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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): m612.
Published online 2009 May 7. doi:  10.1107/S1600536809015724
PMCID: PMC2969723

cis-Bis(nitrato-κ2 O,O′)bis­(triethyl­phosphine oxide-κO)nickel(II)

Abstract

In the title compound, [Ni(NO3)2(C6H15OP)2], the NiII ion, lying on a crystallographic twofold axis, adopts a distorted octa­hedral coordination, consisting of O-donor atoms of two symmetry-related triethyl­phospine oxide and two bidentate nitrate ligands.

Related literature

For the synthesis and the crystal structure of the isotypic CoII complex, see: Alnaji et al. (1991 [triangle]). For the preparation of the precursor trans-[NiCl2(Et3P)2] (Et3P = triethyl­phosphine), see: Jensen (1936 [triangle]). For the synthesis of cis-[Pt(NO3)2(Et3P)2], see: Kuehl et al. (2001 [triangle]).

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Object name is e-65-0m612-scheme1.jpg

Experimental

Crystal data

  • [Ni(NO3)2(C6H15OP)2]
  • M r = 451.03
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m612-efi2.jpg
  • a = 16.954 (2) Å
  • b = 7.8494 (5) Å
  • c = 15.9905 (9) Å
  • β = 92.419 (5)°
  • V = 2126.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.10 mm−1
  • T = 294 K
  • 0.31 × 0.26 × 0.24 mm

Data collection

  • Siemens P4 four-circle diffractometer
  • Absorption correction: ψ scan (ABSPsiScan in PLATON; Spek, 2009 [triangle]) T min = 0.719, T max = 0.770
  • 2351 measured reflections
  • 1829 independent reflections
  • 1641 reflections with I > 2σ(I)
  • R int = 0.047
  • 3 standard reflections every 97 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.073
  • S = 1.05
  • 1829 reflections
  • 118 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: XSCANS (Bruker, 1999 [triangle]); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2008 [triangle]); software used to prepare material for publication: enCIFer (Allen et al., 2004 [triangle]).

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015724/kj2126sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015724/kj2126Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The author thanks Dr Iris M. Oppel and Professor William S. Sheldrick for generous support.

supplementary crystallographic information

Comment

The title complex, cis-[Ni(NO3)2(OPEt3)] (OPEt3 = triethylphosphine oxide), exhibits C2 point symmetry and is located on a twofold crystallographic axis. An ORTEP diagram is depicted in Fig. 1.

As previously observed in the isotypic CoII complex (Alnaji et al., 1991), the triethylphosphine oxide and the nitrate ligands are arranged in a cis geometry about the NiII ion. The bond lengths are comparable to those reported for the CoII complex. The bidentate nitrate ligand binds asymmetrically with Ni—O distances of 2.0738 (16) and 2.1429 (17) Å. This leads to differences in the N—O bond lengths. The N—O distances of the coordinated oxygen atoms are considerably longer than that of the free one (Table 1). The magnitude of the asymmetric bidentate binding is slightly smaller than that reported for the CoII complex.

The O2—Ni1—O3 angle is small, as is expected for a bidentate chelating nitrate ion. The remaining angles about the NiII ion show large deviations from the regular octahedral geometry (see table 1). The P—O—Ni angle exhibits a typical value of 140.8 (1)°.

Experimental

The title compound was obtained as an oxidation product of the metathesis reaction of trans-[NiCl2(Et3P)2] with AgNO3. The synthetic procedure was adapted from the preparation of cis-[Pt(NO3)2(Et3P)2] (Kuehl et al., 2001). trans-[NiCl2(Et3P)2] was prepared according to the literature (Jensen, 1936). 33 mg (0.197) AgNO3 was added to a stirred solution of 36 mg (0.098 mmol) trans-[NiCl2(Et3P)2] in 40 ml acetone. The mixture was stirred 12 h in the dark. The colour changed from red to yellow. The solvent was removed in vacuum and the residue was suspended in 40 ml dichloromethane. Filtration and subsequent evaporation of the solvent yielded a yellow powder. A single-crystal suitable for X-ray diffraction was obtained from methanol-d4 when the solvent was allowed to evaporate slowly at ambient temperature.

Refinement

Hydrogen atoms were placed at geometrically calculated positions and refined with Uiso 1.2 times (1.5 for methyl groups) of their parent atoms and allowing to ride on them. The initial torsion angles of the methyl groups were determined via a difference Fourier analysis and refined, while retaining the tetrahedral geometry.

Figures

Fig. 1.
ORTEP diagram of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are drawn with arbitrary size. Symmetry codes: (i) -x,y,-z + 1/2.

Crystal data

[Ni(NO3)2(C6H15OP)2]F(000) = 952
Mr = 451.03Dx = 1.409 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 50 reflections
a = 16.954 (2) Åθ = 4.7–16.8°
b = 7.8494 (5) ŵ = 1.10 mm1
c = 15.9905 (9) ÅT = 294 K
β = 92.419 (5)°Prism, yellow
V = 2126.1 (3) Å30.31 × 0.26 × 0.24 mm
Z = 4

Data collection

Siemens P4 four-circle diffractometer1641 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.047
graphiteθmax = 25.0°, θmin = 2.9°
ω scansh = −1→20
Absorption correction: ψ scan (ABSPsiScan in PLATON; Spek, 2009)k = −1→9
Tmin = 0.719, Tmax = 0.770l = −18→18
2351 measured reflections3 standard reflections every 97 reflections
1829 independent reflections intensity decay: none

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.073w = 1/[σ2(Fo2) + (0.0309P)2 + 1.435P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1829 reflectionsΔρmax = 0.22 e Å3
118 parametersΔρmin = −0.28 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0039 (5)

Special details

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)

xyzUiso*/Ueq
Ni10.00000.58558 (5)0.25000.04465 (16)
P10.10851 (4)0.30215 (8)0.15778 (3)0.04913 (18)
O10.08156 (10)0.4144 (2)0.22694 (10)0.0585 (4)
O2−0.04216 (10)0.6501 (2)0.13055 (10)0.0596 (4)
O3−0.08635 (10)0.7839 (2)0.23545 (11)0.0644 (5)
O4−0.12961 (13)0.8501 (3)0.10934 (14)0.0895 (6)
N1−0.08784 (12)0.7647 (3)0.15682 (13)0.0587 (5)
C110.13399 (18)0.4234 (3)0.06864 (16)0.0681 (7)
H11A0.15820.34810.02900.082*
H11B0.08600.46820.04180.082*
C120.18933 (19)0.5692 (4)0.0880 (2)0.0799 (8)
H12A0.16680.64270.12860.120*
H12B0.19770.63230.03770.120*
H12C0.23890.52560.11000.120*
C130.19220 (15)0.1817 (3)0.19631 (17)0.0642 (7)
H13A0.23360.26090.21370.077*
H13B0.17720.11980.24570.077*
C140.22625 (19)0.0551 (4)0.1355 (2)0.0910 (10)
H14A0.1884−0.03340.12330.137*
H14B0.27360.00590.16020.137*
H14C0.23830.11270.08470.137*
C150.03471 (17)0.1488 (4)0.12138 (18)0.0722 (7)
H15A0.05880.07150.08260.087*
H15B0.01890.08200.16890.087*
C16−0.03782 (17)0.2241 (4)0.0791 (2)0.0831 (9)
H16A−0.06200.30190.11660.125*
H16B−0.07440.13470.06410.125*
H16C−0.02350.28380.02960.125*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ni10.0491 (2)0.0437 (2)0.0416 (2)0.0000.00704 (16)0.000
P10.0584 (4)0.0457 (3)0.0434 (3)0.0050 (3)0.0032 (2)0.0001 (2)
O10.0626 (9)0.0619 (10)0.0511 (9)0.0137 (8)0.0046 (7)−0.0072 (8)
O20.0711 (11)0.0575 (10)0.0502 (9)0.0081 (9)0.0033 (8)0.0022 (8)
O30.0675 (11)0.0579 (10)0.0683 (11)0.0082 (8)0.0083 (9)−0.0071 (9)
O40.0899 (14)0.0704 (12)0.1056 (16)0.0125 (11)−0.0261 (12)0.0235 (12)
N10.0599 (12)0.0473 (11)0.0682 (14)−0.0036 (10)−0.0041 (10)0.0072 (10)
C110.096 (2)0.0589 (15)0.0500 (13)−0.0035 (14)0.0058 (13)0.0047 (12)
C120.087 (2)0.0734 (19)0.0802 (19)−0.0169 (16)0.0137 (16)0.0077 (15)
C130.0660 (16)0.0587 (15)0.0683 (16)0.0138 (13)0.0091 (12)0.0080 (12)
C140.082 (2)0.0632 (18)0.129 (3)0.0169 (15)0.025 (2)−0.0113 (18)
C150.0865 (19)0.0573 (15)0.0721 (17)−0.0088 (14)−0.0049 (14)0.0011 (14)
C160.086 (2)0.0774 (19)0.084 (2)−0.0173 (17)−0.0143 (16)−0.0025 (16)

Geometric parameters (Å, °)

Ni1—O11.9741 (16)C12—H12A0.9600
Ni1—O1i1.9741 (16)C12—H12B0.9600
Ni1—O2i2.0738 (16)C12—H12C0.9600
Ni1—O22.0738 (16)C13—C141.521 (4)
Ni1—O3i2.1429 (17)C13—H13A0.9700
Ni1—O32.1429 (17)C13—H13B0.9700
P1—O11.5001 (16)C14—H14A0.9600
P1—C111.782 (2)C14—H14B0.9600
P1—C131.793 (2)C14—H14C0.9600
P1—C151.814 (3)C15—C161.499 (4)
O2—N11.270 (3)C15—H15A0.9700
O3—N11.266 (3)C15—H15B0.9700
O4—N11.217 (3)C16—H16A0.9600
C11—C121.503 (4)C16—H16B0.9600
C11—H11A0.9700C16—H16C0.9600
C11—H11B0.9700
O1—Ni1—O1i94.2 (1)H11A—C11—H11B107.6
O1—Ni1—O2i96.97 (7)C11—C12—H12A109.5
O1i—Ni1—O2i102.19 (6)C11—C12—H12B109.5
O1—Ni1—O2102.19 (6)H12A—C12—H12B109.5
O1i—Ni1—O296.97 (7)C11—C12—H12C109.5
O2i—Ni1—O2151.7 (1)H12A—C12—H12C109.5
O1—Ni1—O3i91.95 (7)H12B—C12—H12C109.5
O1i—Ni1—O3i162.74 (7)C14—C13—P1116.2 (2)
O2i—Ni1—O3i61.00 (7)C14—C13—H13A108.2
O2—Ni1—O3i97.47 (7)P1—C13—H13A108.2
O1—Ni1—O3162.74 (7)C14—C13—H13B108.2
O1i—Ni1—O391.95 (7)P1—C13—H13B108.2
O2i—Ni1—O397.47 (7)H13A—C13—H13B107.4
O2—Ni1—O361.00 (7)C13—C14—H14A109.5
O3i—Ni1—O386.8 (1)C13—C14—H14B109.5
O1—P1—C11111.57 (12)H14A—C14—H14B109.5
O1—P1—C13108.53 (11)C13—C14—H14C109.5
C11—P1—C13109.97 (13)H14A—C14—H14C109.5
O1—P1—C15113.50 (12)H14B—C14—H14C109.5
C11—P1—C15106.55 (13)C16—C15—P1115.1 (2)
C13—P1—C15106.58 (13)C16—C15—H15A108.5
P1—O1—Ni1140.8 (1)P1—C15—H15A108.5
N1—O2—Ni193.42 (13)C16—C15—H15B108.5
N1—O3—Ni190.36 (13)P1—C15—H15B108.5
O4—N1—O3122.7 (2)H15A—C15—H15B107.5
O4—N1—O2122.1 (2)C15—C16—H16A109.5
O3—N1—O2115.21 (19)C15—C16—H16B109.5
C12—C11—P1114.3 (2)H16A—C16—H16B109.5
C12—C11—H11A108.7C15—C16—H16C109.5
P1—C11—H11A108.7H16A—C16—H16C109.5
C12—C11—H11B108.7H16B—C16—H16C109.5
P1—C11—H11B108.7

Symmetry codes: (i) −x, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KJ2126).

References

  • Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst.37, 335–338.
  • Alnaji, O., Dartiguenave, M. & Dartiguenave, Y. (1991). Inorg. Chim. Acta, 187, 31–38.
  • Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.
  • Bruker (1999). XSCANS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Jensen, K. A. (1936). Z. Anorg. Allg. Chem.229, 265–281.
  • Kuehl, C. J., Tabellion, F. M., Arif, A. M. & Stang, P. J. (2001). Organometallics, 20, 1956–1959.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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