metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 HgII ion, one nnh ligand (nnh = N′-nicotinoylnicotinohydrazide) and two coordinated chloride ions. The HgII 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 HgII 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[Zhang, S.-S. & Chen, L.-J. (2010). Acta Cryst. E66, m1456.]); Ma et al. (2005[Ma, B.-Q., Mulfort, K. L. & Hupp, J. T. (2005). Inorg. Chem. 44, 4912-4914.]); Tao et al. (2010[Tao, Y., Li, J.-R., Chang, Z. & Bu, X.-H. (2010). Cryst. Growth Des. 10, 564-574.]).

[Scheme 1]

Experimental

Crystal data
  • [HgCl2(C12H10N4O2)]

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.137, Tmax = 0.196

  • 3510 measured reflections

  • 1288 independent reflections

  • 1244 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.016

  • wR(F2) = 0.038

  • S = 1.09

  • 1288 reflections

  • 96 parameters

  • H-atom parameters constrained

  • Δρmax = 0.52 e Å−3

  • Δρmin = −0.57 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


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 HgII center, one nnh ligand and two chloride ions. The HgII 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.

Refinement top

All H atoms were initially located in a difference Fourier map, which were then constrained to an ideal geometry, and refined as riding atoms: C—H = 0.93 (CHaromatic) and N—H = 0.86, with Uiso(H) = 1.2Ueq (C) and Uiso(H) = 1.5Ueq (N).

Structure description 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 HgII center, one nnh ligand and two chloride ions. The HgII 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).

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
[Figure 1] Fig. 1. Coordination environment of HgII 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.].
[Figure 2] Fig. 2. View of the one-dimensional chain.
[Figure 3] Fig. 3. View of the two-dimensional layer via N–H···O hydrogen bonds (red dashed lines).
[Figure 4] 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
Mr = 513.73Dx = 2.349 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 2648 reflections
a = 7.2514 (4) Åθ = 2.9–27.9°
b = 4.7113 (3) ŵ = 10.97 mm1
c = 21.8591 (11) ÅT = 296 K
β = 103.394 (2)°BLOCK, yellow
V = 726.47 (7) Å30.30 × 0.26 × 0.22 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
1288 independent reflections
Radiation source: fine-focus sealed tube1244 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
phi and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.137, Tmax = 0.196k = 55
3510 measured reflectionsl = 1426
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.016Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.038H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0224P)2 + 0.0147P]
where P = (Fo2 + 2Fc2)/3
1288 reflections(Δ/σ)max = 0.001
96 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.57 e Å3
Crystal data top
[HgCl2(C12H10N4O2)]V = 726.47 (7) Å3
Mr = 513.73Z = 2
Monoclinic, P2/cMo Kα radiation
a = 7.2514 (4) ŵ = 10.97 mm1
b = 4.7113 (3) ÅT = 296 K
c = 21.8591 (11) Å0.30 × 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)
Tmin = 0.137, Tmax = 0.196Rint = 0.018
3510 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0160 restraints
wR(F2) = 0.038H-atom parameters constrained
S = 1.09Δρmax = 0.52 e Å3
1288 reflectionsΔρmin = 0.57 e Å3
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
xyzUiso*/Ueq
Hg10.50001.07616 (3)0.75000.03638 (8)
Cl10.81805 (12)1.1749 (2)0.79628 (5)0.0524 (2)
O10.7884 (3)0.1092 (4)0.98476 (12)0.0385 (5)
N10.4508 (3)0.7488 (5)0.83334 (12)0.0348 (6)
N20.9166 (4)0.5412 (5)0.97954 (13)0.0293 (6)
H2A0.90480.70960.96390.035*
C10.6042 (4)0.6598 (6)0.87486 (15)0.0305 (6)
H10.72110.73610.87300.037*
C20.2825 (5)0.6416 (8)0.83653 (16)0.0405 (8)
H20.17410.70540.80820.049*
C30.2644 (5)0.4401 (7)0.88032 (18)0.0423 (8)
H30.14540.36980.88150.051*
C40.4239 (4)0.3429 (7)0.92245 (15)0.0345 (7)
H40.41460.20230.95140.041*
C50.5987 (4)0.4593 (6)0.92072 (15)0.0267 (6)
C60.7733 (4)0.3541 (6)0.96446 (14)0.0264 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.03059 (11)0.04571 (12)0.02898 (11)0.0000.00099 (8)0.000
Cl10.0347 (4)0.0712 (6)0.0475 (5)0.0132 (4)0.0020 (4)0.0076 (5)
O10.0319 (12)0.0234 (10)0.0553 (15)0.0000 (8)0.0000 (11)0.0057 (9)
N10.0289 (13)0.0411 (14)0.0303 (14)0.0040 (11)0.0016 (11)0.0001 (12)
N20.0235 (12)0.0220 (11)0.0361 (15)0.0008 (9)0.0057 (11)0.0066 (10)
C10.0271 (15)0.0304 (14)0.0316 (16)0.0018 (12)0.0017 (13)0.0014 (13)
C20.0293 (17)0.0529 (18)0.0331 (18)0.0022 (14)0.0053 (15)0.0012 (15)
C30.0234 (17)0.058 (2)0.042 (2)0.0087 (14)0.0019 (15)0.0062 (16)
C40.0292 (17)0.0387 (15)0.0339 (17)0.0052 (13)0.0041 (14)0.0009 (14)
C50.0254 (15)0.0255 (13)0.0279 (16)0.0010 (11)0.0032 (13)0.0054 (12)
C60.0251 (15)0.0239 (13)0.0295 (16)0.0008 (11)0.0051 (13)0.0018 (12)
Geometric parameters (Å, º) top
Hg1—Cl12.3405 (9)C1—C51.385 (5)
Hg1—Cl1i2.3405 (9)C1—H10.9300
Hg1—N1i2.475 (2)C2—C31.376 (5)
Hg1—N12.475 (2)C2—H20.9300
O1—C61.232 (3)C3—C41.379 (5)
N1—C11.330 (4)C3—H30.9300
N1—C21.338 (4)C4—C51.390 (4)
N2—C61.344 (4)C4—H40.9300
N2—N2ii1.383 (5)C5—C61.484 (4)
N2—H2A0.8601
Cl1—Hg1—Cl1i157.08 (6)N1—C2—C3122.1 (3)
Cl1—Hg1—N1i98.41 (6)N1—C2—H2118.9
Cl1i—Hg1—N1i95.81 (6)C3—C2—H2118.9
Cl1—Hg1—N195.81 (6)C2—C3—C4119.6 (3)
Cl1i—Hg1—N198.41 (6)C2—C3—H3120.2
N1i—Hg1—N1102.92 (11)C4—C3—H3120.2
C1—N1—C2118.3 (3)C3—C4—C5118.7 (3)
C1—N1—Hg1117.28 (19)C3—C4—H4120.7
C2—N1—Hg1124.2 (2)C5—C4—H4120.7
C6—N2—N2ii119.0 (3)C1—C5—C4117.9 (3)
C6—N2—H2A120.5C1—C5—C6122.1 (3)
N2ii—N2—H2A120.5C4—C5—C6119.9 (3)
N1—C1—C5123.3 (3)O1—C6—N2121.8 (3)
N1—C1—H1118.3O1—C6—C5122.4 (3)
C5—C1—H1118.3N2—C6—C5115.8 (2)
Cl1—Hg1—N1—C112.5 (2)C2—C3—C4—C52.1 (5)
Cl1i—Hg1—N1—C1174.5 (2)N1—C1—C5—C41.1 (5)
N1i—Hg1—N1—C187.6 (2)N1—C1—C5—C6177.0 (3)
Cl1—Hg1—N1—C2172.4 (2)C3—C4—C5—C12.5 (5)
Cl1i—Hg1—N1—C210.4 (3)C3—C4—C5—C6178.5 (3)
N1i—Hg1—N1—C287.6 (3)N2ii—N2—C6—O12.0 (5)
C2—N1—C1—C50.8 (5)N2ii—N2—C6—C5179.5 (3)
Hg1—N1—C1—C5174.6 (2)C1—C5—C6—O1147.0 (3)
C1—N1—C2—C31.3 (5)C4—C5—C6—O128.8 (4)
Hg1—N1—C2—C3173.8 (3)C1—C5—C6—N231.5 (4)
N1—C2—C3—C40.2 (5)C4—C5—C6—N2152.7 (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···AD—HH···AD···AD—H···A
C3—H3···Cl1iii0.932.813.558 (4)138
N2—H2A···O1iv0.862.152.844 (3)137
Symmetry codes: (iii) x1, y1, z; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formula[HgCl2(C12H10N4O2)]
Mr513.73
Crystal system, space groupMonoclinic, P2/c
Temperature (K)296
a, b, c (Å)7.2514 (4), 4.7113 (3), 21.8591 (11)
β (°) 103.394 (2)
V3)726.47 (7)
Z2
Radiation typeMo Kα
µ (mm1)10.97
Crystal size (mm)0.30 × 0.26 × 0.22
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.137, 0.196
No. of measured, independent and
observed [I > 2σ(I)] reflections
3510, 1288, 1244
Rint0.018
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.016, 0.038, 1.09
No. of reflections1288
No. of parameters96
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C3—H3···Cl1i0.932.813.558 (4)138.1
N2—H2A···O1ii0.862.152.844 (3)136.9
Symmetry codes: (i) x1, y1, 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

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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds