mmol) was added, NaOH (0.006 g, 0.15 mmol) was then added to the above solution. The whole mixture was sealed in a close vessel with 30 ml e ther. 4 days later, blue crystals of (I) were obtained.

Refinement top

All H were fixed geometrically and treated as riding on their parent atoms with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of complex (I) with the atom-labelling scheme showing the formation of the infinite chain. Ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 3/2 - x, 1/2 + y, 3/2 - z; (ii) 3/2 - x, y - 1/2, 3/2 - z].
catena-poly[[nitrato(1,10-phenanthroline)copper(II)]-µ-nitrato] top
Crystal data top
[Cu(NO3)3(C10H8N2)]Z = 4
Mr = 367.77F(000) = 740.0
Monoclinic, P21/nDx = 1.815 Mg m−3
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.7832 (15) ŵ = 1.66 mm−1
b = 9.1136 (16) ÅT = 293 K
c = 17.173 (3) ÅBlock, blue
β = 101.686 (2)°0.40 × 0.25 × 0.20 mm
V = 1346.2 (4) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		2595 independent reflections
Radiation source: fine-focus sealed tube2071 reflections with I > 2σ(I)
graphiteRint = 0.025
φ and ω scansθmax = 26.0°, θmin = 2.4°
Absorption correction: ψ scan
(North et al., 1968)		h = −10→10
Tmin = 0.607, Tmax = 0.707k = −11→11
8361 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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H-atom parameters constrained
S = 1.06 w = 1[σ2(Fo2) + (0.0308P)2 + 0.6118P]
where P = (Fo2 + 2Fc2)3
2595 reflections(Δ/σ)max = 0.002
208 parametersΔρmax = 0.27 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
Crystal data top
[Cu(NO3)3(C10H8N2)]V = 1346.2 (4) Å3
Mr = 367.77Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.7832 (15) ŵ = 1.66 mm−1
b = 9.1136 (16) ÅT = 293 K
c = 17.173 (3) Å0.40 × 0.25 × 0.20 mm
β = 101.686 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2595 independent reflections
Absorption correction: ψ scan
(North et al., 1968)		2071 reflections with I > 2σ(I)
Tmin = 0.607, Tmax = 0.707Rint = 0.025
8361 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.064Δρmax = 0.27 e Å−3
S = 1.06Δρmin = −0.27 e Å−3
2595 reflectionsAbsolute structure: ?
208 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
Cu10.83503 (3)0.42791 (3)0.696821 (13)0.03409 (9)
N10.70510 (18)0.36714 (18)0.59243 (9)0.0336 (3)
N20.89172 (19)0.59365 (17)0.63144 (10)0.0348 (4)
N31.0982 (2)0.4773 (2)0.81600 (10)0.0411 (4)
N40.88410 (19)0.12873 (19)0.72182 (10)0.0375 (4)
O10.95129 (17)0.50491 (18)0.79780 (8)0.0459 (4)
O21.1715 (2)0.5285 (2)0.87827 (10)0.0624 (5)
O31.1543 (2)0.4000 (3)0.77103 (11)0.0764 (6)
O40.87904 (17)0.00535 (16)0.75191 (9)0.0459 (4)
O50.9548 (2)0.15217 (19)0.66849 (11)0.0620 (5)
O60.81196 (16)0.23479 (15)0.74821 (8)0.0387 (3)
C10.6044 (2)0.2574 (2)0.57589 (12)0.0409 (5)
H10.58430.19960.61730.049*
C20.5276 (3)0.2260 (2)0.49841 (13)0.0447 (5)
H20.45630.14940.48890.054*
C30.5575 (2)0.3078 (2)0.43656 (12)0.0415 (5)
H30.50780.28630.38470.050*
C40.6639 (2)0.4248 (2)0.45183 (11)0.0356 (4)
C50.7326 (2)0.4513 (2)0.53139 (11)0.0308 (4)
C60.7046 (3)0.5186 (3)0.39209 (12)0.0439 (5)
H60.66340.50010.33870.053*
C70.8020 (3)0.6335 (3)0.41217 (12)0.0443 (5)
H70.82700.69230.37230.053*
C80.8675 (2)0.6664 (2)0.49334 (12)0.0372 (4)
C90.8347 (2)0.5732 (2)0.55247 (11)0.0316 (4)
C100.9630 (3)0.7881 (2)0.51904 (14)0.0469 (5)
H100.98970.85270.48210.056*
C111.0165 (3)0.8110 (2)0.59846 (14)0.0492 (5)
H111.07740.89260.61590.059*
C120.9792 (2)0.7110 (2)0.65335 (13)0.0430 (5)
H121.01710.72740.70720.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.04125 (15)0.03153 (14)0.02821 (13)−0.00254 (10)0.00398 (10)−0.00099 (9)
N10.0400 (9)0.0289 (8)0.0312 (8)−0.0026 (7)0.0059 (7)0.0014 (7)
N20.0376 (8)0.0304 (8)0.0365 (8)−0.0013 (7)0.0075 (7)−0.0034 (7)
N30.0447 (10)0.0394 (9)0.0374 (9)0.0016 (8)0.0040 (8)0.0007 (8)
N40.0375 (9)0.0358 (9)0.0382 (9)−0.0020 (8)0.0052 (7)0.0025 (8)
O10.0427 (8)0.0510 (9)0.0400 (8)0.0055 (7)−0.0014 (6)−0.0121 (7)
O20.0539 (10)0.0664 (11)0.0564 (10)0.0050 (9)−0.0136 (8)−0.0195 (9)
O30.0592 (11)0.1147 (17)0.0551 (11)0.0235 (11)0.0110 (9)−0.0262 (11)
O40.0466 (8)0.0337 (8)0.0578 (9)0.0045 (7)0.0120 (7)0.0140 (7)
O50.0791 (12)0.0495 (10)0.0710 (11)0.0040 (9)0.0474 (10)0.0071 (9)
O60.0498 (8)0.0342 (7)0.0333 (7)0.0056 (6)0.0110 (6)0.0023 (6)
C10.0478 (11)0.0329 (10)0.0406 (11)−0.0070 (9)0.0059 (9)0.0033 (9)
C20.0480 (12)0.0345 (11)0.0478 (12)−0.0085 (9)0.0006 (10)−0.0035 (10)
C30.0483 (12)0.0398 (11)0.0336 (10)0.0003 (10)0.0016 (9)−0.0060 (9)
C40.0406 (10)0.0344 (10)0.0320 (9)0.0036 (9)0.0078 (8)−0.0020 (8)
C50.0345 (9)0.0275 (9)0.0311 (9)0.0027 (8)0.0085 (8)0.0003 (7)
C60.0508 (12)0.0518 (13)0.0296 (10)0.0008 (11)0.0097 (9)0.0013 (9)
C70.0515 (12)0.0473 (12)0.0374 (11)0.0019 (11)0.0168 (10)0.0093 (10)
C80.0380 (10)0.0352 (10)0.0416 (10)0.0028 (9)0.0153 (9)0.0033 (9)
C90.0333 (9)0.0285 (9)0.0342 (9)0.0028 (8)0.0097 (8)−0.0014 (8)
C100.0501 (12)0.0370 (12)0.0572 (13)−0.0063 (10)0.0197 (11)0.0067 (10)
C110.0481 (12)0.0358 (12)0.0638 (14)−0.0119 (10)0.0117 (11)−0.0036 (11)
C120.0463 (11)0.0367 (11)0.0439 (11)−0.0051 (9)0.0042 (9)−0.0064 (9)
Geometric parameters (Å, °) top
Cu1—O11.9558 (14)C2—C31.366 (3)
Cu1—O61.9975 (14)C2—H20.9300
Cu1—N11.9985 (16)C3—C41.407 (3)
Cu1—N22.0042 (17)C3—H30.9300
Cu1—O4i2.3407 (15)C4—C51.398 (3)
N1—C11.327 (3)C4—C61.435 (3)
N1—C51.360 (2)C5—C91.428 (3)
N2—C121.326 (3)C6—C71.352 (3)
N2—C91.360 (2)C6—H60.9300
N3—O31.221 (2)C7—C81.428 (3)
N3—O21.224 (2)C7—H70.9300
N3—O11.289 (2)C8—C91.398 (3)
N4—O51.225 (2)C8—C101.407 (3)
N4—O41.242 (2)C10—C111.366 (3)
N4—O61.287 (2)C10—H100.9300
O4—Cu1ii2.3407 (15)C11—C121.397 (3)
C1—C21.394 (3)C11—H110.9300
C1—H10.9300C12—H120.9300
O1—Cu1—O690.34 (6)C2—C3—C4119.57 (18)
O1—Cu1—N1174.57 (6)C2—C3—H3120.2
O6—Cu1—N193.53 (6)C4—C3—H3120.2
O1—Cu1—N294.70 (7)C5—C4—C3116.87 (18)
O6—Cu1—N2166.06 (6)C5—C4—C6118.35 (18)
N1—Cu1—N282.41 (7)C3—C4—C6124.78 (19)
O1—Cu1—O4i82.72 (6)N1—C5—C4123.17 (17)
O6—Cu1—O4i86.47 (6)N1—C5—C9116.37 (17)
N1—Cu1—O4i93.71 (6)C4—C5—C9120.45 (17)
N2—Cu1—O4i107.04 (6)C7—C6—C4121.03 (19)
C1—N1—C5118.36 (17)C7—C6—H6119.5
C1—N1—Cu1129.46 (14)C4—C6—H6119.5
C5—N1—Cu1112.15 (12)C6—C7—C8121.37 (19)
C12—N2—C9117.93 (17)C6—C7—H7119.3
C12—N2—Cu1130.12 (14)C8—C7—H7119.3
C9—N2—Cu1111.86 (12)C9—C8—C10116.66 (19)
O3—N3—O2124.37 (19)C9—C8—C7118.70 (19)
O3—N3—O1118.15 (18)C10—C8—C7124.64 (19)
O2—N3—O1117.47 (18)N2—C9—C8123.56 (18)
O5—N4—O4122.36 (18)N2—C9—C5116.42 (17)
O5—N4—O6119.50 (17)C8—C9—C5119.99 (18)
O4—N4—O6118.14 (16)C11—C10—C8119.8 (2)
N3—O1—Cu1117.52 (12)C11—C10—H10120.1
N4—O4—Cu1ii121.92 (12)C8—C10—H10120.1
N4—O6—Cu1113.88 (11)C10—C11—C12119.6 (2)
N1—C1—C2122.10 (19)C10—C11—H11120.2
N1—C1—H1119.0C12—C11—H11120.2
C2—C1—H1119.0N2—C12—C11122.4 (2)
C3—C2—C1119.9 (2)N2—C12—H12118.8
C3—C2—H2120.1C11—C12—H12118.8
C1—C2—H2120.1
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, −z+3/2.
Acknowledgements top

The authors are grateful for the support of this work by the Natural Science Foundation of Jiangxi Province (grant Nos. 0520036 and 0620029).

references
References top

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

McFadden, D. L. & McPhail, A. T. (1975). J. Chem. Soc. Dalton Trans. pp. 1993–1998.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

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