(4,5-Diaza­fluoren-9-one-κ² N,N′)bis­(thio­cyanato-κS)mercury(II)

Abstract

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,

• a = 10.570 (2) Å

• b = 16.112 (3) Å

• c = 8.3390 (17) Å

• β = 94.35 (3)°

• V = 1416.1 (5) ų

• 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[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(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.

Figures

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.

Crystal data

[Hg(NCS)2(C11H6N2O)]	F(000) = 928
Mr = 498.95	Dx = 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

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

Refinement

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(Fo2) + (0.0771P)2] where P = (Fo2 + 2Fc2)/3
1903 reflections	(Δ/σ)max < 0.001
97 parameters	Δρmax = 4.61 e Å−3
0 restraints	Δρmin = −1.81 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

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.