metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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(4,5-Di­aza­fluoren-9-one-κ2N,N′)bis­­(thio­cyanato-κS)mercury(II)

aDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
*Correspondence e-mail: n-safari@cc.sbu.ac.ir

(Received 24 February 2011; accepted 3 March 2011; online 9 March 2011)

In the title compound, [Hg(NCS)2(C11H6N2O)], the HgII atom, lying on a twofold rotation axis, is four-coordinated in a distorted tetra­hedral geometry by an N,N′-bidentate diaza­fluoren-9-one ligand and two thio­cyanate anions. In the crystal, inter­molecular C—H⋯N and C—H⋯O hydrogen bonds are effective in the stabilization of the structure.

Related literature

For general background to metal complexes with diaza­fluoren-9-one ligands, see: Biju & Rajasekharan (2008[Biju, A. R. & Rajasekharan, M. V. (2008). Polyhedron, 27, 2065-2068.]); Kulkarni et al. (2002[Kulkarni, P., Padhye, S., Sinn, E., Anson, C. E. & Powell, A. K. (2002). Inorg. Chim. Acta, 332, 167-175.]); Menon & Rajasekharan (1998[Menon, S. & Rajasekharan, M. V. (1998). Polyhedron, 17, 2463-2476.]); Shi et al. (1995[Shi, X.-H., You, X.-Z., Li, C. & Xiong, R.-G. (1995). Transition Met. Chem. 20, 191-195.]); Wu & Xu (2004[Wu, Z.-Y. & Xu, D.-J. (2004). Acta Cryst. E60, m839-m841.]); Zhang et al. (2004[Zhang, R.-L., Zhao, J.-S., Yang, S.-Y. & Ng, S. W. (2004). Acta Cryst. E60, m262-m263.]). For related structures, see: Ravikumar & Lakshmi (1994[Ravikumar, K. & Lakshmi, N. V. (1994). Z. Kristallogr. 209, 56-57.]); Safari et al. (2009[Safari, N., Amani, V., Abedi, A., Notash, B. & Ng, S. W. (2009). Acta Cryst. E65, m372.]). For the synthesis of the ligand, see: Henderson et al. (1984[Henderson, L. J. Jr, Fronczek, F. R. & Cherry, W. R. (1984). J. Am. Chem. Soc. 106, 5876-5879.]).

[Scheme 1]

Experimental

Crystal data
  • [Hg(NCS)2(C11H6N2O)]

  • Mr = 498.95

  • Monoclinic, C 2/c

  • a = 10.570 (2) Å

  • b = 16.112 (3) Å

  • c = 8.3390 (17) Å

  • β = 94.35 (3)°

  • V = 1416.1 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 11.17 mm−1

  • T = 298 K

  • 0.45 × 0.30 × 0.25 mm

Data collection
  • Stoe IPDS-2T diffractometer

  • Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005[Stoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.023, Tmax = 0.059

  • 4787 measured reflections

  • 1903 independent reflections

  • 1737 reflections with I > 2σ(I)

  • Rint = 0.098

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.118

  • S = 1.09

  • 1903 reflections

  • 97 parameters

  • H-atom parameters constrained

  • Δρmax = 4.61 e Å−3

  • Δρmin = −1.82 e Å−3

Table 1
Selected bond lengths (Å)

Hg1—S1 2.4098 (17)
Hg1—N1 2.483 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2⋯N2i 0.93 2.56 3.276 (10) 134
C4—H4⋯O1ii 0.93 2.59 3.366 (8) 142
Symmetry codes: (i) [-x+1, y, -z-{\script{1\over 2}}]; (ii) -x+1, -y+1, -z.

Data collection: X-AREA (Stoe & Cie, 2005[Stoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

Henderson et al. (1984) first reported the synthesis of diazafluoren-9-one (dafone) and Ravikumar & Lakshmi (1994) determined the structure of this compound. Dafone is a bidentate ligand and numerous complexes with dafone have been prepared, such as that of cobalt (Shi et al., 1995), copper (Kulkarni et al., 2002; Menon & Rajasekharan, 1998), zinc (Zhang et al., 2004), manganese (Wu & Xu, 2004) and silver (Biju & Rajasekharan, 2008). For further investigation of the dafone complexes, we synthesized the title compound.

The asymmetric unit of the title compound (Fig. 1) contains a half molecule. The HgII atom, lying on a twofold rotation axis, is four-coordinated in a distorted tetrahedral geometry by an N,N'-bidentate dafone ligand and two thiocyanate anions. The Hg—N and Hg—S bond lengths (Table 1) and angles are within normal range as observed in [Hg(SCN)2(dm4bt)] (dm4bt = 2,2'-dimethyl-4,4'-bi-1,3-thiazole) (Safari et al., 2009). In the crystal, intermolecular C—H···O and C—H···N hydrogen bonds stabilize the structure (Table 2, Fig. 2).

Related literature top

For general background to metal complexes with diazafluoren-9-one ligands, see: Biju & Rajasekharan (2008); Kulkarni et al. (2002); Menon & Rajasekharan (1998); Shi et al. (1995); Wu & Xu (2004); Zhang et al. (2004). For related structures, see: Ravikumar & Lakshmi (1994); Safari et al. (2009). For the synthesis of the ligand, see: Henderson et al. (1984).

Experimental top

For the preparation of the title compound, a solution of dafone (0.13 g, 0.71 mmol) in methanol (20 ml) was added to a solution of Hg(SCN)2 (0.23 g, 0.71 mmol) in methanol (20 ml) at room temperature and the yellow powder was formed. Crystals suitable for X-ray diffraction were obtained by methanol vapor diffusion into a DMSO solution of the complex. The crystals were isolated after one week (yield: 0.28 g, 79%).

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The highest residual electron density was found at 0.90 Å from Hg1 atom and the deepest hole at 0.84 Å from Hg1 atom.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) -x+1, y, -z+1/2.]
[Figure 2] Fig. 2. The packing diagram of the title compound. Intermolecular C—H···O and C—H···N hydrogen bonds are shown as blue dashed lines.
(4,5-Diazafluoren-9-one-κ2N,N')bis(thiocyanato- κS)mercury(II) top
Crystal data top
[Hg(NCS)2(C11H6N2O)]F(000) = 928
Mr = 498.95Dx = 2.340 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1903 reflections
a = 10.570 (2) Åθ = 2.3–29.1°
b = 16.112 (3) ŵ = 11.17 mm1
c = 8.3390 (17) ÅT = 298 K
β = 94.35 (3)°Block, yellow
V = 1416.1 (5) Å30.45 × 0.30 × 0.25 mm
Z = 4
Data collection top
Stoe IPDS-2T
diffractometer
1903 independent reflections
Radiation source: fine-focus sealed tube1737 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.098
ω scansθmax = 29.1°, θmin = 2.3°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)
h = 1414
Tmin = 0.023, Tmax = 0.059k = 1922
4787 measured reflectionsl = 119
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0771P)2]
where P = (Fo2 + 2Fc2)/3
1903 reflections(Δ/σ)max < 0.001
97 parametersΔρmax = 4.61 e Å3
0 restraintsΔρmin = 1.82 e Å3
Crystal data top
[Hg(NCS)2(C11H6N2O)]V = 1416.1 (5) Å3
Mr = 498.95Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.570 (2) ŵ = 11.17 mm1
b = 16.112 (3) ÅT = 298 K
c = 8.3390 (17) Å0.45 × 0.30 × 0.25 mm
β = 94.35 (3)°
Data collection top
Stoe IPDS-2T
diffractometer
1903 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)
1737 reflections with I > 2σ(I)
Tmin = 0.023, Tmax = 0.059Rint = 0.098
4787 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 1.09Δρmax = 4.61 e Å3
1903 reflectionsΔρmin = 1.82 e Å3
97 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C70.7118 (6)0.0950 (5)0.0048 (8)0.0493 (13)
Hg10.50000.072315 (18)0.25000.04567 (15)
N10.4449 (4)0.1960 (3)0.0815 (6)0.0365 (9)
C10.4721 (4)0.2635 (3)0.1663 (6)0.0320 (9)
C20.3956 (5)0.2094 (4)0.0707 (7)0.0422 (11)
H20.37350.16370.13500.051*
C50.4558 (5)0.3449 (3)0.1142 (7)0.0377 (10)
C30.3766 (6)0.2879 (4)0.1349 (7)0.0453 (12)
H30.34380.29370.24090.054*
C40.4063 (5)0.3591 (4)0.0419 (8)0.0456 (12)
H40.39350.41240.08270.055*
S10.68555 (17)0.01847 (11)0.1348 (2)0.0576 (4)
O10.50000.4758 (4)0.25000.0586 (17)
C60.50000.4016 (6)0.25000.0432 (17)
N20.7356 (8)0.1448 (6)0.0831 (10)0.083 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C70.049 (3)0.058 (4)0.041 (3)0.004 (3)0.005 (2)0.002 (3)
Hg10.0541 (2)0.03049 (19)0.0543 (2)0.0000.01618 (14)0.000
N10.0374 (19)0.029 (2)0.043 (2)0.0004 (16)0.0032 (16)0.0006 (17)
C10.0334 (19)0.022 (2)0.040 (3)0.0006 (16)0.0044 (17)0.0012 (16)
C20.046 (3)0.040 (3)0.040 (3)0.004 (2)0.002 (2)0.001 (2)
C50.035 (2)0.028 (2)0.050 (3)0.0014 (18)0.0046 (19)0.005 (2)
C30.046 (3)0.047 (3)0.043 (3)0.007 (2)0.005 (2)0.007 (2)
C40.046 (3)0.035 (3)0.056 (3)0.005 (2)0.006 (2)0.015 (2)
S10.0623 (9)0.0412 (8)0.0715 (11)0.0171 (7)0.0201 (8)0.0072 (7)
O10.072 (4)0.023 (3)0.081 (5)0.0000.007 (4)0.000
C60.038 (3)0.033 (4)0.060 (5)0.0000.011 (3)0.000
N20.077 (4)0.104 (7)0.070 (5)0.003 (4)0.021 (3)0.025 (4)
Geometric parameters (Å, º) top
C7—N21.128 (11)C2—H20.9300
C7—S11.679 (8)C5—C41.385 (8)
Hg1—S12.4098 (17)C5—C61.502 (8)
Hg1—N12.483 (5)C3—C41.407 (9)
N1—C11.316 (7)C3—H30.9300
N1—C21.352 (7)C4—H40.9300
C1—C51.388 (6)O1—C61.195 (12)
C1—C1i1.473 (10)C6—C5i1.502 (8)
C2—C31.382 (8)
N2—C7—S1176.4 (8)C3—C2—H2118.5
S1i—Hg1—S1137.80 (9)C4—C5—C1118.7 (5)
S1i—Hg1—N1i103.08 (11)C4—C5—C6132.9 (5)
S1—Hg1—N1i110.60 (12)C1—C5—C6108.4 (5)
S1i—Hg1—N1110.60 (12)C2—C3—C4120.9 (5)
S1—Hg1—N1103.08 (11)C2—C3—H3119.6
N1i—Hg1—N173.2 (2)C4—C3—H3119.6
C1—N1—C2115.2 (5)C5—C4—C3115.8 (5)
C1—N1—Hg1109.0 (3)C5—C4—H4122.1
C2—N1—Hg1135.7 (4)C3—C4—H4122.1
N1—C1—C5126.5 (5)C7—S1—Hg199.9 (2)
N1—C1—C1i124.4 (3)O1—C6—C5i127.5 (4)
C5—C1—C1i109.1 (3)O1—C6—C5127.5 (4)
N1—C2—C3122.9 (6)C5i—C6—C5105.0 (7)
N1—C2—H2118.5
S1i—Hg1—N1—C197.7 (3)N1—C1—C5—C6179.7 (4)
S1—Hg1—N1—C1108.1 (3)C1i—C1—C5—C60.8 (6)
N1i—Hg1—N1—C10.3 (2)N1—C2—C3—C41.1 (9)
S1i—Hg1—N1—C282.2 (5)C1—C5—C4—C30.0 (8)
S1—Hg1—N1—C271.9 (5)C6—C5—C4—C3179.5 (5)
N1i—Hg1—N1—C2179.8 (6)C2—C3—C4—C50.6 (9)
C2—N1—C1—C50.5 (8)S1i—Hg1—S1—C7150.1 (3)
Hg1—N1—C1—C5179.5 (4)N1i—Hg1—S1—C769.2 (3)
C2—N1—C1—C1i179.2 (6)N1—Hg1—S1—C77.5 (3)
Hg1—N1—C1—C1i0.8 (7)C4—C5—C6—O10.7 (7)
C1—N1—C2—C31.1 (8)C1—C5—C6—O1179.7 (3)
Hg1—N1—C2—C3179.0 (4)C4—C5—C6—C5i179.3 (7)
N1—C1—C5—C40.0 (8)C1—C5—C6—C5i0.3 (3)
C1i—C1—C5—C4178.9 (5)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N2ii0.932.563.276 (10)134
C4—H4···O1iii0.932.593.366 (8)142
Symmetry codes: (ii) x+1, y, z1/2; (iii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Hg(NCS)2(C11H6N2O)]
Mr498.95
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)10.570 (2), 16.112 (3), 8.3390 (17)
β (°) 94.35 (3)
V3)1416.1 (5)
Z4
Radiation typeMo Kα
µ (mm1)11.17
Crystal size (mm)0.45 × 0.30 × 0.25
Data collection
DiffractometerStoe IPDS2T
diffractometer
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe & Cie, 2005)
Tmin, Tmax0.023, 0.059
No. of measured, independent and
observed [I > 2σ(I)] reflections
4787, 1903, 1737
Rint0.098
(sin θ/λ)max1)0.685
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.118, 1.09
No. of reflections1903
No. of parameters97
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)4.61, 1.82

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
Hg1—S12.4098 (17)Hg1—N12.483 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N2i0.932.563.276 (10)134
C4—H4···O1ii0.932.593.366 (8)142
Symmetry codes: (i) x+1, y, z1/2; (ii) x+1, y+1, z.
 

Acknowledgements

We thank the Graduate Study Councils of Shahid Beheshti University for financial support.

References

First citationBiju, A. R. & Rajasekharan, M. V. (2008). Polyhedron, 27, 2065–2068.  Web of Science CSD CrossRef CAS Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
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First citationHenderson, L. J. Jr, Fronczek, F. R. & Cherry, W. R. (1984). J. Am. Chem. Soc. 106, 5876–5879.  CSD CrossRef CAS Web of Science Google Scholar
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First citationStoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany.  Google Scholar
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First citationZhang, R.-L., Zhao, J.-S., Yang, S.-Y. & Ng, S. W. (2004). Acta Cryst. E60, m262–m263.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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