Buy article online - an online subscription or single-article purchase is required to access this article.
The reaction of 2-methyl-1,3-benzothiazole (mebta) with mercury(II) chloride in methanol in a 1:1 molar ratio resulted in the formation of single crystals of the title compound, [HgCl2(C8H7NS)]n. The molecules exist as continuous chlorine-bridged chains in which Hg atoms lie in distorted trigonal bipyramidal environments. The equatorial positions are occupied by an N atom from the ligand [2.236 (8) Å] and two Cl atoms [2.428 (3) and 2.459 (3) Å]. The two axial Hg—Cl contacts to two neighbouring molecules [2.874 (3) and 2.964 (3) Å] are significantly shorter than the sum of the respective van der Waals radii, and form close to linear Cl—Hg—Cl sequences [177.80 (7)°].
Supporting information
CCDC reference: 158228
Mercury(II) chloride (0.3 g, 1.1 mmol) was dissolved in methanol (30 ml). Into
this solution, a methanol solution of 2-methyl-1,3-benzothiazole (0.36 g, 2.4 mmol; in 20 ml) was added slowly. After a short time, the crystallization of
the product began. The reaction mixture was left overnight in a cool place.
The crystals were filtered off, washed with methanol and dried. Yield: 75%.
Analysis calculated for C8H7Cl2HgNS: N 3.33, S 7.62, Hg 47.68%. Found: N
3.32, S 7.68, Hg 47.65%. The IR spectrum in the region 4000–450 cm-1 was
recorded on a Perkin- Elmer FT—IR spectrometer Model 1600 using a KBr disk.
IR max. (cm-1): 3060 (w-m), 2994(w-m), 2920(w-m), 2845(w), 1636(w),
1616(w),1589(w), 1566(m), 1493(s), 1456(s),
1434(s), 1379(m-s), 1320(m), 1286(m-s),
1253(s), 1201(versus), 1154(m-s), 1139(w-m), 1066(w),
1009(w), 942(vw), 888(m-s), 760(versus), 726(s),
706(m-s), 669(w), 654(m), 628(w), 588(w), 568(w),542(w), 529(w),
510(w-m).
All H atoms were included in calculated positions as riding atoms, with
SHELXL97 (Sheldrick, 1997b) default parameters.
Data collection: STADI4 (Stoe & Cie, 1995); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Catena-(2-methyl-benzo-1-thia-3-azolium-µ-dichloromercurate(II))
top
Crystal data top
[HgCl2(C8H7NS)] | F(000) = 768 |
Mr = 420.70 | Dx = 2.639 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.346 (1) Å | Cell parameters from 27 reflections |
b = 9.6957 (6) Å | θ = 8.2–18.0° |
c = 14.915 (1) Å | µ = 15.19 mm−1 |
β = 94.69 (3)° | T = 293 K |
V = 1058.76 (17) Å3 | Prismatic, colourless |
Z = 4 | 0.54 × 0.22 × 0.15 mm |
Data collection top
Philips PW1100 updated by Stoe diffractometer | 1629 reflections with I > 2σ(I) |
Radiation source: Sealed X-ray tube | Rint = 0.017 |
Graphite monochromator | θmax = 27.0°, θmin = 2.5° |
θ/2θ scans | h = −9→9 |
Absorption correction: integration (Stoe & Cie, 1995) | k = 0→12 |
Tmin = 0.047, Tmax = 0.153 | l = 0→19 |
2364 measured reflections | 4 standard reflections every 120 min |
2279 independent reflections | intensity decay: 2.2% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0887P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2279 reflections | Δρmax = 2.18 e Å−3 |
119 parameters | Δρmin = −2.74 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0026 (4) |
Crystal data top
[HgCl2(C8H7NS)] | V = 1058.76 (17) Å3 |
Mr = 420.70 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.346 (1) Å | µ = 15.19 mm−1 |
b = 9.6957 (6) Å | T = 293 K |
c = 14.915 (1) Å | 0.54 × 0.22 × 0.15 mm |
β = 94.69 (3)° | |
Data collection top
Philips PW1100 updated by Stoe diffractometer | 1629 reflections with I > 2σ(I) |
Absorption correction: integration (Stoe & Cie, 1995) | Rint = 0.017 |
Tmin = 0.047, Tmax = 0.153 | 4 standard reflections every 120 min |
2364 measured reflections | intensity decay: 2.2% |
2279 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.06 | Δρmax = 2.18 e Å−3 |
2279 reflections | Δρmin = −2.74 e Å−3 |
119 parameters | |
Special details top
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 | Uiso*/Ueq | |
Hg | 0.24985 (5) | 0.06439 (4) | 0.01208 (3) | 0.0448 (2) | |
Cl1 | 0.4387 (4) | −0.1001 (3) | 0.10017 (17) | 0.0460 (6) | |
Cl2 | 0.0541 (3) | −0.0193 (3) | −0.11823 (16) | 0.0435 (6) | |
S1 | 0.2955 (4) | 0.5257 (3) | 0.11267 (19) | 0.0490 (7) | |
C2 | 0.2888 (13) | 0.3470 (10) | 0.1153 (6) | 0.038 (2) | |
C21 | 0.3131 (17) | 0.2736 (12) | 0.2009 (7) | 0.056 (3) | |
H211 | 0.3311 | 0.3390 | 0.2491 | 0.083* | |
H212 | 0.4178 | 0.2144 | 0.2009 | 0.083* | |
H213 | 0.2064 | 0.2193 | 0.2088 | 0.083* | |
N3 | 0.2620 (11) | 0.2916 (8) | 0.0373 (5) | 0.0370 (18) | |
C4 | 0.2382 (13) | 0.3864 (11) | −0.0348 (6) | 0.0349 (19) | |
C5 | 0.2504 (11) | 0.5249 (13) | −0.0040 (6) | 0.037 (2) | |
C6 | 0.2323 (13) | 0.6329 (11) | −0.0624 (8) | 0.045 (2) | |
H6 | 0.2443 | 0.7233 | −0.0420 | 0.054* | |
C7 | 0.1960 (17) | 0.6050 (12) | −0.1525 (9) | 0.059 (3) | |
H7 | 0.1802 | 0.6775 | −0.1932 | 0.071* | |
C8 | 0.1823 (16) | 0.4684 (12) | −0.1841 (8) | 0.053 (3) | |
H8 | 0.1573 | 0.4513 | −0.2452 | 0.063* | |
C9 | 0.2059 (15) | 0.3601 (12) | −0.1246 (6) | 0.045 (2) | |
H9 | 0.1998 | 0.2696 | −0.1455 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Hg | 0.0501 (3) | 0.0338 (3) | 0.0499 (3) | 0.00136 (17) | 0.00107 (17) | 0.00100 (16) |
Cl1 | 0.0449 (15) | 0.0474 (14) | 0.0458 (13) | 0.0073 (11) | 0.0047 (10) | 0.0097 (10) |
Cl2 | 0.0428 (14) | 0.0475 (13) | 0.0400 (12) | −0.0062 (11) | 0.0021 (10) | −0.0016 (10) |
S1 | 0.0629 (19) | 0.0352 (13) | 0.0489 (15) | −0.0016 (12) | 0.0044 (12) | −0.0127 (11) |
C2 | 0.032 (5) | 0.038 (5) | 0.042 (5) | −0.008 (4) | 0.003 (4) | −0.006 (4) |
C21 | 0.069 (8) | 0.048 (6) | 0.047 (6) | −0.004 (6) | −0.008 (5) | 0.006 (5) |
N3 | 0.046 (5) | 0.029 (4) | 0.036 (4) | 0.001 (4) | 0.003 (3) | −0.004 (3) |
C4 | 0.036 (5) | 0.032 (5) | 0.037 (5) | 0.001 (4) | 0.006 (4) | 0.004 (4) |
C5 | 0.026 (5) | 0.049 (6) | 0.034 (5) | 0.003 (4) | 0.000 (4) | −0.004 (4) |
C6 | 0.034 (5) | 0.030 (5) | 0.070 (7) | −0.008 (4) | −0.001 (5) | 0.001 (5) |
C7 | 0.063 (8) | 0.045 (6) | 0.069 (8) | 0.005 (6) | 0.002 (6) | 0.018 (6) |
C8 | 0.061 (8) | 0.055 (7) | 0.043 (6) | 0.004 (6) | 0.008 (5) | 0.008 (5) |
C9 | 0.058 (7) | 0.047 (6) | 0.029 (5) | 0.005 (5) | −0.002 (4) | 0.002 (4) |
Geometric parameters (Å, º) top
Hg—N3 | 2.236 (8) | C21—H213 | 0.9600 |
Hg—Cl1 | 2.428 (3) | N3—C4 | 1.415 (13) |
Hg—Cl2 | 2.459 (3) | C4—C9 | 1.365 (13) |
Hg—Cl2i | 2.874 (3) | C4—C5 | 1.420 (16) |
Hg—Cl1ii | 2.964 (3) | C5—C6 | 1.362 (15) |
Cl1—Hgii | 2.964 (3) | C6—C7 | 1.375 (17) |
Cl2—Hgi | 2.874 (3) | C6—H6 | 0.9300 |
S1—C2 | 1.734 (10) | C7—C8 | 1.406 (16) |
S1—C5 | 1.744 (9) | C7—H7 | 0.9300 |
C2—N3 | 1.282 (12) | C8—C9 | 1.376 (14) |
C2—C21 | 1.459 (14) | C8—H8 | 0.9300 |
C21—H211 | 0.9600 | C9—H9 | 0.9300 |
C21—H212 | 0.9600 | | |
| | | |
N3—Hg—Cl1 | 122.9 (2) | C2—N3—C4 | 114.7 (9) |
N3—Hg—Cl2 | 118.1 (2) | C2—N3—Hg | 124.5 (7) |
Cl1—Hg—Cl2 | 118.84 (9) | C4—N3—Hg | 120.8 (6) |
N3—Hg—Cl2i | 94.6 (2) | C9—C4—N3 | 128.7 (10) |
Cl1—Hg—Cl2i | 92.12 (8) | C9—C4—C5 | 119.8 (9) |
Cl2—Hg—Cl2i | 87.40 (8) | N3—C4—C5 | 111.5 (8) |
N3—Hg—Cl1ii | 87.6 (2) | C6—C5—C4 | 121.2 (9) |
Cl1—Hg—Cl1ii | 87.08 (8) | C6—C5—S1 | 129.5 (10) |
Cl2—Hg—Cl1ii | 91.18 (8) | C4—C5—S1 | 109.2 (8) |
Cl2i—Hg—Cl1ii | 177.80 (7) | C5—C6—C7 | 118.4 (10) |
Hg—Cl1—Hgii | 92.92 (8) | C5—C6—H6 | 120.8 |
Hg—Cl2—Hgi | 92.60 (8) | C7—C6—H6 | 120.8 |
C2—S1—C5 | 90.9 (5) | C6—C7—C8 | 121.0 (11) |
N3—C2—C21 | 126.0 (9) | C6—C7—H7 | 119.5 |
N3—C2—S1 | 113.6 (7) | C8—C7—H7 | 119.5 |
C21—C2—S1 | 120.4 (7) | C9—C8—C7 | 120.1 (11) |
C2—C21—H211 | 109.5 | C9—C8—H8 | 120.0 |
C2—C21—H212 | 109.5 | C7—C8—H8 | 120.0 |
H211—C21—H212 | 109.5 | C4—C9—C8 | 119.4 (10) |
C2—C21—H213 | 109.5 | C4—C9—H9 | 120.3 |
H211—C21—H213 | 109.5 | C8—C9—H9 | 120.3 |
H212—C21—H213 | 109.5 | | |
| | | |
C5—S1—C2—N3 | 2.0 (8) | C2—S1—C5—C6 | 179.9 (9) |
C5—S1—C2—C21 | −178.2 (9) | C2—S1—C5—C4 | −1.8 (7) |
C21—C2—N3—C4 | 178.5 (10) | C4—C5—C6—C7 | 2.0 (15) |
S1—C2—N3—C4 | −1.7 (11) | S1—C5—C6—C7 | −179.9 (8) |
C2—N3—C4—C9 | −179.3 (9) | C5—C6—C7—C8 | −1.6 (17) |
C2—N3—C4—C5 | 0.3 (12) | C6—C7—C8—C9 | −0.2 (19) |
C9—C4—C5—C6 | −0.7 (14) | N3—C4—C9—C8 | 178.4 (10) |
N3—C4—C5—C6 | 179.7 (8) | C5—C4—C9—C8 | −1.1 (15) |
C9—C4—C5—S1 | −179.2 (8) | C7—C8—C9—C4 | 1.6 (18) |
N3—C4—C5—S1 | 1.2 (10) | | |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z. |
Experimental details
Crystal data |
Chemical formula | [HgCl2(C8H7NS)] |
Mr | 420.70 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.346 (1), 9.6957 (6), 14.915 (1) |
β (°) | 94.69 (3) |
V (Å3) | 1058.76 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 15.19 |
Crystal size (mm) | 0.54 × 0.22 × 0.15 |
|
Data collection |
Diffractometer | Philips PW1100 updated by Stoe diffractometer |
Absorption correction | Integration (Stoe & Cie, 1995) |
Tmin, Tmax | 0.047, 0.153 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2364, 2279, 1629 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.135, 1.06 |
No. of reflections | 2279 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.18, −2.74 |
Selected geometric parameters (Å, º) topHg—N3 | 2.236 (8) | Hg—Cl2i | 2.874 (3) |
Hg—Cl1 | 2.428 (3) | Hg—Cl1ii | 2.964 (3) |
Hg—Cl2 | 2.459 (3) | | |
| | | |
N3—Hg—Cl1 | 122.9 (2) | N3—Hg—Cl1ii | 87.6 (2) |
N3—Hg—Cl2 | 118.1 (2) | Cl1—Hg—Cl1ii | 87.08 (8) |
Cl1—Hg—Cl2 | 118.84 (9) | Cl2—Hg—Cl1ii | 91.18 (8) |
N3—Hg—Cl2i | 94.6 (2) | Cl2i—Hg—Cl1ii | 177.80 (7) |
Cl1—Hg—Cl2i | 92.12 (8) | Hg—Cl1—Hgii | 92.92 (8) |
Cl2—Hg—Cl2i | 87.40 (8) | Hg—Cl2—Hgi | 92.60 (8) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Mercury(II) forms complexes with heterocyclic ligands, which may contain nitrogen, oxygen, sulfur or a combination of these as parts of endocyclic groups. Such complexes can be used as models for better understanding of mercury binding in biological systems as well as its toxicological behaviour. It is also of interest to get more information on the role of halide ions in such systems. Since the activities of many enzymes depend upon the interaction of a thiazole group with a metal ion we choose mebta as a model molecule. It is a well known fact that mercury(II) halides form two types of complexes with a neutral ligand depending upon the stoichiometric ratio of the reactants i.e. HgX2L and HgX2L2, respectively. Until now, the only known mercury(II) addition compounds are of the type HgX2L (X = Cl-, Br-, I-), HgNO3·L and Hg(ClO4)2. 1.5L (L = 2-aminobenzothiazole) (Giusti et al., 1982). On the basis of the IR spectral investigations, the authors exclude a coordination of NH2-bta through the amino nitrogen atom and support its coordination through the ring nitrogen. Almost as a rule, 2-substituted derivatives of bta (scheme bta) act as σ-monodentate ligand through the ring nitrogen atom. The only known example of an N,N'-bidentate coordination of NH2-bta is reported for some dimolybdenum 2-aminobenzothiazolato complexes (Cotton et al., 1981). The 2-aminobenzothiazolato anion is formed after deprotonation of one amino proton with n-butyllithium. It was established that the majority of the structures of 1:1 complexes of mercury(II) halides or pseudohalides with various neutral ligands in the solid state consists of discrete halogen-bridged dimeric molecules with the mercury atom in a tetrahedral environment (Dean, 1978). But this cannot be safely assumed for all 1:1 complexes and other more associated structures are also known (Bell et al., 1981; Einstein et al., 1983; Álvarez-Larena et al., 1997). Recently we found that due to ring opening of bta by the mercury(II) ion, di-µ-chloro-bis[2-ammoniobenzenethiolato-S)chloromercury(II)] was obtained (Davidović et al., 1998), while mebta reacts with the ion in the same manner as the other 2-substituted bta derivatives do, resulting in complexes coordinated through the ring nitrogen atom. The structure of (2-mercaptobenzo- thiazolato)methylmercury(II) is the only one reported so far (Bravo et al., 1985). The stereochemistry of mercury in the solid state is characterized by a few typical modes of ligand binding. The characteristic coordination (m) consists of m covalently bonded ligands, while the effective coordination (m + n) include n additionally bonded ligands at distances shorter than the sum of the van der Waals radii of Hg and donor atom of the ligand (Grdenić, 1965). \sch
The title compound, (I), is a chlorine-bridged polymer (Fig.1) containing mercury atoms with slightly distorted trigonal bipyramidal coordination, (3 + 2). The equatorial positions are occupied by the N atom of the benzothiazole ligand [2.236 (8) Å] and the two terminal Cl atoms [2.428 (3) and 2.459 (3) Å]. The coordination of mercury is an almost regular triangle, with the angles around mercury varying from 118.1 (2) (N3—Hg—Cl2) to 122.9 (2)° (N3—Hg—Cl1), and these four atoms are essentially coplanar. The two axial Hg—Cl contacts [2.874 (3) and 2.964 (3) Å] are close to collinear [177.80 (7)°], with bridging angles, Hg—Cl(1)—Hgi and Hg—Cl(2)—Hgii, of 92.92 (8) and 92.60 (8)°, respectively, [(i) = -x + 1, -y, -z; (ii) = -x, -y, -z]. The Hg—Cl (terminal) and Hg—N distances are longer than expected (sums of the covalent radii are 2.38 and 2.13 Å) for characteristic trigonal coordination and are in agreement with bond lenghts previously reported for chloro-bridged polymeric mercury structures (Biscarini et al., 1977; Bell et al., 1981; Álvarez-Larena et al., 1997).
The molecular parameters for the benzothiazole ligand have expected values. Within the fused benzene ring the C—C bond lengths range from 1.420 (16) to 1.365 (13) Å; the latter one is significantly different from the standard C—C (benzene) value of 1.397 Å. Such differences are common, particularly in fused-ring systems (Oughtred, 1982). The C2—S1—C5 angle [90.9 (5)°] is typical of S-containing five-membered heterocyclic molecules. The S1—C2 [1.734 (10) Å] and S1—C5 [1.744 (9) Å] bond lengths imply a partial π character. Significant differences exist between the C2—N3 [1.282 (12) Å] and C4—N3 [1.415 (13)] bonds, suggesting localization of π-electron density in the S1—C2—N3 moiety. The solid state IR-spectrum of the title compound in the region of 4000–450 cm-1 is in agreement with X-ray diffraction data with respect to the mode of coordination. In the spectral range of 1650–1470 cm-1, which is associated with ν(C=C) + ν(C=N) vibrations, a significant shift of the very strong absorption band toward lower frequencies (from 1529 cm-1 to 1493 cm-1; and of reduced intensity) is observed. The shift of the ν(C—S) toward higher frequencies (from 641 to 654 cm -1) implies an increased dπ-pπ contribution between sulfur and ring π-system.