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

Notash, B.; Safari, N.; Amani, V.

doi:10.1107/S1600536811008142

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m418

doi:10.1107/S1600536811008142

Open

access

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

Behrouz Notash,^a Nasser Safari ^a ^* and Vahid Amani ^a

^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 Hg^II 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 ); 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

Crystal data

[Hg(NCS)₂(C₁₁H₆N₂O)]
M_r = 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 ) T_min = 0.023, T_max = 0.059
4787 measured reflections
1903 independent reflections
1737 reflections with I > 2σ(I)
R_int = 0.098

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.118
S = 1.09
1903 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 4.61 e Å⁻³
Δρ_min = −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	D⋯A	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); cell refinement: X-AREA; data reduction: X-AREA; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008142/hy2412sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008142/hy2412Isup2.hkl

checkCIF report

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 Hg^II 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%).

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

	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.]
	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
M_r = 498.95	D_x = 2.340 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1903 reflections
a = 10.570 (2) Å	θ = 2.3–29.1°
b = 16.112 (3) Å	µ = 11.17 mm⁻¹
c = 8.3390 (17) Å	T = 298 K
β = 94.35 (3)°	Block, yellow
V = 1416.1 (5) Å³	0.45 × 0.30 × 0.25 mm
Z = 4

Data collection top

Stoe IPDS-2T diffractometer	1903 independent reflections
Radiation source: fine-focus sealed tube	1737 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.098
ω scans	θ_max = 29.1°, θ_min = 2.3°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	h = −14→14
T_min = 0.023, T_max = 0.059	k = −19→22
4787 measured reflections	l = −11→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0771P)²] where P = (F_o² + 2F_c²)/3
1903 reflections	(Δ/σ)_max < 0.001
97 parameters	Δρ_max = 4.61 e Å⁻³
0 restraints	Δρ_min = −1.82 e Å⁻³

Crystal data top

[Hg(NCS)₂(C₁₁H₆N₂O)]	V = 1416.1 (5) Å³
M_r = 498.95	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 10.570 (2) Å	µ = 11.17 mm⁻¹
b = 16.112 (3) Å	T = 298 K
c = 8.3390 (17) Å	0.45 × 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)
T_min = 0.023, T_max = 0.059	R_int = 0.098
4787 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.09	Δρ_max = 4.61 e Å⁻³
1903 reflections	Δρ_min = −1.82 e Å⁻³
97 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C7	0.7118 (6)	0.0950 (5)	0.0048 (8)	0.0493 (13)
Hg1	0.5000	0.072315 (18)	0.2500	0.04567 (15)
N1	0.4449 (4)	0.1960 (3)	0.0815 (6)	0.0365 (9)
C1	0.4721 (4)	0.2635 (3)	0.1663 (6)	0.0320 (9)
C2	0.3956 (5)	0.2094 (4)	−0.0707 (7)	0.0422 (11)
H2	0.3735	0.1637	−0.1350	0.051*
C5	0.4558 (5)	0.3449 (3)	0.1142 (7)	0.0377 (10)
C3	0.3766 (6)	0.2879 (4)	−0.1349 (7)	0.0453 (12)
H3	0.3438	0.2937	−0.2409	0.054*
C4	0.4063 (5)	0.3591 (4)	−0.0419 (8)	0.0456 (12)
H4	0.3935	0.4124	−0.0827	0.055*
S1	0.68555 (17)	0.01847 (11)	0.1348 (2)	0.0576 (4)
O1	0.5000	0.4758 (4)	0.2500	0.0586 (17)
C6	0.5000	0.4016 (6)	0.2500	0.0432 (17)
N2	0.7356 (8)	0.1448 (6)	−0.0831 (10)	0.083 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.049 (3)	0.058 (4)	0.041 (3)	0.004 (3)	0.005 (2)	−0.002 (3)
Hg1	0.0541 (2)	0.03049 (19)	0.0543 (2)	0.000	0.01618 (14)	0.000
N1	0.0374 (19)	0.029 (2)	0.043 (2)	0.0004 (16)	0.0032 (16)	0.0006 (17)
C1	0.0334 (19)	0.022 (2)	0.040 (3)	0.0006 (16)	0.0044 (17)	0.0012 (16)
C2	0.046 (3)	0.040 (3)	0.040 (3)	0.004 (2)	0.002 (2)	0.001 (2)
C5	0.035 (2)	0.028 (2)	0.050 (3)	0.0014 (18)	0.0046 (19)	0.005 (2)
C3	0.046 (3)	0.047 (3)	0.043 (3)	0.007 (2)	0.005 (2)	0.007 (2)
C4	0.046 (3)	0.035 (3)	0.056 (3)	0.005 (2)	0.006 (2)	0.015 (2)
S1	0.0623 (9)	0.0412 (8)	0.0715 (11)	0.0171 (7)	0.0201 (8)	0.0072 (7)
O1	0.072 (4)	0.023 (3)	0.081 (5)	0.000	0.007 (4)	0.000
C6	0.038 (3)	0.033 (4)	0.060 (5)	0.000	0.011 (3)	0.000
N2	0.077 (4)	0.104 (7)	0.070 (5)	0.003 (4)	0.021 (3)	0.025 (4)

Geometric parameters (Å, º) top

C7—N2	1.128 (11)	C2—H2	0.9300
C7—S1	1.679 (8)	C5—C4	1.385 (8)
Hg1—S1	2.4098 (17)	C5—C6	1.502 (8)
Hg1—N1	2.483 (5)	C3—C4	1.407 (9)
N1—C1	1.316 (7)	C3—H3	0.9300
N1—C2	1.352 (7)	C4—H4	0.9300
C1—C5	1.388 (6)	O1—C6	1.195 (12)
C1—C1ⁱ	1.473 (10)	C6—C5ⁱ	1.502 (8)
C2—C3	1.382 (8)

N2—C7—S1	176.4 (8)	C3—C2—H2	118.5
S1ⁱ—Hg1—S1	137.80 (9)	C4—C5—C1	118.7 (5)
S1ⁱ—Hg1—N1ⁱ	103.08 (11)	C4—C5—C6	132.9 (5)
S1—Hg1—N1ⁱ	110.60 (12)	C1—C5—C6	108.4 (5)
S1ⁱ—Hg1—N1	110.60 (12)	C2—C3—C4	120.9 (5)
S1—Hg1—N1	103.08 (11)	C2—C3—H3	119.6
N1ⁱ—Hg1—N1	73.2 (2)	C4—C3—H3	119.6
C1—N1—C2	115.2 (5)	C5—C4—C3	115.8 (5)
C1—N1—Hg1	109.0 (3)	C5—C4—H4	122.1
C2—N1—Hg1	135.7 (4)	C3—C4—H4	122.1
N1—C1—C5	126.5 (5)	C7—S1—Hg1	99.9 (2)
N1—C1—C1ⁱ	124.4 (3)	O1—C6—C5ⁱ	127.5 (4)
C5—C1—C1ⁱ	109.1 (3)	O1—C6—C5	127.5 (4)
N1—C2—C3	122.9 (6)	C5ⁱ—C6—C5	105.0 (7)
N1—C2—H2	118.5

S1ⁱ—Hg1—N1—C1	97.7 (3)	N1—C1—C5—C6	−179.7 (4)
S1—Hg1—N1—C1	−108.1 (3)	C1ⁱ—C1—C5—C6	−0.8 (6)
N1ⁱ—Hg1—N1—C1	−0.3 (2)	N1—C2—C3—C4	−1.1 (9)
S1ⁱ—Hg1—N1—C2	−82.2 (5)	C1—C5—C4—C3	0.0 (8)
S1—Hg1—N1—C2	71.9 (5)	C6—C5—C4—C3	179.5 (5)
N1ⁱ—Hg1—N1—C2	179.8 (6)	C2—C3—C4—C5	0.6 (9)
C2—N1—C1—C5	−0.5 (8)	S1ⁱ—Hg1—S1—C7	150.1 (3)
Hg1—N1—C1—C5	179.5 (4)	N1ⁱ—Hg1—S1—C7	−69.2 (3)
C2—N1—C1—C1ⁱ	−179.2 (6)	N1—Hg1—S1—C7	7.5 (3)
Hg1—N1—C1—C1ⁱ	0.8 (7)	C4—C5—C6—O1	0.7 (7)
C1—N1—C2—C3	1.1 (8)	C1—C5—C6—O1	−179.7 (3)
Hg1—N1—C2—C3	−179.0 (4)	C4—C5—C6—C5ⁱ	−179.3 (7)
N1—C1—C5—C4	0.0 (8)	C1—C5—C6—C5ⁱ	0.3 (3)
C1ⁱ—C1—C5—C4	178.9 (5)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N2ⁱⁱ	0.93	2.56	3.276 (10)	134
C4—H4···O1ⁱⁱⁱ	0.93	2.59	3.366 (8)	142

Symmetry codes: (ii) −x+1, y, −z−1/2; (iii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Hg(NCS)₂(C₁₁H₆N₂O)]
M_r	498.95
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	10.570 (2), 16.112 (3), 8.3390 (17)
β (°)	94.35 (3)
V (Å³)	1416.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	11.17
Crystal size (mm)	0.45 × 0.30 × 0.25

Data collection
Diffractometer	Stoe IPDS2T diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)
T_min, T_max	0.023, 0.059
No. of measured, independent and observed [I > 2σ(I)] reflections	4787, 1903, 1737
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.118, 1.09
No. of reflections	1903
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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—S1

2.4098 (17)

Hg1—N1

2.483 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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−1/2; (ii) −x+1, −y+1, −z.

Acknowledgements

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

References

Biju, A. R. & Rajasekharan, M. V. (2008). Polyhedron, 27, 2065–2068. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Henderson, 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
Kulkarni, P., Padhye, S., Sinn, E., Anson, C. E. & Powell, A. K. (2002). Inorg. Chim. Acta, 332, 167–175. CrossRef CAS Google Scholar
Menon, S. & Rajasekharan, M. V. (1998). Polyhedron, 17, 2463–2476. Web of Science CSD CrossRef CAS Google Scholar
Ravikumar, K. & Lakshmi, N. V. (1994). Z. Kristallogr. 209, 56–57. CrossRef CAS Web of Science Google Scholar
Safari, N., Amani, V., Abedi, A., Notash, B. & Ng, S. W. (2009). Acta Cryst. E65, m372. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, X.-H., You, X.-Z., Li, C. & Xiong, R.-G. (1995). Transition Met. Chem. 20, 191–195. CAS Google Scholar
Stoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wu, Z.-Y. & Xu, D.-J. (2004). Acta Cryst. E60, m839–m841. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, 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