metal-organic compounds
catena-Poly[[dichloridomercury(II)]-μ-{N-[(E)-pyridin-2-ylmethylidene-κN]pyridin-3-amine-κ2N1:N3}]
aDepartment of Chemistry, Islamic Azad University University, Karaj, Iran, and bDepartment of Chemistry, Alzahra University, Tehran, Iran
*Correspondence e-mail: Mahmoudi_Ali@yahoo.com
In the title coordination polymer, [HgCl2(C11H9N3)]n, the HgII ion is coordinated by three N atoms from two N-[(E)-pyridin-2-ylmethylidene]pyridin-3-amine (L) ligands and two chloride anions in a distorted trigonal–bipyramidal geometry. The two pyridine rings in L form a dihedral angle of 50.0 (2)°. L ligands bridge adjacent HgCl2 units into polymeric chains propagating in [010]. The crystal packing is further stabilized by weak intermolecular C—H⋯Cl hydrogen bonds and π–π interactions between the pyridine rings, with a centroid–centroid separation of 3.529 (9) Å.
Related literature
For related structures and applications of coordination polymers, see: Moulton & Zaworotko (2001); Fei et al. (2000). For the synthesis of the ligand and the index of trigonality, see: Dehghanpour et al. (2012).
Experimental
Crystal data
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Refinement
|
Data collection: COLLECT (Nonius, 2002); cell DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812035775/cv5327sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812035775/cv5327Isup2.hkl
The title complex was prepared by the reaction of HgCl2 (27.1 mg, 0.1 mmol) and pyridin-3-ylpyridin-2-ylmethyleneamine (18.3 mg, 0.1 mmol) in 25 ml of acetonitrile at room temperature. The solution was allowed to stand at room temperature and yellow crystals of the title compound suitable for X-ray analysis precipitated within few days.
H atoms were placed in calculated positions with C—H = 0.95 Å, and included in the
in a riding-motion approximation, with Uiso(H)= 1.2Ueq(C).Many studies has recently been focused on coordination polymers due to their useful properties applicable to catalysis,
conductivity, luminescence (Moulton & Zaworotko, 2001). Nitrogen heterocyclic ligands have been employed in the design and synthesis of many novel coordination polymers (Fei et al., 2000). Herewith we report the synthesis and of a novel Hg(II) complex based on pyridin-3-ylpyridin-2-ylmethyleneamine (PyPy).The τ, (Dehghanpour et al., 2012) which is a measure of trigonal distortion, is 0.59 for the title structure indicating a distorted trigonal–bipyramidal environment of Hg(II).
of the title polymeric complex, consisting of one Hg(II) ion, one PyPy ligand and two chloride anions, is shown in Fig. 1. The coordination geometry around Hg(II) is a distorted trigonal–bipyramidal geometry, with the Hg (II) ion being surrounded by two Cl, two N atoms from one PyPy ligand and one N atom from adjacent PyPy ligand. The structural indexThe interplanar angles between the chelate ring (N1—C5—C6—N2) and pyridine ring (N1—C1—C2—C3—C4—C5) is 0.92 (3)° and interplanar angles between the two pyridine rings in the ligand (N1—C1—C2—C3—C4—C5 ring and N3—C11—C7—C8—C9—C10 ring) is 50.0 (2)°. Each PyPy ligand has been chelate HgCl2 unit (via N, N' atoms) and also bridge to another HgCl2 unit (with N" atom), resulting into a chain propagated in [010].
These chains interact via π–π interactions between adjacent pyridine ringe (N3/C7—C11) related by inversion center, and the distance between their centroids is equal to 3.529 (9) Å. The C—H···Cl interactions (Table 1) are also observed in the crystal structure.
For related structures and applications of coordination polymers, see: Moulton & Zaworotko (2001); Fei et al. (2000). For the synthesis of the ligand and the index of trigonality, see: Dehghanpour et al. (2012).
Data collection: COLLECT (Nonius, 2002); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. A view of the structure of the title complex, with displacement ellipsoids drawn at the 50% probability level [symmetry codes: (a) 1/2 - x, -1/2 + y, 1/2 - z; (b) 1/2 - x, -1/2 + y, 1/2 - z]. |
[HgCl2(C11H9N3)] | F(000) = 840 |
Mr = 454.70 | Dx = 2.412 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 8560 reflections |
a = 7.5645 (5) Å | θ = 3.0–27.5° |
b = 13.1057 (9) Å | µ = 12.70 mm−1 |
c = 12.7017 (5) Å | T = 150 K |
β = 96.077 (4)° | Plate, yellow |
V = 1252.15 (13) Å3 | 0.15 × 0.08 × 0.02 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 2837 independent reflections |
Radiation source: fine-focus sealed tube | 2164 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
φ scans and ω scans with κ offsets | h = −9→9 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −15→16 |
Tmin = 0.566, Tmax = 0.889 | l = −16→16 |
8560 measured reflections |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3 |
2837 reflections | (Δ/σ)max = 0.002 |
154 parameters | Δρmax = 2.45 e Å−3 |
0 restraints | Δρmin = −3.10 e Å−3 |
[HgCl2(C11H9N3)] | V = 1252.15 (13) Å3 |
Mr = 454.70 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.5645 (5) Å | µ = 12.70 mm−1 |
b = 13.1057 (9) Å | T = 150 K |
c = 12.7017 (5) Å | 0.15 × 0.08 × 0.02 mm |
β = 96.077 (4)° |
Nonius KappaCCD diffractometer | 2837 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2164 reflections with I > 2σ(I) |
Tmin = 0.566, Tmax = 0.889 | Rint = 0.059 |
8560 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.09 | Δρmax = 2.45 e Å−3 |
2837 reflections | Δρmin = −3.10 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Hg1 | 0.26173 (3) | 0.14916 (2) | 0.252995 (19) | 0.02692 (14) | |
Cl1 | −0.0045 (3) | 0.16859 (19) | 0.13060 (18) | 0.0509 (6) | |
Cl2 | 0.5101 (2) | 0.27229 (14) | 0.25673 (14) | 0.0296 (4) | |
N1 | 0.2620 (7) | 0.0445 (4) | 0.4086 (4) | 0.0249 (13) | |
N2 | 0.1391 (8) | 0.2435 (5) | 0.4036 (4) | 0.0295 (14) | |
N3 | 0.0833 (8) | 0.5128 (4) | 0.3314 (4) | 0.0261 (13) | |
C1 | 0.3228 (9) | −0.0520 (6) | 0.4171 (5) | 0.0275 (16) | |
H1A | 0.3673 | −0.0821 | 0.3572 | 0.033* | |
C2 | 0.3237 (10) | −0.1096 (6) | 0.5084 (6) | 0.0316 (18) | |
H2A | 0.3702 | −0.1770 | 0.5113 | 0.038* | |
C3 | 0.2552 (9) | −0.0670 (6) | 0.5963 (5) | 0.0293 (16) | |
H3A | 0.2501 | −0.1055 | 0.6592 | 0.035* | |
C4 | 0.1954 (9) | 0.0319 (6) | 0.5895 (6) | 0.0272 (16) | |
H4A | 0.1513 | 0.0636 | 0.6487 | 0.033* | |
C5 | 0.1999 (9) | 0.0854 (6) | 0.4950 (5) | 0.0257 (16) | |
C6 | 0.1330 (9) | 0.1915 (6) | 0.4877 (5) | 0.0284 (16) | |
H6A | 0.0849 | 0.2213 | 0.5467 | 0.034* | |
C7 | 0.0619 (11) | 0.3439 (5) | 0.3945 (6) | 0.0299 (17) | |
C8 | −0.1065 (10) | 0.3615 (6) | 0.4214 (6) | 0.0308 (17) | |
H8A | −0.1701 | 0.3091 | 0.4527 | 0.037* | |
C9 | −0.1826 (10) | 0.4570 (6) | 0.4022 (6) | 0.0319 (18) | |
H9A | −0.2995 | 0.4714 | 0.4191 | 0.038* | |
C10 | −0.0815 (9) | 0.5309 (6) | 0.3574 (5) | 0.0254 (16) | |
H10A | −0.1311 | 0.5969 | 0.3447 | 0.030* | |
C11 | 0.1534 (10) | 0.4210 (6) | 0.3503 (5) | 0.0284 (16) | |
H11A | 0.2703 | 0.4080 | 0.3328 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.02627 (19) | 0.0269 (2) | 0.0285 (2) | −0.00027 (12) | 0.00688 (13) | −0.00040 (11) |
Cl1 | 0.0333 (12) | 0.0627 (16) | 0.0536 (14) | −0.0076 (10) | −0.0097 (9) | 0.0062 (11) |
Cl2 | 0.0272 (9) | 0.0266 (10) | 0.0357 (9) | −0.0027 (7) | 0.0071 (7) | −0.0009 (8) |
N1 | 0.020 (3) | 0.028 (4) | 0.027 (3) | −0.006 (3) | 0.006 (2) | −0.001 (3) |
N2 | 0.027 (3) | 0.035 (4) | 0.026 (3) | −0.008 (3) | 0.001 (2) | 0.001 (3) |
N3 | 0.030 (3) | 0.022 (3) | 0.027 (3) | 0.003 (3) | 0.007 (2) | −0.003 (3) |
C1 | 0.022 (4) | 0.030 (4) | 0.031 (4) | 0.000 (3) | 0.006 (3) | −0.008 (3) |
C2 | 0.020 (4) | 0.032 (5) | 0.041 (4) | −0.001 (3) | −0.005 (3) | 0.004 (3) |
C3 | 0.027 (4) | 0.033 (4) | 0.028 (4) | 0.000 (3) | 0.001 (3) | −0.001 (3) |
C4 | 0.023 (4) | 0.033 (5) | 0.026 (4) | −0.003 (3) | 0.002 (3) | 0.002 (3) |
C5 | 0.019 (4) | 0.029 (4) | 0.029 (4) | 0.001 (3) | 0.002 (3) | −0.001 (3) |
C6 | 0.019 (4) | 0.038 (5) | 0.029 (4) | −0.001 (3) | 0.003 (3) | −0.002 (4) |
C7 | 0.038 (4) | 0.027 (4) | 0.025 (4) | 0.004 (3) | 0.007 (3) | 0.003 (3) |
C8 | 0.031 (4) | 0.033 (5) | 0.028 (4) | −0.006 (3) | 0.005 (3) | −0.002 (3) |
C9 | 0.023 (4) | 0.042 (5) | 0.031 (4) | −0.001 (3) | 0.006 (3) | −0.001 (4) |
C10 | 0.028 (4) | 0.029 (4) | 0.018 (3) | 0.004 (3) | −0.004 (3) | 0.002 (3) |
C11 | 0.031 (4) | 0.025 (4) | 0.030 (4) | 0.004 (3) | 0.011 (3) | 0.000 (3) |
Hg1—N1 | 2.406 (5) | C2—H2A | 0.9500 |
Hg1—Cl1 | 2.424 (2) | C3—C4 | 1.373 (11) |
Hg1—N3i | 2.445 (6) | C3—H3A | 0.9500 |
Hg1—Cl2 | 2.4732 (17) | C4—C5 | 1.393 (10) |
Hg1—N2 | 2.535 (6) | C4—H4A | 0.9500 |
N1—C1 | 1.347 (9) | C5—C6 | 1.480 (11) |
N1—C5 | 1.349 (8) | C6—H6A | 0.9500 |
N2—C6 | 1.272 (9) | C7—C8 | 1.373 (11) |
N2—C7 | 1.438 (9) | C7—C11 | 1.378 (10) |
N3—C11 | 1.327 (9) | C8—C9 | 1.388 (11) |
N3—C10 | 1.345 (8) | C8—H8A | 0.9500 |
N3—Hg1ii | 2.445 (6) | C9—C10 | 1.393 (10) |
C1—C2 | 1.384 (10) | C9—H9A | 0.9500 |
C1—H1A | 0.9500 | C10—H10A | 0.9500 |
C2—C3 | 1.395 (10) | C11—H11A | 0.9500 |
N1—Hg1—Cl1 | 121.03 (14) | C4—C3—H3A | 120.8 |
N1—Hg1—N3i | 89.13 (19) | C2—C3—H3A | 120.8 |
Cl1—Hg1—N3i | 101.53 (15) | C3—C4—C5 | 119.4 (7) |
N1—Hg1—Cl2 | 114.93 (14) | C3—C4—H4A | 120.3 |
Cl1—Hg1—Cl2 | 121.44 (7) | C5—C4—H4A | 120.3 |
N3i—Hg1—Cl2 | 94.98 (14) | N1—C5—C4 | 122.9 (7) |
N1—Hg1—N2 | 68.1 (2) | N1—C5—C6 | 118.0 (6) |
Cl1—Hg1—N2 | 95.00 (15) | C4—C5—C6 | 119.1 (6) |
N3i—Hg1—N2 | 156.61 (19) | N2—C6—C5 | 120.9 (6) |
Cl2—Hg1—N2 | 90.30 (14) | N2—C6—H6A | 119.6 |
C1—N1—C5 | 117.0 (6) | C5—C6—H6A | 119.6 |
C1—N1—Hg1 | 124.9 (4) | C8—C7—C11 | 119.8 (7) |
C5—N1—Hg1 | 118.2 (5) | C8—C7—N2 | 120.9 (7) |
C6—N2—C7 | 120.5 (6) | C11—C7—N2 | 119.1 (6) |
C6—N2—Hg1 | 114.9 (5) | C7—C8—C9 | 119.2 (7) |
C7—N2—Hg1 | 124.3 (4) | C7—C8—H8A | 120.4 |
C11—N3—C10 | 118.6 (6) | C9—C8—H8A | 120.4 |
C11—N3—Hg1ii | 122.8 (5) | C8—C9—C10 | 117.6 (7) |
C10—N3—Hg1ii | 118.6 (5) | C8—C9—H9A | 121.2 |
N1—C1—C2 | 123.4 (6) | C10—C9—H9A | 121.2 |
N1—C1—H1A | 118.3 | N3—C10—C9 | 122.8 (7) |
C2—C1—H1A | 118.3 | N3—C10—H10A | 118.6 |
C1—C2—C3 | 118.9 (7) | C9—C10—H10A | 118.6 |
C1—C2—H2A | 120.6 | N3—C11—C7 | 122.1 (7) |
C3—C2—H2A | 120.6 | N3—C11—H11A | 119.0 |
C4—C3—C2 | 118.4 (7) | C7—C11—H11A | 119.0 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···Cl2iii | 0.95 | 2.82 | 3.700 (8) | 154 |
C6—H6A···Cl2iii | 0.95 | 2.79 | 3.666 (7) | 154 |
C10—H10A···Cl2ii | 0.95 | 2.83 | 3.545 (8) | 132 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [HgCl2(C11H9N3)] |
Mr | 454.70 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 7.5645 (5), 13.1057 (9), 12.7017 (5) |
β (°) | 96.077 (4) |
V (Å3) | 1252.15 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 12.70 |
Crystal size (mm) | 0.15 × 0.08 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.566, 0.889 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8560, 2837, 2164 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.116, 1.09 |
No. of reflections | 2837 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.45, −3.10 |
Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···Cl2i | 0.95 | 2.82 | 3.700 (8) | 154 |
C6—H6A···Cl2i | 0.95 | 2.79 | 3.666 (7) | 154 |
C10—H10A···Cl2ii | 0.95 | 2.83 | 3.545 (8) | 132 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
Acknowledgements
The authors acknowledge the Islamic Azad University University Research Councils for partial support of this work.
References
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Many studies has recently been focused on coordination polymers due to their useful properties applicable to catalysis, chirality, conductivity, luminescence (Moulton & Zaworotko, 2001). Nitrogen heterocyclic ligands have been employed in the design and synthesis of many novel coordination polymers (Fei et al., 2000). Herewith we report the synthesis and crystal structure of a novel Hg(II) complex based on pyridin-3-ylpyridin-2-ylmethyleneamine (PyPy).
The asymmetric unit of the title polymeric complex, consisting of one Hg(II) ion, one PyPy ligand and two chloride anions, is shown in Fig. 1. The coordination geometry around Hg(II) is a distorted trigonal–bipyramidal geometry, with the Hg (II) ion being surrounded by two Cl, two N atoms from one PyPy ligand and one N atom from adjacent PyPy ligand. The structural index τ, (Dehghanpour et al., 2012) which is a measure of trigonal distortion, is 0.59 for the title structure indicating a distorted trigonal–bipyramidal environment of Hg(II).
The interplanar angles between the chelate ring (N1—C5—C6—N2) and pyridine ring (N1—C1—C2—C3—C4—C5) is 0.92 (3)° and interplanar angles between the two pyridine rings in the ligand (N1—C1—C2—C3—C4—C5 ring and N3—C11—C7—C8—C9—C10 ring) is 50.0 (2)°. Each PyPy ligand has been chelate HgCl2 unit (via N, N' atoms) and also bridge to another HgCl2 unit (with N" atom), resulting into a chain propagated in [010].
These chains interact via π–π interactions between adjacent pyridine ringe (N3/C7—C11) related by inversion center, and the distance between their centroids is equal to 3.529 (9) Å. The C—H···Cl interactions (Table 1) are also observed in the crystal structure.