catena-Poly[[dichloridomercury(II)]-N′-nicotinoylnicotinohydrazide]

Ma, T.; Wang, Y.; Wang, F.; Li, F.

doi:10.1107/S1600536812008884

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m367

doi:10.1107/S1600536812008884

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catena-Poly[[dichloridomercury(II)]-N′-nicotinoylnicotinohydrazide]

Teng Ma,^a Yuanlu Wang,^a Fengliang Wang ^a and Fei Li ^a ^*

^aCollege of Pharmacy, Nanjing Medical University, Nanjing 210029, People's Republic of China
^*Correspondence e-mail: nanjinglf@gmail.com

(Received 17 February 2012; accepted 28 February 2012; online 3 March 2012)

The title complex, [HgCl₂(C₁₂H₁₀N₄O₂)]_n, is composed of one Hg^II ion, one nnh ligand (nnh = N′-nicotinoylnicotinohydrazide) and two coordinated chloride ions. The Hg^II ion shows a distorted tetrahedral geometry, being surrounded by two N atoms from two nnh ligands and two chloride ions. Due to the bridging role of nnh, the Hg^II atoms are connected into polymeric chains along the c axis, which are further interlinked via N—H⋯O and C—H⋯Cl hydrogen-bonding interactions, forming a three-dimensional network.

Related literature

For the coordination systems of N-donor heterocyclic groups, see: Zhang & Chen (2010 ); Ma et al. (2005 ); Tao et al. (2010 ).

Experimental

Crystal data

[HgCl₂(C₁₂H₁₀N₄O₂)]
M_r = 513.73
Monoclinic, P 2/c
a = 7.2514 (4) Å
b = 4.7113 (3) Å
c = 21.8591 (11) Å
β = 103.394 (2)°
V = 726.47 (7) Å³
Z = 2
Mo Kα radiation
μ = 10.97 mm⁻¹
T = 296 K
0.30 × 0.26 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.137, T_max = 0.196
3510 measured reflections
1288 independent reflections
1244 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.038
S = 1.09
1288 reflections
96 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl1ⁱ	0.93	2.81	3.558 (4)	138
N2—H2A⋯O1ⁱⁱ	0.86	2.15	2.844 (3)	137
Symmetry codes: (i) x-1, y-1, z; (ii) x, y+1, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812008884/hp2029sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008884/hp2029Isup2.hkl

checkCIF report

Comment top

Flexible ligands containing N-donor heterocyclic groups, such as pyridyl, pyrazinyl, and triazolyl (see: Zhang et al., 2010; Ma et al., 2005; Tao et al., 2010), have been widely studied in the realm of metal-organic coordination assemblies. With regard to this, N'-nicotinoylnicotinohydrazide (nnh), an interesting ligand with flexible spacer and multiple binding sites, has attract our attention. Herein, we report the title complex [Hg(nnh)Cl₂]_n, which crystallizes in the monoclinic space group P2/c, and shows a one-dimensional polymeric array and H-bonding supramolecular network.

As shown in Fig.1, the asymmetric unit of the complex is provided by a Hg^II center, one nnh ligand and two chloride ions. The Hg^II ion is tetra-coordinated to two nitrogen atoms from two nnh ligands with the Hg—N distance of 2.475 (2) Å, as well as two chloride ions with the Hg—Cl distance of 2.3405 (9) Å. The adjacent Hg centers are bridged by the nnh ligands to afford a one-dimensional zigzag chain with the Hg···Hg separation of ca 12.8371 (6) Å (see Fig. 2).

Notably, H-bonding interactions do play a decisive role in the crystal packing arrangement. As shown in Fig. 3, the adjacent one-dimensional arrays are linked to form a two-dimensional layer via N2—H2A···O2ⁱ [symmetry operation (i) = x, 1 + y, z] hydrogen bonding between the nnh ligands from different chains. Furthermore, such two-dimensional layers are interlinked by the weak hydrogen bonds C3—H3···Clⁱⁱ [symmetry operation (ii) = -1 + x, -1 + y, z] to generate a three-dimensional supramolecular network (see Fig. 4).

Related literature top

For the coordination systems of N-donor heterocyclic groups, see: Zhang & Chen (2010); Ma et al. (2005); Tao et al. (2010).

Experimental top

A CH₃OH solution (10 ml) of nnh (24.2 mg, 0.1 mmol) was carefully layered onto an aqueous solution of HgCl₂ (27.1 mg, 0.1 mmol) in a straight glass tube. After evaporating the solvents slowly for ca one month, suitable yellow block single crystals for X-ray analysis were produced.

Structure description top

For the coordination systems of N-donor heterocyclic groups, see: Zhang & Chen (2010); Ma et al. (2005); Tao et al. (2010).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Coordination environment of Hg^II in the title complex showing displacement ellipsoids for all non-H atoms drawn at the 30% probability level. [Symmetry code (A): 1 - x, y, 3/2 - z.].
	Fig. 2. View of the one-dimensional chain.
	Fig. 3. View of the two-dimensional layer via N–H···O hydrogen bonds (red dashed lines).
	Fig. 4. View of the three-dimensional network via C–H···Cl hydrogen bonds (green dashed lines).

catena-Poly[[dichloridomercury(II)]-N'- nicotinoylnicotinohydrazide] top

Crystal data top

[HgCl₂(C₁₂H₁₀N₄O₂)]	F(000) = 480
M_r = 513.73	D_x = 2.349 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 2648 reflections
a = 7.2514 (4) Å	θ = 2.9–27.9°
b = 4.7113 (3) Å	µ = 10.97 mm⁻¹
c = 21.8591 (11) Å	T = 296 K
β = 103.394 (2)°	BLOCK, yellow
V = 726.47 (7) Å³	0.30 × 0.26 × 0.22 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1288 independent reflections
Radiation source: fine-focus sealed tube	1244 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.137, T_max = 0.196	k = −5→5
3510 measured reflections	l = −14→26

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)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.038	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0224P)² + 0.0147P] where P = (F_o² + 2F_c²)/3
1288 reflections	(Δ/σ)_max = 0.001
96 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

[HgCl₂(C₁₂H₁₀N₄O₂)]	V = 726.47 (7) Å³
M_r = 513.73	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 7.2514 (4) Å	µ = 10.97 mm⁻¹
b = 4.7113 (3) Å	T = 296 K
c = 21.8591 (11) Å	0.30 × 0.26 × 0.22 mm
β = 103.394 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1288 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1244 reflections with I > 2σ(I)
T_min = 0.137, T_max = 0.196	R_int = 0.018
3510 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	0 restraints
wR(F²) = 0.038	H-atom parameters constrained
S = 1.09	Δρ_max = 0.52 e Å⁻³
1288 reflections	Δρ_min = −0.57 e Å⁻³
96 parameters

Special details top

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
Hg1	0.5000	1.07616 (3)	0.7500	0.03638 (8)
Cl1	0.81805 (12)	1.1749 (2)	0.79628 (5)	0.0524 (2)
O1	0.7884 (3)	0.1092 (4)	0.98476 (12)	0.0385 (5)
N1	0.4508 (3)	0.7488 (5)	0.83334 (12)	0.0348 (6)
N2	0.9166 (4)	0.5412 (5)	0.97954 (13)	0.0293 (6)
H2A	0.9048	0.7096	0.9639	0.035*
C1	0.6042 (4)	0.6598 (6)	0.87486 (15)	0.0305 (6)
H1	0.7211	0.7361	0.8730	0.037*
C2	0.2825 (5)	0.6416 (8)	0.83653 (16)	0.0405 (8)
H2	0.1741	0.7054	0.8082	0.049*
C3	0.2644 (5)	0.4401 (7)	0.88032 (18)	0.0423 (8)
H3	0.1454	0.3698	0.8815	0.051*
C4	0.4239 (4)	0.3429 (7)	0.92245 (15)	0.0345 (7)
H4	0.4146	0.2023	0.9514	0.041*
C5	0.5987 (4)	0.4593 (6)	0.92072 (15)	0.0267 (6)
C6	0.7733 (4)	0.3541 (6)	0.96446 (14)	0.0264 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.03059 (11)	0.04571 (12)	0.02898 (11)	0.000	−0.00099 (8)	0.000
Cl1	0.0347 (4)	0.0712 (6)	0.0475 (5)	−0.0132 (4)	0.0020 (4)	−0.0076 (5)
O1	0.0319 (12)	0.0234 (10)	0.0553 (15)	0.0000 (8)	0.0000 (11)	0.0057 (9)
N1	0.0289 (13)	0.0411 (14)	0.0303 (14)	0.0040 (11)	−0.0016 (11)	−0.0001 (12)
N2	0.0235 (12)	0.0220 (11)	0.0361 (15)	−0.0008 (9)	−0.0057 (11)	0.0066 (10)
C1	0.0271 (15)	0.0304 (14)	0.0316 (16)	−0.0018 (12)	0.0017 (13)	−0.0014 (13)
C2	0.0293 (17)	0.0529 (18)	0.0331 (18)	0.0022 (14)	−0.0053 (15)	−0.0012 (15)
C3	0.0234 (17)	0.058 (2)	0.042 (2)	−0.0087 (14)	0.0019 (15)	−0.0062 (16)
C4	0.0292 (17)	0.0387 (15)	0.0339 (17)	−0.0052 (13)	0.0041 (14)	−0.0009 (14)
C5	0.0254 (15)	0.0255 (13)	0.0279 (16)	−0.0010 (11)	0.0032 (13)	−0.0054 (12)
C6	0.0251 (15)	0.0239 (13)	0.0295 (16)	0.0008 (11)	0.0051 (13)	−0.0018 (12)

Geometric parameters (Å, º) top

Hg1—Cl1	2.3405 (9)	C1—C5	1.385 (5)
Hg1—Cl1ⁱ	2.3405 (9)	C1—H1	0.9300
Hg1—N1ⁱ	2.475 (2)	C2—C3	1.376 (5)
Hg1—N1	2.475 (2)	C2—H2	0.9300
O1—C6	1.232 (3)	C3—C4	1.379 (5)
N1—C1	1.330 (4)	C3—H3	0.9300
N1—C2	1.338 (4)	C4—C5	1.390 (4)
N2—C6	1.344 (4)	C4—H4	0.9300
N2—N2ⁱⁱ	1.383 (5)	C5—C6	1.484 (4)
N2—H2A	0.8601

Cl1—Hg1—Cl1ⁱ	157.08 (6)	N1—C2—C3	122.1 (3)
Cl1—Hg1—N1ⁱ	98.41 (6)	N1—C2—H2	118.9
Cl1ⁱ—Hg1—N1ⁱ	95.81 (6)	C3—C2—H2	118.9
Cl1—Hg1—N1	95.81 (6)	C2—C3—C4	119.6 (3)
Cl1ⁱ—Hg1—N1	98.41 (6)	C2—C3—H3	120.2
N1ⁱ—Hg1—N1	102.92 (11)	C4—C3—H3	120.2
C1—N1—C2	118.3 (3)	C3—C4—C5	118.7 (3)
C1—N1—Hg1	117.28 (19)	C3—C4—H4	120.7
C2—N1—Hg1	124.2 (2)	C5—C4—H4	120.7
C6—N2—N2ⁱⁱ	119.0 (3)	C1—C5—C4	117.9 (3)
C6—N2—H2A	120.5	C1—C5—C6	122.1 (3)
N2ⁱⁱ—N2—H2A	120.5	C4—C5—C6	119.9 (3)
N1—C1—C5	123.3 (3)	O1—C6—N2	121.8 (3)
N1—C1—H1	118.3	O1—C6—C5	122.4 (3)
C5—C1—H1	118.3	N2—C6—C5	115.8 (2)

Cl1—Hg1—N1—C1	−12.5 (2)	C2—C3—C4—C5	2.1 (5)
Cl1ⁱ—Hg1—N1—C1	−174.5 (2)	N1—C1—C5—C4	1.1 (5)
N1ⁱ—Hg1—N1—C1	87.6 (2)	N1—C1—C5—C6	177.0 (3)
Cl1—Hg1—N1—C2	172.4 (2)	C3—C4—C5—C1	−2.5 (5)
Cl1ⁱ—Hg1—N1—C2	10.4 (3)	C3—C4—C5—C6	−178.5 (3)
N1ⁱ—Hg1—N1—C2	−87.6 (3)	N2ⁱⁱ—N2—C6—O1	−2.0 (5)
C2—N1—C1—C5	0.8 (5)	N2ⁱⁱ—N2—C6—C5	179.5 (3)
Hg1—N1—C1—C5	−174.6 (2)	C1—C5—C6—O1	−147.0 (3)
C1—N1—C2—C3	−1.3 (5)	C4—C5—C6—O1	28.8 (4)
Hg1—N1—C2—C3	173.8 (3)	C1—C5—C6—N2	31.5 (4)
N1—C2—C3—C4	−0.2 (5)	C4—C5—C6—N2	−152.7 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱⁱⁱ	0.93	2.81	3.558 (4)	138
N2—H2A···O1^iv	0.86	2.15	2.844 (3)	137

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

Experimental details

Crystal data
Chemical formula	[HgCl₂(C₁₂H₁₀N₄O₂)]
M_r	513.73
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	296
a, b, c (Å)	7.2514 (4), 4.7113 (3), 21.8591 (11)
β (°)	103.394 (2)
V (Å³)	726.47 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	10.97
Crystal size (mm)	0.30 × 0.26 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.137, 0.196
No. of measured, independent and observed [I > 2σ(I)] reflections	3510, 1288, 1244
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.038, 1.09
No. of reflections	1288
No. of parameters	96
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.57

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱ	0.93	2.81	3.558 (4)	138.1
N2—H2A···O1ⁱⁱ	0.86	2.15	2.844 (3)	136.9

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

Acknowledgements

We acknowledge the staff of the Shanghai Institute of Materia Medica for their active cooperation in this work. We also thank the Instrument Analysis and Research Center of Nanjing University for the structural characterization.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ma, B.-Q., Mulfort, K. L. & Hupp, J. T. (2005). Inorg. Chem. 44, 4912–4914. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tao, Y., Li, J.-R., Chang, Z. & Bu, X.-H. (2010). Cryst. Growth Des. 10, 564–574. Web of Science CrossRef CAS Google Scholar
Zhang, S.-S. & Chen, L.-J. (2010). Acta Cryst. E66, m1456. Web of Science CSD CrossRef IUCr Journals Google Scholar