Crystal structure of di-μ-chlorido-bis­(chlorido­{N1,N1-diethyl-N4-[(pyridin-2-yl-κN)methyl­idene]benzene-1,4-di­amine-κN4}mercury(II))

Faizi, M.S.H.; Dege, N.; Goleva, K.

doi:10.1107/S2056989017005874

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 73| Part 6| June 2017| Pages 809-812

https://doi.org/10.1107/S2056989017005874

Open

access

Crystal structure of di-μ-chlorido-bis(chlorido{N¹,N¹-diethyl-N⁴-[(pyridin-2-yl-κN)methylidene]benzene-1,4-diamine-κN⁴}mercury(II))

Md. Serajul Haque Faizi,^a Necmi Dege ^b and Kateryna Goleva ^c ^*

^aDepartment of Chemistry, College of Science, Sultan Qaboos University, PO Box 36 Al-Khod 123, Muscat, Sultanate of Oman, ^bOndokuz Mayıs University, Arts and Sciences Faculty, Department of Physics, 55139 Samsun, Turkey, and ^cDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64, Vladimirska Str., Kiev 01601, Ukraine
^*Correspondence e-mail: ekaterina_goleva@list.ru

Edited by G. Smith, Queensland University of Technology, Australia (Received 18 February 2017; accepted 19 April 2017; online 5 May 2017)

The title dinuclear mercury(II) complex, [Hg₂Cl₄(C₁₆H₁₉N₃)₂], synthesized from the pyridine-derived Schiff base (E)-N¹,N¹-diethyl-N⁴-[(pyridin-2-yl)methylidene]benzene-1,4-diamine (DPMBD), has inversion symmetry. The five-coordinated Hg^II atoms have distorted square-pyramidal stereochemistry comprising two N-atom donors from bidentate chelate BPMBD ligands and three Cl-atom donors, two bridging and one monodentate. The dihedral angle between the benzene and the pyridine rings in the BPMBD ligand is 7.55 (4)°. In the crystal, the dinuclear molecules are linked by weak C—H⋯Cl hydrogen bonds, forming zigzag ribbons lying parallel to [001]. Also present in the structure are π–π interactions between benzene and pyridine rings [minimum ring-centroid separation = 3.698 (8) Å].

Keywords: crystal structure; binuclear mercury(II) complex; five-coordinated mercury(II) ions; distorted square-pyramidal coordination; DPMBD; Schiff base.

CCDC reference: 1531593

1. Chemical context

Mercury is one of the most prevalent toxic metals in the environment and gains access to the body orally or dermally, causing cell dysfunction that consequently leads to health problems (Mandal et al., 2012 ). Schiff base complexes of 2-pyridinecarboxaldehyde and its derivatives have been found to be good herbicides, used for the protection of plants (Hughes & Prince, 1978 ). Transition metal complexes of pyridyl Schiff bases have found applications in catalysis (Kasselouri et al., 1993 ). Pyridyl derivatives of Schiff bases are important building blocks for many important compounds, widely used in biological applications such as antioxidative, anticancer agents, as fluorescent probes in industry, in coordination chemistry and in catalysis (Jursic et al., 2002 ; Song et al., 2011 ; Motswainyana et al., 2013 ; Das et al., 2013 ). Our research interest focuses on a study of Schiff bases derived from N¹,N¹-diethyl-p-phenylenediamine and their metal complexes (Faizi & Hussain, 2014 ; Faizi et al., 2015 ). We report herein the synthesis and the crystal structure of a new complex of mercury(II), [Hg₂Cl₄(C₁₆H₁₉N₃)₂], with the pyridine-derived Schiff base (E)-N¹,N¹-diethyl-N⁴-[(pyridin-2-yl)methylidene]benzene-1,4-diamine (DPMBD).

2. Structural commentary

The dinuclear molecule of the title complex is generated by inversion symmetry (Fig. 1). The Schiff base-derived ligand (DPMBD) coordinates to the Hg^II atom in a bidentate chelating mode through the N atoms of the pyridine ring (N1) and the imine group (N2) [Hg1—N = 2.317 (9) and 2.437 (8) Å, respectively].

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 40% probability level. The unlabelled atoms are related to the labelled atoms by inversion symmetry (symmetry operation: −x + 2, −y + 1, −z + 1).

The five-coordinated Hg²⁺ ion has a distorted square-pyramidal geometry completed by three Hg—Cl bonds, one monodentate [Hg1—Cl2 = 2.402 (4) Å] and two bridging Hg1—Cl1 [2.459 (3) Å] and Hg1—Cl1ⁱ [2.999 (3) Å; symmetry code: (i) −x + 2, −y + 1, −z + 1]. The environment of a five-coordinated mercuric ion is common among Hg²⁺ complexes (Baul et al., 2004 ). The longest Hg—Cl distance bridges across the centre of inversion, giving an Hg⋯Hgⁱ separation of 4.1985 (16) Å. The observed Hg—Cl and Hg—N bond lengths and bond angles are considered normal for this type of Hg^II complex (Faizi & Prisyazhnaya, 2015 ; Faizi & Sen, 2014 ). The benzene and pyridine rings of the DPMBD ligand form a dihedral angle of 7.55 (4)°.

3. Supramolecular features

In the crystal, molecules are linked by C—H⋯Cl hydrogen bonds, forming a sheet like arrangement parallel to [001] (see Table 1 and Fig. 2 for details). The centroid-to-centroid distance between inversion-related benzene rings (−x + 1, −y + 2, −z + 1) is 3.879 (6) Å, indicating a weak π–π interaction along the c axis (Fig. 2). Also present is a benzene–pyridine ring interaction with Cg⋯Cg (−x + 1, −y + 1, −z + 1) = 3.698 (8) Å (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Cl1ⁱ	0.93	2.74	3.578 (9)	151
C1—H1⋯Cl1ⁱⁱ	0.93	2.89	3.471 (12)	122
C1—H1⋯Cl2ⁱⁱⁱ	0.93	2.97	3.623 (11)	129
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y+1, -z+1; (iii) -x+2, -y+2, -z+1.

Figure 2
The crystal packing of the title compound, viewed along the c axis, with hydrogen bonds (Table 1

) shown as dashed lines.

Figure 3
The crystal packing of the title compound, viewed approximately along the c axis. The π–π interactions between the benzene and pyridine rings are shown as dotted lines.

4. Database survey

A search of the Cambridge Structure Database (Version 5.37 with updates May 2016; Groom et al., 2016 ) reveals that there is no entry in the literature for a dichloridomercury(II) complex with (E)-N¹,N¹-diethyl-N4-(pyridin-2-ylmethylene)benzene-1,4-diamine that has been structurally characterized. A dihalomercury(II) complex has been reported by Baul et al. (2013 ) in which the Hg^II atom is coordinated by the bis-chelating N-heterocyclic ligand [(E)-N-(pyridin-2-ylmethylidene)arylamine)], two bridging Cl ligands and one terminal Cl ligand. Similar Hg^II complexes have also been reported with a slight modification of the ligand (Nejad et al., 2010 ), viz. di-μ-chlorido-bis{chlorido[2-(phenyliminomethyl)-pyridine-κ²N,N′]mercury(II)} (Salehzadeh et al., 2011 ) di-μ-chlorido-bis{chlorido[4-nitro-N-(pyridin-2-ylmethylidene-κN)aniline-κN]mercury(II)} (Hoseyni et al., 2012 ), di-μ-chlorido-bis{chlorido[2,3-dimethyl-N-(pyridin-2-ylmethylidene)aniline-κ²N,N′]mercury(II)} (Faizi & Prisyazhnaya, 2015) and di-μ-chlorido-bis-(chlorido{N¹-phenyl-N⁴)-[(pyridin-2-yl-κN)methylidene]benzene-1,4-diamine-κN⁴} mercury(II)). All of the above compounds show the Hg^II ion in a distorted square-pyramidal coordination environment formed by the N atoms of the diimine ligand, two bridging Cl atoms and one monodentate Cl atom, as found in the title compound, one of the bridging Hg—Cl bonds being significantly longer than the other.

5. Synthesis and crystallization

The iminopyridyl compound (E)-N¹,N¹-diethyl-N⁴-[(pyridin-2-yl)methylidene]benzene-1,4-diamine (DPMBD) was prepared by adding portionwise pyridine-2-carbaldehyde (0.29 g, 2.71 mmol) to a methanolic solution (50 ml) of N¹,N¹-diethyl-p-phenylenediamine (0.50 g, 2.71 mmol). The reaction mixture was stirred for 3 h at room temperature and filtered. The resulting yellow powder was washed with methanol (2 × 3 ml) and hexane (3 × 10 ml). The compound was recrystallized from hot MeOH to give yellow crystals, which were dried in a vacuum desiccator to give the pure product (yield: 0.60 g, 80%).

The title compound was prepared by reacting DPMBD (0.10 g, 0.39 mmol) with mercury(II) chloride (0.05 g, 0.18 mmol) in methanol (5 ml), with vigorous stirring for 2 h at room temperature. The red precipitate that formed was filtered off and redissolved in dimethylformamide. Crystals of the red title complex (yield: 0.31 g, 76%) suitable for X-ray analysis were obtained within 3 d by slow evaporation of the dimethylformamide.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms bonded to C atoms were placed in calculated positions with C—H = 0.93–0.97 Å and included in the refinement in a riding-model approximation with U_iso(H) = 1.5U_eq(C) (for methyl H) and U_iso(H) = 1.2U_eq(C) (for other H atoms).

Table 2
Experimental details

Crystal data
Chemical formula	[Hg₂Cl₄(C₁₆H₁₉N₃)₂]
M_r	1049.66
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	8.329 (3), 8.565 (3), 12.936 (4)
α, β, γ (°)	89.043 (8), 81.107 (7), 84.206 (7)
V (Å³)	907.1 (5)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	8.78
Crystal size (mm)	0.20 × 0.15 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.944, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	6272, 3303, 2779
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.156, 1.06
No. of reflections	3303
No. of parameters	158
No. of restraints	57
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.56, −2.43
Computer programs: APEX2 and SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and DIAMOND (Brandenburg & Putz, 2006 ).

Supporting information

CCDC reference: 1531593

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017005874/zs2377sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017005874/zs2377Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenberg & Putz, 2006); software used to prepare material for publication: DIAMOND (Brandenberg & Putz, 2006).

Di-µ-chlorido-bis(chlorido{N¹,N¹-diethyl-N⁴-[(pyridin-2-yl-κN)methylidene]benzene-1,4-diamine-κN⁴}mercury(II)) top

Crystal data top

[Hg₂Cl₄(C₁₆H₁₉N₃)₂]	Z = 1
M_r = 1049.66	F(000) = 500
Triclinic, P1	D_x = 1.921 Mg m⁻³
a = 8.329 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.565 (3) Å	Cell parameters from 3407 reflections
c = 12.936 (4) Å	θ = 2.7–26.6°
α = 89.043 (8)°	µ = 8.78 mm⁻¹
β = 81.107 (7)°	T = 100 K
γ = 84.206 (7)°	Needle, red
V = 907.1 (5) Å³	0.20 × 0.15 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	3303 independent reflections
Radiation source: sealed tube	2779 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
φ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→10
T_min = 0.944, T_max = 0.981	k = −7→10
6272 measured reflections	l = −15→15

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.054	w = 1/[σ²(F_o²) + (0.0936P)² + 2.7873P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.156	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 2.56 e Å⁻³
3303 reflections	Δρ_min = −2.43 e Å⁻³
158 parameters	Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
57 restraints	Extinction coefficient: 0.0154 (18)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Hg1	0.81436 (5)	0.66012 (4)	0.57709 (3)	0.0580 (3)
Cl1	0.8912 (3)	0.3764 (3)	0.5896 (2)	0.0565 (6)
Cl2	0.8896 (4)	0.8431 (4)	0.6955 (3)	0.0756 (8)
N2	0.5206 (9)	0.6438 (8)	0.5996 (6)	0.0418 (16)
N1	0.7065 (10)	0.8114 (9)	0.4494 (7)	0.0486 (18)
C5	0.5464 (11)	0.8065 (10)	0.4459 (7)	0.0425 (19)
C7	0.4285 (19)	0.564 (2)	0.6811 (12)	0.0965 (13)
C6	0.4541 (11)	0.7127 (10)	0.5239 (7)	0.045 (2)
H6	0.345407	0.701618	0.519674	0.054*
C4	0.4711 (14)	0.8919 (12)	0.3733 (8)	0.054 (2)
H4	0.361040	0.884616	0.371099	0.064*
C8	0.2645 (12)	0.5445 (14)	0.6857 (8)	0.060 (3)
H8	0.207736	0.588526	0.634069	0.072*
C2	0.7167 (15)	0.9953 (13)	0.3116 (9)	0.062 (3)
H2	0.776639	1.064049	0.268772	0.075*
C10	0.266 (2)	0.389 (2)	0.8458 (13)	0.1012 (7)
C1	0.7883 (14)	0.9042 (13)	0.3803 (10)	0.062 (3)
H1	0.899938	0.905612	0.379875	0.075*
C12	0.505 (2)	0.498 (2)	0.7587 (12)	0.1012 (7)
H12	0.613677	0.512565	0.760116	0.121*
N3	0.1794 (12)	0.3036 (16)	0.9288 (8)	0.1012 (9)
C3	0.5551 (16)	0.9872 (13)	0.3044 (9)	0.063 (3)
H3	0.505047	1.044522	0.254433	0.075*
C9	0.186 (2)	0.462 (2)	0.7646 (13)	0.1012 (7)
H9	0.075706	0.452541	0.766178	0.121*
C11	0.424 (2)	0.409 (2)	0.8348 (13)	0.1012 (7)
H11	0.484613	0.359696	0.882884	0.121*
C15	0.2584 (16)	0.2780 (17)	1.0150 (10)	0.1012 (7)
H15A	0.182347	0.272105	1.079438	0.121*
H15B	0.331868	0.357020	1.021477	0.121*
C16	0.3500 (18)	0.1193 (16)	0.9831 (12)	0.1012 (7)
H16A	0.413710	0.082530	1.036072	0.152*
H16B	0.273224	0.045619	0.975182	0.152*
H16C	0.420937	0.129507	0.917922	0.152*
C13	0.0131 (13)	0.3113 (19)	0.9350 (12)	0.1012 (7)
H13A	−0.023986	0.413409	0.909047	0.121*
H13B	−0.033164	0.307139	1.008496	0.121*
C14	−0.059 (2)	0.1883 (19)	0.8782 (12)	0.1012 (7)
H14A	−0.176271	0.208254	0.889439	0.152*
H14B	−0.019235	0.192811	0.804657	0.152*
H14C	−0.028458	0.086028	0.904586	0.152*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.0436 (3)	0.0551 (3)	0.0792 (4)	−0.00681 (18)	−0.0217 (2)	0.0087 (2)
Cl1	0.0404 (12)	0.0548 (13)	0.0761 (16)	−0.0047 (10)	−0.0161 (11)	0.0139 (11)
Cl2	0.0711 (19)	0.0739 (18)	0.089 (2)	−0.0146 (15)	−0.0278 (16)	−0.0072 (15)
N2	0.039 (4)	0.037 (4)	0.052 (4)	−0.007 (3)	−0.010 (3)	0.000 (3)
N1	0.042 (4)	0.041 (4)	0.065 (5)	−0.007 (3)	−0.012 (4)	−0.004 (3)
C5	0.040 (5)	0.039 (4)	0.049 (5)	−0.001 (4)	−0.012 (4)	−0.010 (4)
C7	0.080 (2)	0.124 (2)	0.089 (2)	−0.025 (2)	−0.018 (2)	0.032 (2)
C6	0.039 (5)	0.042 (4)	0.057 (5)	−0.005 (4)	−0.018 (4)	−0.007 (4)
C4	0.056 (6)	0.054 (6)	0.053 (5)	0.000 (5)	−0.022 (5)	0.002 (4)
C8	0.038 (5)	0.087 (8)	0.058 (6)	−0.011 (5)	−0.012 (4)	0.020 (5)
C2	0.073 (8)	0.052 (6)	0.060 (6)	−0.010 (5)	−0.003 (5)	0.007 (5)
C10	0.0849 (13)	0.1288 (13)	0.0928 (13)	−0.0231 (13)	−0.0184 (12)	0.0329 (13)
C1	0.046 (6)	0.056 (6)	0.083 (7)	−0.009 (5)	−0.005 (5)	0.009 (5)
C12	0.0849 (13)	0.1288 (13)	0.0928 (13)	−0.0231 (13)	−0.0184 (12)	0.0329 (13)
N3	0.0848 (16)	0.1290 (17)	0.0927 (15)	−0.0230 (16)	−0.0183 (15)	0.0330 (16)
C3	0.077 (8)	0.049 (5)	0.064 (6)	0.003 (5)	−0.018 (6)	0.002 (5)
C9	0.0849 (13)	0.1288 (13)	0.0928 (13)	−0.0231 (13)	−0.0184 (12)	0.0329 (13)
C11	0.0849 (13)	0.1288 (13)	0.0928 (13)	−0.0231 (13)	−0.0184 (12)	0.0329 (13)
C15	0.0849 (13)	0.1288 (13)	0.0928 (13)	−0.0231 (13)	−0.0184 (12)	0.0329 (13)
C16	0.0849 (13)	0.1288 (13)	0.0928 (13)	−0.0231 (13)	−0.0184 (12)	0.0329 (13)
C13	0.0849 (13)	0.1288 (13)	0.0928 (13)	−0.0231 (13)	−0.0184 (12)	0.0329 (13)
C14	0.0849 (13)	0.1288 (13)	0.0928 (13)	−0.0231 (13)	−0.0184 (12)	0.0329 (13)

Geometric parameters (Å, º) top

Hg1—Cl1	2.459 (3)	C11—C12	1.37 (2)
Hg1—Cl2	2.402 (4)	C13—C14	1.52 (2)
Hg1—N1	2.317 (9)	C15—C16	1.52 (2)
Hg1—N2	2.437 (8)	C1—H1	0.9300
Hg1—Cl1ⁱ	2.999 (3)	C2—H2	0.9300
N1—C1	1.339 (15)	C3—H3	0.9300
N1—C5	1.346 (13)	C4—H4	0.9300
N2—C6	1.302 (12)	C6—H6	0.9300
N2—C7	1.414 (18)	C8—H8	0.9300
N3—C10	1.43 (2)	C9—H9	0.9300
N3—C13	1.370 (15)	C11—H11	0.9300
N3—C15	1.384 (17)	C12—H12	0.9300
C1—C2	1.342 (17)	C13—H13A	0.9700
C2—C3	1.372 (19)	C13—H13B	0.9700
C3—C4	1.360 (16)	C14—H14A	0.9600
C4—C5	1.370 (14)	C14—H14B	0.9600
C5—C6	1.453 (13)	C14—H14C	0.9600
C7—C8	1.385 (19)	C15—H15A	0.9700
C7—C12	1.36 (2)	C15—H15B	0.9700
C8—C9	1.35 (2)	C16—H16A	0.9600
C9—C10	1.43 (2)	C16—H16B	0.9600
C10—C11	1.33 (2)	C16—H16C	0.9600

Cl1—Hg1—Cl2	121.69 (10)	N1—C1—H1	118.00
Cl1—Hg1—N1	131.9 (2)	C2—C1—H1	118.00
Cl1—Hg1—N2	96.06 (17)	C1—C2—H2	120.00
Cl1—Hg1—Cl1ⁱ	79.90 (8)	C3—C2—H2	120.00
Cl2—Hg1—N1	105.7 (2)	C2—C3—H3	121.00
Cl2—Hg1—N2	112.60 (19)	C4—C3—H3	121.00
Cl1ⁱ—Hg1—Cl2	102.68 (10)	C3—C4—H4	120.00
N1—Hg1—N2	71.2 (3)	C5—C4—H4	120.00
Cl1ⁱ—Hg1—N1	82.2 (2)	N2—C6—H6	119.00
Cl1ⁱ—Hg1—N2	140.17 (19)	C5—C6—H6	119.00
Hg1—Cl1—Hg1ⁱ	100.10 (8)	C7—C8—H8	120.00
Hg1—N1—C1	125.9 (7)	C9—C8—H8	120.00
Hg1—N1—C5	116.6 (6)	C8—C9—H9	119.00
C1—N1—C5	117.5 (9)	C10—C9—H9	119.00
Hg1—N2—C6	112.2 (6)	C10—C11—H11	118.00
Hg1—N2—C7	125.9 (8)	C12—C11—H11	117.00
C6—N2—C7	121.8 (10)	C7—C12—H12	120.00
C10—N3—C13	117.2 (12)	C11—C12—H12	120.00
C10—N3—C15	114.4 (11)	N3—C13—H13A	108.00
C13—N3—C15	123.0 (11)	N3—C13—H13B	108.00
N1—C1—C2	123.0 (11)	C14—C13—H13A	108.00
C1—C2—C3	120.1 (11)	C14—C13—H13B	108.00
C2—C3—C4	117.3 (11)	H13A—C13—H13B	107.00
C3—C4—C5	120.9 (11)	C13—C14—H14A	109.00
N1—C5—C4	121.0 (9)	C13—C14—H14B	110.00
N1—C5—C6	118.1 (8)	C13—C14—H14C	110.00
C4—C5—C6	120.8 (9)	H14A—C14—H14B	109.00
N2—C6—C5	121.3 (8)	H14A—C14—H14C	109.00
N2—C7—C8	124.1 (13)	H14B—C14—H14C	110.00
N2—C7—C12	118.6 (14)	N3—C15—H15A	112.00
C8—C7—C12	117.2 (14)	N3—C15—H15B	112.00
C7—C8—C9	120.6 (12)	C16—C15—H15A	112.00
C8—C9—C10	122.8 (15)	C16—C15—H15B	112.00
N3—C10—C9	121.5 (14)	H15A—C15—H15B	110.00
N3—C10—C11	125.2 (15)	C15—C16—H16A	109.00
C9—C10—C11	113.3 (15)	C15—C16—H16B	109.00
C10—C11—C12	125.2 (16)	C15—C16—H16C	109.00
C7—C12—C11	120.7 (16)	H16A—C16—H16B	109.00
N3—C13—C14	118.6 (13)	H16A—C16—H16C	109.00
N3—C15—C16	98.2 (11)	H16B—C16—H16C	109.00

Cl2—Hg1—Cl1—Hg1ⁱ	−98.74 (12)	C7—N2—C6—C5	174.3 (10)
N1—Hg1—Cl1—Hg1ⁱ	69.9 (3)	Hg1—N2—C7—C8	−173.5 (10)
N2—Hg1—Cl1—Hg1ⁱ	139.95 (19)	Hg1—N2—C7—C12	4.6 (19)
Cl1ⁱ—Hg1—Cl1—Hg1ⁱ	0.00 (7)	C6—N2—C7—C8	3 (2)
Cl1—Hg1—N1—C1	−104.6 (8)	C6—N2—C7—C12	−178.5 (12)
Cl1—Hg1—N1—C5	76.4 (7)	C13—N3—C10—C9	−8 (2)
Cl2—Hg1—N1—C1	65.4 (9)	C13—N3—C10—C11	172.1 (16)
Cl2—Hg1—N1—C5	−113.6 (6)	C15—N3—C10—C9	−162.9 (15)
N2—Hg1—N1—C1	174.4 (9)	C15—N3—C10—C11	17 (2)
N2—Hg1—N1—C5	−4.6 (6)	C10—N3—C13—C14	91.1 (18)
Cl1ⁱ—Hg1—N1—C1	−35.7 (8)	C15—N3—C13—C14	−116.5 (16)
Cl1ⁱ—Hg1—N1—C5	145.3 (7)	C10—N3—C15—C16	−92.0 (14)
Cl1—Hg1—N2—C6	−125.6 (6)	C13—N3—C15—C16	114.9 (15)
Cl1—Hg1—N2—C7	51.6 (10)	N1—C1—C2—C3	−5.1 (18)
Cl2—Hg1—N2—C6	106.4 (6)	C1—C2—C3—C4	4.0 (17)
Cl2—Hg1—N2—C7	−76.5 (10)	C2—C3—C4—C5	−0.7 (16)
N1—Hg1—N2—C6	6.7 (6)	C3—C4—C5—N1	−1.7 (15)
N1—Hg1—N2—C7	−176.1 (10)	C3—C4—C5—C6	175.9 (9)
Cl1ⁱ—Hg1—N2—C6	−44.1 (7)	N1—C5—C6—N2	4.7 (13)
Cl1ⁱ—Hg1—N2—C7	133.1 (9)	C4—C5—C6—N2	−173.0 (9)
Cl1—Hg1—Cl1ⁱ—Hg1ⁱ	0.00 (9)	N2—C7—C8—C9	177.8 (14)
Cl2—Hg1—Cl1ⁱ—Hg1ⁱ	120.45 (11)	C12—C7—C8—C9	0 (2)
N1—Hg1—Cl1ⁱ—Hg1ⁱ	−135.1 (2)	N2—C7—C12—C11	−174.8 (14)
N2—Hg1—Cl1ⁱ—Hg1ⁱ	−87.4 (3)	C8—C7—C12—C11	3 (2)
Hg1—N1—C1—C2	−176.5 (9)	C7—C8—C9—C10	−1 (2)
C5—N1—C1—C2	2.6 (16)	C8—C9—C10—N3	179.4 (14)
Hg1—N1—C5—C4	179.9 (7)	C8—C9—C10—C11	−1 (2)
Hg1—N1—C5—C6	2.3 (10)	N3—C10—C11—C12	−176.2 (16)
C1—N1—C5—C4	0.8 (14)	C9—C10—C11—C12	4 (3)
C1—N1—C5—C6	−176.9 (9)	C10—C11—C12—C7	−6 (3)
Hg1—N2—C6—C5	−8.5 (10)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cl1ⁱⁱ	0.93	2.74	3.578 (9)	151
C1—H1···Cl1ⁱ	0.93	2.89	3.471 (12)	122
C1—H1···Cl2ⁱⁱⁱ	0.93	2.97	3.623 (11)	129

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

Acknowledgements

The authors are grateful to the Department of Chemistry, Taras Shevchenko National University of Kyiv, 64, Vladimirska Str., Kiev 01601, Ukraine, for financial support and Dr Igor Fritsky for important discussions.

References

Baul, T. S. B., Kundu, S., Mitra, S., Höpfl, H., Tiekink, E. R. T. & Lindend, A. (2013). Dalton Trans. 42, 1905–1920. PubMed Google Scholar
Baul, T. S. B., Lycka, A., Butcher, R. & Smith, E. F. (2004). Polyhedron, 23, 2323–2329. Google Scholar
Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2003). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Das, P., Mandal, A. K., Reddy, G. U., Baidya, M., Ghosh, S. K. & Das, A. (2013). Org. Biomol. Chem. 11, 6604–6614. Web of Science CrossRef CAS PubMed Google Scholar
Faizi, M. S. H. & Hussain, S. (2014). Acta Cryst. E70, m197. CSD CrossRef IUCr Journals Google Scholar
Faizi, M. S. H. & Prisyazhnaya, E. V. (2015). Acta Cryst. E71, m175–m176. Web of Science CSD CrossRef IUCr Journals Google Scholar
Faizi, M. S. H. & Sen, P. (2014). Acta Cryst. E70, m173. CSD CrossRef IUCr Journals Google Scholar
Faizi, M. S. H., Siddiqui, N. & Javed, S. (2015). Acta Cryst. E71, o49–o50. Web of Science CSD CrossRef IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hoseyni, S. J., Talei Bavil Olyai, M. R. & Notash, B. (2012). Acta Cryst. E68, m1294. CSD CrossRef IUCr Journals Google Scholar
Hughes, M. & Prince, R. H. (1978). J. Inorg. Nucl. Chem. 40, 719–723. CrossRef CAS Web of Science Google Scholar
Jursic, B. S., Douelle, F., Bowdy, K. & Stevens, E. D. (2002). Tetrahedron Lett. 43, 5361–5365. Web of Science CSD CrossRef CAS Google Scholar
Kasselouri, S., Garoufis, G., Kalkanis, A., Perlepes, S. P. & Hadjiliadis, N. (1993). Transition Met. Chem. 18, 531–536. CrossRef CAS Web of Science Google Scholar
Mandal, A. K., Suresh, M., Das, P., Suresh, E., Baidya, M., Ghosh, S. K. & Das, A. (2012). Org. Lett. 14, 2980–2983. Web of Science CSD CrossRef CAS PubMed Google Scholar
Motswainyana, W. M., Onani, M. O., Madiehe, A. M., Saibu, M., Jacobs, J. & van Meervelt, L. (2013). Inorg. Chim. Acta, 400, 197–202. Web of Science CSD CrossRef CAS Google Scholar
Nejad, M. F., Olyai, M. R. T. B. & Khavasi, H. R. (2010). Z. Kristallogr. New Cryst. Struct. 225, 717–718. CAS Google Scholar
Salehzadeh, S., Dehghanpour, S., Khalaj, M. & Rahimishakiba, M. (2011). Acta Cryst. E67, m327. 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
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Song, S., Zhao, W., Wang, L., Redshaw, C., Wang, F. & Sun, W.-H. (2011). J. Organomet. Chem. 696, 3029–3035. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.