Bis[1,3-bis­(2-cyano­phen­yl)triazenido]mercury(II)

Rofouei, M.K.; Barghamadi, M.; Taghdiri, M.; Attar Gharamaleki, J.

doi:10.1107/S1600536809035326

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Pages m1185-m1186

doi:10.1107/S1600536809035326

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Bis[1,3-bis(2-cyanophenyl)triazenido]mercury(II)

Mohammad Kazem Rofouei,^a ^* Marzieh Barghamadi,^a Mehdi Taghdiri ^b and Jafar Attar Gharamaleki ^c

^aFaculty of Chemistry, Tarbiat Moallem University, Tehran, Iran, ^bDepartment of Chemistry, Payame Noor University, Ardakan, Yazd, Iran, and ^cYoung Researchers Club, Islamic Azad University, North Tehran Branch, Tehran, Iran
^*Correspondence e-mail: rofouei_mk@yahoo.com

(Received 17 August 2009; accepted 1 September 2009; online 9 September 2009)

In the title compound, [Hg(C₁₄H₈N₅)₂], the central atom is four-coordinated by two bidentate 1,3-bis(2-cyanophenyl)triazenide ligands in a distorted square-planar geometry. The asymmteric unit is composed of one ligand molecule and one Hg^II ion, which is disordered over two sites, one lying on an inversion center and the other on a general position with site-occupancy factors of 0.2378 (7) and 0.3811 (7), respectively. The monomeric molecules of the complex are linked into pairs through non-classical C—H⋯N hydrogen bonds. The resulting dimeric units are assembled by translation along the crystallographic c axis into chains linked through secondary π–π interactions [centroid–centroid distances = 3.685 (2) and 3.574 (2) Å], as well as C—H⋯π stacking interactions, resulting in a two-dimensional architecture.

Related literature

For transition metal complexes containing 1,3-diaryltriazenide ions, see: Vrieze & Van Koten (1987 ); Hursthouse et al. (1993 ). For metal–η-arene π-interactions in Hg^II complexes, see: Horner et al. (2006 ). For related crystal structures, see: Rofouei et al. (2006 ); Melardi et al. (2008 ); Payehghadr et al. (2006 ); Melardi et al. (2007 ); Hematyar & Rofouei (2008 ); Rofouei et al. (2009 ).

Experimental

Crystal data

[Hg(C₁₄H₈N₅)₂]
M_r = 693.50
Monoclinic, C 2/c
a = 23.0721 (12) Å
b = 7.7307 (4) Å
c = 15.6680 (8) Å
β = 110.481 (1)°
V = 2617.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 5.92 mm⁻¹
T = 100 K
0.21 × 0.20 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.296, T_max = 0.629
15538 measured reflections
3479 independent reflections
2876 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.085
S = 0.99
3479 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 2.67 e Å⁻³
Δρ_min = −1.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯N4ⁱ	0.95	2.61	3.428 (5)	145
C6—H6A⋯N5ⁱⁱ	0.95	2.61	3.522 (5)	160
C10—H10A⋯Cg2ⁱⁱⁱ	0.95	2.96	3.629 (2)	129
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg2 is the centroid of C7–C12 ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035326/pv2202sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035326/pv2202Isup2.hkl

checkCIF report

Comment top

Triazenes are characterized by a diazoamino group (NN—N) commonly adopting a trans configuration in the ground state. Recently, the study of transition metal complexes containing 1,3-diaryltriazenide ions has been increased due to the potential reactivity of these ligands (Vrieze & Koten, 1987). This anion is a three-atom donor ligand that can act as a monodentate group, a chelating ligand or a bridging ligand between two metal centers (Hursthouse et al., 1993).

Several bisdiaryl symmetric and asymmetric-substituted triazenide complex polymers of Hg(II) which have a remarkable ability to self-assemble in different manners through metal-η-arene π-interactions have been reported (Horner et al., 20006). Hg(II) is a diamagnetic ion and maintains d¹⁰ electron configuration which minimizes intrinsic coordination geometry preferences while favoring coordination by softer ligands. We have previously reported the synthesis of [1,3-bis(2-methoxy)phenyl]triazene ligand (Rofouei et al., 2006) and its Ag(I) complex (Payehghadr et al., 2006). In addition, we have reported the Hg(II) complexes with this ligand by using HgCl₂ (Melardi et al., 2007), HgBr₂ (Hematyar and Rofouei, 2008), Hg(CH₃COO)₂ and Hg(SCN)₂ (Rofouei et al., 2009) as starting materials. In this paper, a new Hg(II) complex of a recently synthesized ligand ([1,3-bis(2-cyano)phenyl]triazene) (Melardi et al., 2008) is reported. Mercury(II) acetate was used as the starting material.

The molecular structure of the title compound is shown in Fig. 1. There is a high disorder of Hg atom in the complex. The Hg(II) atom was disordered over 3 sites (only 2 of them are symmetrically independent). Hg1:Hg1A:Hg2 atoms are disordered in ratio 0.38:0.38:0.24. The central atom in this compound is coordinated by two symmetrically related triazenide ions. Each Hg^II atom is four-coordinated by two nitrogen atoms N1, and N3 of two 1,3-bis(2-cyano)phenyl]triazene fragments which act as bidentate ligands. The arrangement of the four donor atoms around Hg(II) atom results in a distorted square planar geometry.

In the lattice of the title compound, the monomeric [Hg(C₁₄H₈N₅)₂] molecules are linked into pairs through non-classical C–H···N hydrogen bonds (details are provided in Table 1). The resulting dimeric units are assembled by translation along the crystallographic c axis to unidimensional chains linked through secondary π–interactions. Consequently, 1-D chains formed by C–H···N hydrogen bonds are connected with one another by π-π and C–H···π stacking interactions, resulting in the 2-D architecture(Fig. 2). These π-π stacking interactions are present between aromatic rings with centroid-centroid distances of 3.685 (2) and 3.574 (2) Å and also between C–H group of phenyl rings with aromatic rings with H···π distance of 2.96 Å for C10—H10A···Cg; Cg is the centroid of C7—C12 ring.

Related literature top

For transition metal complexes containing 1,3-diaryltriazenide ions, see: Vrieze & Van Koten (1987); Hursthouse et al. (1993). For metal–η-arene π-interactions in Hg(II) complexes, see: Horner et al. (2006). For related crystal structures, see: Rofouei et al. (2006); Melardi et al. (2008); Payehghadr et al. (2006); Melardi et al. (2007); Hematyar & Rofouei (2008); Rofouei et al. (2009). Cg2 is the centroid of C7–C12 ring.

Experimental top

Anhydrous methanolic solution of [1,3-bis(2-cyano)phenyl]triazene (0.247 g) was added to anhydrous methanolic solution of mercury(II) acetate ( 0.160 g). After several hours, the mixture was filtered, the product washed with methanol, the yellow precipitate thus obtained was dissolved in diethyl ether and stored in a freezer. After 14 days, well formed orange-red crystals were produced which decompose above 523 K.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, with ellipsoids drawn at 50% probability level: Hg1 has been omitted for clarity. Symmetry code to generate atoms with label "a": -x + 1, y, -z + 1/2.
	Fig. 2. The unit cell packing diagram of the title compound along b crystal axes showing π-π and C–H···π stacking interactions. Hydrogen atoms have been excluded for clarity.

Bis[1,3-bis(2-cyanophenyl)triazenido]mercury(II) top

Crystal data top

[Hg(C₁₄H₈N₅)₂]	F(000) = 1336
M_r = 693.50	D_x = 1.759 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3560 reflections
a = 23.0721 (12) Å	θ = 2.8–30.1°
b = 7.7307 (4) Å	µ = 5.92 mm⁻¹
c = 15.6680 (8) Å	T = 100 K
β = 110.481 (1)°	Plate, orange
V = 2617.9 (2) Å³	0.21 × 0.20 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3479 independent reflections
Radiation source: fine-focus sealed tube	2876 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 29.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −31→31
T_min = 0.296, T_max = 0.629	k = −10→10
15538 measured reflections	l = −21→21

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.04P)² + 7P] where P = (F_o² + 2F_c²)/3
3479 reflections	(Δ/σ)_max = 0.001
183 parameters	Δρ_max = 2.67 e Å⁻³
0 restraints	Δρ_min = −1.12 e Å⁻³

Crystal data top

[Hg(C₁₄H₈N₅)₂]	V = 2617.9 (2) Å³
M_r = 693.50	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 23.0721 (12) Å	µ = 5.92 mm⁻¹
b = 7.7307 (4) Å	T = 100 K
c = 15.6680 (8) Å	0.21 × 0.20 × 0.08 mm
β = 110.481 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3479 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2876 reflections with I > 2σ(I)
T_min = 0.296, T_max = 0.629	R_int = 0.044
15538 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 0.99	Δρ_max = 2.67 e Å⁻³
3479 reflections	Δρ_min = −1.12 e Å⁻³
183 parameters

Special details top

Experimental. ¹H NMR and ¹³C NMR of the free ligand and the title compound were recorded in DMSO as solvent:

For the free ligand, hydrogen atoms of the aromatic ring appear at δ = 7.27–7.86 ppm (4H) and hydrogen atom of NH group appears at δ = 13.45 ppm (1H); in ¹³C NMR we have resonances at 118, 124, 128, 133, 134 and 135 ppm which belong to the carbon atoms of aromatic ring.

In ¹H NMR spectra of the title complex, the resonance for the hydrogen atom of NH group has completely disappeared and the hydrogen atoms of aromatic ring now appear at δ = 7.27–7.86 ppm (4H); in ¹³C NMR spectra, carbon atoms of aromatic ring have resonances at 103, 118, 120, 125, 133 and 149 ppm. These data support the structure presented in this article.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Hg1	0.467164 (12)	0.37562 (3)	0.213648 (18)	0.01852 (8)	0.3811 (7)
Hg2	0.5000	0.44451 (8)	0.2500	0.01852 (8)	0.2378 (7)
C1	0.46005 (11)	0.2107 (3)	0.02350 (18)	0.0190 (5)
C2	0.40569 (13)	0.1222 (4)	0.0192 (2)	0.0256 (6)
C3	0.37257 (13)	0.0268 (4)	−0.0586 (2)	0.0313 (7)
H3A	0.3360	−0.0328	−0.0611	0.038*
C4	0.39267 (15)	0.0190 (4)	−0.1315 (2)	0.0337 (7)
H4A	0.3703	−0.0458	−0.1842	0.040*
C5	0.44625 (14)	0.1073 (4)	−0.1270 (2)	0.0288 (6)
H5A	0.4600	0.1022	−0.1774	0.035*
C6	0.48006 (12)	0.2024 (4)	−0.05072 (18)	0.0215 (5)
H6A	0.5165	0.2615	−0.0491	0.026*
C7	0.62706 (12)	0.5268 (3)	0.19697 (18)	0.0183 (5)
C8	0.65811 (13)	0.6146 (4)	0.27876 (19)	0.0216 (5)
C9	0.71486 (13)	0.6961 (4)	0.2931 (2)	0.0256 (6)
H9A	0.7353	0.7553	0.3487	0.031*
C10	0.74111 (13)	0.6907 (4)	0.2268 (2)	0.0269 (6)
H10A	0.7797	0.7459	0.2364	0.032*
C11	0.71085 (13)	0.6038 (4)	0.1457 (2)	0.0244 (6)
H11A	0.7290	0.6007	0.0999	0.029*
C12	0.65480 (12)	0.5218 (4)	0.13037 (18)	0.0199 (5)
H12A	0.6351	0.4620	0.0747	0.024*
C13	0.38358 (14)	0.1295 (4)	0.0939 (3)	0.0359 (8)
C14	0.63072 (15)	0.6272 (4)	0.3485 (2)	0.0287 (6)
N1	0.49222 (10)	0.2999 (3)	0.10491 (16)	0.0209 (5)
N2	0.54323 (10)	0.3720 (3)	0.10789 (15)	0.0192 (5)
N3	0.56967 (10)	0.4507 (3)	0.18522 (15)	0.0189 (5)
N4	0.36490 (15)	0.1358 (5)	0.1528 (3)	0.0531 (9)
N5	0.60964 (15)	0.6392 (4)	0.4044 (2)	0.0416 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.01873 (13)	0.01983 (13)	0.02026 (13)	−0.00001 (10)	0.01092 (9)	−0.00188 (10)
Hg2	0.01873 (13)	0.01983 (13)	0.02026 (13)	−0.00001 (10)	0.01092 (9)	−0.00188 (10)
C1	0.0150 (12)	0.0155 (12)	0.0251 (13)	0.0019 (10)	0.0053 (10)	0.0025 (10)
C2	0.0172 (13)	0.0223 (14)	0.0358 (16)	0.0018 (11)	0.0074 (11)	0.0029 (12)
C3	0.0189 (14)	0.0213 (15)	0.0452 (18)	−0.0002 (11)	0.0005 (13)	0.0025 (13)
C4	0.0314 (16)	0.0237 (15)	0.0330 (17)	0.0033 (12)	−0.0052 (13)	−0.0015 (12)
C5	0.0332 (16)	0.0246 (15)	0.0239 (14)	0.0079 (12)	0.0040 (12)	0.0015 (11)
C6	0.0206 (13)	0.0160 (12)	0.0265 (14)	0.0048 (10)	0.0065 (11)	0.0036 (11)
C7	0.0154 (12)	0.0180 (12)	0.0210 (12)	0.0014 (9)	0.0058 (10)	0.0033 (10)
C8	0.0237 (13)	0.0199 (13)	0.0208 (13)	0.0030 (10)	0.0073 (11)	0.0030 (10)
C9	0.0232 (14)	0.0235 (14)	0.0252 (14)	−0.0004 (11)	0.0022 (11)	−0.0012 (11)
C10	0.0156 (13)	0.0256 (14)	0.0374 (16)	0.0002 (11)	0.0065 (12)	0.0041 (13)
C11	0.0217 (13)	0.0246 (15)	0.0316 (15)	0.0025 (11)	0.0152 (12)	0.0040 (11)
C12	0.0169 (12)	0.0222 (14)	0.0216 (13)	0.0020 (10)	0.0080 (10)	0.0029 (10)
C13	0.0229 (15)	0.0358 (18)	0.052 (2)	−0.0071 (13)	0.0167 (15)	0.0026 (15)
C14	0.0357 (16)	0.0265 (15)	0.0241 (14)	−0.0007 (13)	0.0106 (13)	−0.0005 (12)
N1	0.0177 (11)	0.0189 (11)	0.0291 (12)	−0.0018 (9)	0.0120 (9)	−0.0014 (9)
N2	0.0177 (10)	0.0186 (11)	0.0220 (11)	0.0002 (9)	0.0080 (9)	0.0024 (9)
N3	0.0193 (11)	0.0187 (11)	0.0209 (11)	−0.0009 (9)	0.0098 (9)	−0.0006 (9)
N4	0.0406 (18)	0.064 (2)	0.067 (2)	−0.0130 (16)	0.0348 (17)	−0.0032 (18)
N5	0.0542 (19)	0.0458 (18)	0.0313 (15)	−0.0025 (14)	0.0231 (14)	−0.0045 (13)

Geometric parameters (Å, º) top

Hg1—Hg2	0.9381 (4)	C5—H5A	0.9500
Hg1—Hg1ⁱ	1.5445 (5)	C6—H6A	0.9500
Hg1—N1	2.066 (2)	C7—N3	1.401 (3)
Hg1—N3ⁱ	2.124 (2)	C7—C12	1.403 (4)
Hg1—N3	2.620 (2)	C7—C8	1.405 (4)
Hg2—Hg1ⁱ	0.9381 (4)	C8—C9	1.399 (4)
Hg2—N3	2.181 (2)	C8—C14	1.444 (4)
Hg2—N3ⁱ	2.181 (2)	C9—C10	1.374 (4)
Hg2—N1	2.483 (2)	C9—H9A	0.9500
Hg2—N1ⁱ	2.483 (2)	C10—C11	1.390 (4)
C1—C6	1.395 (4)	C10—H10A	0.9500
C1—C2	1.409 (4)	C11—C12	1.384 (4)
C1—N1	1.411 (3)	C11—H11A	0.9500
C2—C3	1.401 (4)	C12—H12A	0.9500
C2—C13	1.432 (5)	C13—N4	1.148 (5)
C3—C4	1.376 (5)	C14—N5	1.145 (4)
C3—H3A	0.9500	N1—N2	1.288 (3)
C4—C5	1.392 (5)	N2—N3	1.301 (3)
C4—H4A	0.9500	N3—Hg1ⁱ	2.124 (2)
C5—C6	1.388 (4)

N1—Hg1—N3ⁱ	173.18 (9)	C9—C8—C7	121.0 (3)
N1—Hg1—N3	52.63 (8)	C9—C8—C14	118.7 (3)
N3ⁱ—Hg1—N3	133.38 (8)	C7—C8—C14	120.3 (3)
N3—Hg2—N3ⁱ	177.49 (12)	C10—C9—C8	120.0 (3)
N3—Hg2—N1	54.04 (8)	C10—C9—H9A	120.0
N3ⁱ—Hg2—N1	127.37 (8)	C8—C9—H9A	120.0
N3—Hg2—N1ⁱ	127.37 (8)	C9—C10—C11	119.5 (3)
N3ⁱ—Hg2—N1ⁱ	54.04 (8)	C9—C10—H10A	120.2
N1—Hg2—N1ⁱ	126.46 (11)	C11—C10—H10A	120.2
C6—C1—C2	119.1 (3)	C12—C11—C10	121.4 (3)
C6—C1—N1	123.6 (2)	C12—C11—H11A	119.3
C2—C1—N1	117.3 (2)	C10—C11—H11A	119.3
C3—C2—C1	120.1 (3)	C11—C12—C7	120.0 (3)
C3—C2—C13	119.3 (3)	C11—C12—H12A	120.0
C1—C2—C13	120.5 (3)	C7—C12—H12A	120.0
C4—C3—C2	120.4 (3)	N4—C13—C2	178.9 (4)
C4—C3—H3A	119.8	N5—C14—C8	178.9 (4)
C2—C3—H3A	119.8	N2—N1—C1	115.4 (2)
C3—C4—C5	119.2 (3)	N2—N1—Hg1	111.29 (18)
C3—C4—H4A	120.4	C1—N1—Hg1	132.34 (17)
C5—C4—H4A	120.4	N2—N1—Hg2	89.96 (16)
C6—C5—C4	121.6 (3)	C1—N1—Hg2	153.44 (17)
C6—C5—H5A	119.2	N1—N2—N3	111.2 (2)
C4—C5—H5A	119.2	N2—N3—C7	115.6 (2)
C5—C6—C1	119.5 (3)	N2—N3—Hg1ⁱ	112.79 (16)
C5—C6—H6A	120.3	C7—N3—Hg1ⁱ	128.55 (17)
C1—C6—H6A	120.3	N2—N3—Hg2	103.97 (16)
N3—C7—C12	123.1 (2)	C7—N3—Hg2	139.87 (18)
N3—C7—C8	118.7 (2)	N2—N3—Hg1	84.13 (14)
C12—C7—C8	118.2 (2)	C7—N3—Hg1	159.80 (18)

N1—Hg1—Hg2—Hg1ⁱ	−80.24 (7)	N3ⁱ—Hg2—N1—N2	171.78 (14)
N3ⁱ—Hg1—Hg2—Hg1ⁱ	103.00 (6)	N1ⁱ—Hg2—N1—N2	−118.98 (15)
N3—Hg1—Hg2—Hg1ⁱ	−79.11 (7)	Hg1—Hg2—N1—C1	12.3 (4)
Hg1ⁱ—Hg1—Hg2—N3	79.11 (7)	Hg1ⁱ—Hg2—N1—C1	124.7 (4)
N1—Hg1—Hg2—N3	−1.13 (10)	N3—Hg2—N1—C1	−169.1 (4)
N3ⁱ—Hg1—Hg2—N3	−177.89 (11)	N3ⁱ—Hg2—N1—C1	8.4 (4)
Hg1ⁱ—Hg1—Hg2—N3ⁱ	−103.00 (6)	N1ⁱ—Hg2—N1—C1	77.6 (4)
N1—Hg1—Hg2—N3ⁱ	176.76 (9)	Hg1ⁱ—Hg2—N1—Hg1	112.41 (8)
N3—Hg1—Hg2—N3ⁱ	177.89 (11)	N3—Hg2—N1—Hg1	178.67 (12)
Hg1ⁱ—Hg1—Hg2—N1	80.24 (7)	N3ⁱ—Hg2—N1—Hg1	−3.92 (11)
N3ⁱ—Hg1—Hg2—N1	−176.76 (9)	N1ⁱ—Hg2—N1—Hg1	65.32 (5)
N3—Hg1—Hg2—N1	1.13 (10)	C1—N1—N2—N3	−179.9 (2)
Hg1ⁱ—Hg1—Hg2—N1ⁱ	−52.59 (5)	Hg1—N1—N2—N3	9.9 (3)
N1—Hg1—Hg2—N1ⁱ	−132.83 (10)	Hg2—N1—N2—N3	8.2 (2)
N3ⁱ—Hg1—Hg2—N1ⁱ	50.42 (8)	N1—N2—N3—C7	177.2 (2)
N3—Hg1—Hg2—N1ⁱ	−131.70 (9)	N1—N2—N3—Hg1ⁱ	15.2 (3)
C6—C1—C2—C3	0.3 (4)	N1—N2—N3—Hg2	−9.6 (2)
N1—C1—C2—C3	−178.1 (2)	N1—N2—N3—Hg1	−7.29 (19)
C6—C1—C2—C13	−179.4 (3)	C12—C7—N3—N2	0.6 (4)
N1—C1—C2—C13	2.2 (4)	C8—C7—N3—N2	179.8 (2)
C1—C2—C3—C4	−0.2 (4)	C12—C7—N3—Hg1ⁱ	159.3 (2)
C13—C2—C3—C4	179.5 (3)	C8—C7—N3—Hg1ⁱ	−21.6 (4)
C2—C3—C4—C5	−0.1 (4)	C12—C7—N3—Hg2	−169.1 (2)
C3—C4—C5—C6	0.3 (4)	C8—C7—N3—Hg2	10.1 (4)
C4—C5—C6—C1	−0.1 (4)	C12—C7—N3—Hg1	−166.4 (4)
C2—C1—C6—C5	−0.1 (4)	C8—C7—N3—Hg1	12.7 (7)
N1—C1—C6—C5	178.1 (2)	Hg1—Hg2—N3—N2	6.87 (18)
N3—C7—C8—C9	−178.6 (2)	Hg1ⁱ—Hg2—N3—N2	114.18 (16)
C12—C7—C8—C9	0.6 (4)	N1—Hg2—N3—N2	5.75 (14)
N3—C7—C8—C14	−0.7 (4)	N1ⁱ—Hg2—N3—N2	117.46 (16)
C12—C7—C8—C14	178.4 (3)	Hg1—Hg2—N3—C7	177.3 (3)
C7—C8—C9—C10	−0.2 (4)	Hg1ⁱ—Hg2—N3—C7	−75.4 (3)
C14—C8—C9—C10	−178.1 (3)	N1—Hg2—N3—C7	176.2 (3)
C8—C9—C10—C11	0.0 (4)	N1ⁱ—Hg2—N3—C7	−72.1 (3)
C9—C10—C11—C12	−0.3 (4)	N1—Hg2—N3—Hg1ⁱ	−108.43 (9)
C10—C11—C12—C7	0.7 (4)	N1ⁱ—Hg2—N3—Hg1ⁱ	3.28 (9)
N3—C7—C12—C11	178.3 (2)	Hg1ⁱ—Hg2—N3—Hg1	107.31 (8)
C8—C7—C12—C11	−0.8 (4)	N1—Hg2—N3—Hg1	−1.12 (10)
C6—C1—N1—N2	−1.5 (4)	N1ⁱ—Hg2—N3—Hg1	110.59 (11)
C2—C1—N1—N2	176.7 (2)	Hg2—Hg1—N3—N2	−173.30 (17)
C6—C1—N1—Hg1	166.1 (2)	Hg1ⁱ—Hg1—N3—N2	143.26 (16)
C2—C1—N1—Hg1	−15.7 (4)	N1—Hg1—N3—N2	5.33 (14)
C6—C1—N1—Hg2	160.0 (3)	N3ⁱ—Hg1—N3—N2	−170.43 (12)
C2—C1—N1—Hg2	−21.7 (5)	Hg2—Hg1—N3—C7	−5.0 (5)
Hg2—Hg1—N1—N2	−4.62 (19)	Hg1ⁱ—Hg1—N3—C7	−48.5 (5)
Hg1ⁱ—Hg1—N1—N2	−38.93 (18)	N1—Hg1—N3—C7	173.6 (5)
N3—Hg1—N1—N2	−5.75 (15)	N3ⁱ—Hg1—N3—C7	−2.2 (6)
Hg1ⁱ—Hg1—N1—C1	153.1 (2)	Hg2—Hg1—N3—Hg1ⁱ	43.45 (5)
N3—Hg1—N1—C1	−173.7 (3)	N1—Hg1—N3—Hg1ⁱ	−137.93 (11)
Hg1ⁱ—Hg1—N1—Hg2	−34.32 (4)	N3ⁱ—Hg1—N3—Hg1ⁱ	46.32 (14)
N3—Hg1—N1—Hg2	−1.13 (10)	Hg1ⁱ—Hg1—N3—Hg2	−43.45 (5)
Hg1—Hg2—N1—N2	175.70 (18)	N1—Hg1—N3—Hg2	178.63 (12)
Hg1ⁱ—Hg2—N1—N2	−71.89 (15)	N3ⁱ—Hg1—N3—Hg2	2.87 (14)
N3—Hg2—N1—N2	−5.63 (14)

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
C4—H4A···N4ⁱⁱ	0.95	2.61	3.428 (5)	145
C6—H6A···N5ⁱⁱⁱ	0.95	2.61	3.522 (5)	160
C10—H10A···Cg2^iv	0.95	2.96	3.629 (2)	129

Symmetry codes: (ii) x, −y, z−1/2; (iii) x, −y+1, z−1/2; (iv) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Hg(C₁₄H₈N₅)₂]
M_r	693.50
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	23.0721 (12), 7.7307 (4), 15.6680 (8)
β (°)	110.481 (1)
V (Å³)	2617.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.92
Crystal size (mm)	0.21 × 0.20 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.296, 0.629
No. of measured, independent and observed [I > 2σ(I)] reflections	15538, 3479, 2876
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.085, 0.99
No. of reflections	3479
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.67, −1.12

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···N4ⁱ	0.95	2.61	3.428 (5)	145
C6—H6A···N5ⁱⁱ	0.95	2.61	3.522 (5)	160
C10—H10A···Cg2ⁱⁱⁱ	0.95	2.96	3.629 (2)	129

Symmetry codes: (i) x, −y, z−1/2; (ii) x, −y+1, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2.

References

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Volume 65| Part 10| October 2009| Pages m1185-m1186

doi:10.1107/S1600536809035326

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