Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026025/lh2375sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026025/lh2375Isup2.hkl |
CCDC reference: 654871
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.044
- wR factor = 0.098
- Data-to-parameter ratio = 19.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ? PLAT431_ALERT_2_C Short Inter HL..A Contact Cl1 .. O1 .. 2.98 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Some crystal structures that contain the title molecule in cocrystals have been reported previously (Suzuki et al., 1997; Sekine, Jomoto et al., 2003; Sekine, Mitsumori et al., 2003).
For related literature, see: Frisch et al. (2003); Fujii et al. (2005); Glendening et al. (2001); Kato et al. (2007); Lewis et al. (1973); Wiberg (1968).
Single crystals of (I) suitable for X-ray diffraction were obtained as follows:
4-Chloro-2-methylisothiazolin-3-one was extracted from 'Kathon WT', which was purchased from Rohm and Hass, by 1,2-dichloroethane and was dried with anhydrous MgSO4. Crude crystals were obtained by evaporation of the solvents and were recrystallized from ligroin. Elemental analysis, found: C 31.87, H 2.52, N 9.20%; calcd. for C4H4ClNOS: C 32.11, H 2.70, N 9.36%.
H atoms were placed in calculated positions [C—H = 0.95 & 0.98 Å] and included in the refinement in the riding-model approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.
The title compound, 5-Chloro-2-methylisothiazolin-3-one (I) is widely used as a biocide. Some molecular structures which contain (I) as co-crystals have been reported previously (Suzuki et al., 1997; Sekine, Jomoto et al., 2003; Sekine, Mitsumori et al., 2003) but there are no reports on the crystal structure of (I) itself. We are interested in the relationship between the crystal structures of isothiazolines and their biocidal activities (Kato et al., 2007) and report here the crystal structure of (I).
The molecular structure of (I), with the atom-labelling scheme, is shown in Fig. 1. Selected bond lengths and angles are shown in Table 1. The C1—C2 bond length is slightly longer than that previously reported (1.441 (3) Å, Sekine, Mitsumori et al., 2003; 1.438 (4) Å, Sekine, Jomoto et al., 2003; 1.437 Å, Suzuki et al., 1997). The five-membered ring (S1/N1/C1—C3) is planar and the largest deviation from the plane being for atom N1 [0.0086 (12) Å]. The deviation of the C4 atom in the methyl group from the five-membered ring is 0.2214 (36) Å despite the N1 atom with sp3-hybridization state. The planarity around the N1 atom indicates the delocalization of the lone pair of electrons on the N1 atom. An intermolecular interaction between Cl1 and O1 is observed (Fig. 2) and its distance is 2.9811 (19) Å. This distance is the same as reported previously (2.981 (2) Å, Fujii et al., 2005). The Cl1 atom accepts the lone pair electrons of O1 and this intermolecular interaction stabilizes the crystal structure.
We performed the DFT calculations on (I) and 2-methylisothiazolin-3-one (II) by the B3LYP method for elucidating its electronic structure using the Gaussian03 package program (Frisch et al., 2003). The 6–31+G(d,p) basis set was used for all the elements. The optimized geometry shows a good agreement with the crystal structure. The Wiberg bond indices (Wiberg, 1968) were evaluated by natural-bond orbital (NBO) analysis (Glendening et al., 2001) and these values are shown in Fig. 3. The almost Wiberg bond indices, except that of the C1—N1 bond, in (I) tend to be lower than those in (II). This may be due to the electron-withdrawing Cl on the C3 instead of H, and decreases the electron density on the five-membered ring. These results correspond to the higher activity of (I) as a biocide compared to that of (II) since the ease of cleavage of the N1—S1 bond is claimed to give rise to the biocidal activity (Lewis et al., 1973).
Some crystal structures that contain the title molecule in cocrystals have been reported previously (Suzuki et al., 1997; Sekine, Jomoto et al., 2003; Sekine, Mitsumori et al., 2003).
For related literature, see: Frisch et al. (2003); Fujii et al. (2005); Glendening et al. (2001); Kato et al. (2007); Lewis et al. (1973); Wiberg (1968).
Data collection: SMART-W2K/NT (Bruker, 2003); cell refinement: SAINT-W2K/NT (Bruker, 2003); data reduction: SAINT-W2K/NT; program(s) used to solve structure: SHELXTL-NT (Bruker, 2003); program(s) used to refine structure: SHELXTL-NT; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL-NT.
C4H4ClNOS | F(000) = 304 |
Mr = 149.59 | Dx = 1.621 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 824 reflections |
a = 8.0290 (16) Å | θ = 2.7–24.8° |
b = 13.978 (3) Å | µ = 0.86 mm−1 |
c = 5.7375 (11) Å | T = 173 K |
β = 107.812 (4)° | Needle, colorless |
V = 613.1 (2) Å3 | 0.40 × 0.09 × 0.09 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1474 independent reflections |
Radiation source: fine-focus sealed tube | 1157 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.0°, θmin = 2.7° |
φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick 1996) | k = −14→18 |
Tmin = 0.726, Tmax = 0.927 | l = −7→7 |
4451 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0484P)2] where P = (Fo2 + 2Fc2)/3 |
1474 reflections | (Δ/σ)max = 0.001 |
74 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C4H4ClNOS | V = 613.1 (2) Å3 |
Mr = 149.59 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0290 (16) Å | µ = 0.86 mm−1 |
b = 13.978 (3) Å | T = 173 K |
c = 5.7375 (11) Å | 0.40 × 0.09 × 0.09 mm |
β = 107.812 (4)° |
Bruker SMART CCD area-detector diffractometer | 1474 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick 1996) | 1157 reflections with I > 2σ(I) |
Tmin = 0.726, Tmax = 0.927 | Rint = 0.044 |
4451 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.33 e Å−3 |
1474 reflections | Δρmin = −0.27 e Å−3 |
74 parameters |
Geometry. Distance SDEV 2.9811 (0.0019) O1 - Cl1_$1 Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 0.2147 (0.0078) x + 12.2058 (0.0061) y - 2.6112 (0.0038) z = 5.0659 (0.0082) * -0.0061 (0.0013) C1 * -0.0006 (0.0014) C2 * 0.0052 (0.0013) C3 * 0.0086 (0.0012) N1 * -0.0071 (0.0010) S1 - 0.0161 (0.0029) O1 - 0.2214 (0.0036) C4 0.0272 (0.0032) Cl1 Rms deviation of fitted atoms = 0.0061 |
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 | ||
C1 | 0.5852 (3) | 0.59959 (15) | 0.8169 (4) | 0.0214 (5) | |
C2 | 0.4002 (3) | 0.57570 (16) | 0.7183 (4) | 0.0222 (5) | |
H1 | 0.3505 | 0.5427 | 0.5683 | 0.027* | |
C3 | 0.3088 (3) | 0.60554 (16) | 0.8631 (4) | 0.0229 (5) | |
C4 | 0.7856 (3) | 0.66864 (17) | 1.2057 (4) | 0.0287 (6) | |
H2A | 0.8755 | 0.6419 | 1.1412 | 0.043* | |
H2B | 0.7960 | 0.6397 | 1.3651 | 0.043* | |
H2C | 0.8014 | 0.7380 | 1.2246 | 0.043* | |
Cl1 | 0.08933 (8) | 0.59406 (5) | 0.81908 (12) | 0.0338 (2) | |
N1 | 0.6122 (2) | 0.64805 (13) | 1.0356 (4) | 0.0229 (4) | |
O1 | 0.7041 (2) | 0.58234 (11) | 0.7303 (3) | 0.0289 (4) | |
S1 | 0.43218 (8) | 0.66265 (4) | 1.12464 (11) | 0.02660 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0250 (12) | 0.0201 (11) | 0.0199 (12) | −0.0007 (9) | 0.0080 (10) | 0.0019 (9) |
C2 | 0.0236 (12) | 0.0230 (12) | 0.0192 (12) | −0.0016 (9) | 0.0051 (10) | −0.0019 (9) |
C3 | 0.0206 (12) | 0.0241 (12) | 0.0239 (12) | −0.0002 (9) | 0.0067 (10) | 0.0021 (9) |
C4 | 0.0272 (14) | 0.0339 (14) | 0.0231 (13) | −0.0033 (11) | 0.0049 (11) | −0.0032 (10) |
Cl1 | 0.0209 (3) | 0.0439 (4) | 0.0370 (4) | 0.0012 (3) | 0.0094 (3) | 0.0014 (3) |
N1 | 0.0209 (10) | 0.0271 (11) | 0.0210 (10) | −0.0021 (8) | 0.0069 (8) | −0.0039 (8) |
O1 | 0.0247 (9) | 0.0386 (10) | 0.0253 (10) | −0.0027 (7) | 0.0103 (7) | −0.0061 (7) |
S1 | 0.0271 (3) | 0.0308 (4) | 0.0248 (3) | −0.0009 (3) | 0.0123 (3) | −0.0056 (2) |
C1—O1 | 1.227 (3) | C3—S1 | 1.721 (2) |
C1—N1 | 1.383 (3) | C4—N1 | 1.464 (3) |
C1—C2 | 1.458 (3) | C4—H2A | 0.9800 |
C2—C3 | 1.332 (3) | C4—H2B | 0.9800 |
C2—H1 | 0.9500 | C4—H2C | 0.9800 |
C3—Cl1 | 1.710 (2) | N1—S1 | 1.686 (2) |
O1—C1—N1 | 122.5 (2) | N1—C4—H2B | 109.5 |
O1—C1—C2 | 128.7 (2) | H2A—C4—H2B | 109.5 |
N1—C1—C2 | 108.8 (2) | N1—C4—H2C | 109.5 |
C3—C2—C1 | 112.1 (2) | H2A—C4—H2C | 109.5 |
C3—C2—H1 | 123.9 | H2B—C4—H2C | 109.5 |
C1—C2—H1 | 123.9 | C1—N1—C4 | 123.7 (2) |
C2—C3—Cl1 | 128.16 (19) | C1—N1—S1 | 115.04 (16) |
C2—C3—S1 | 114.15 (18) | C4—N1—S1 | 120.17 (16) |
Cl1—C3—S1 | 117.69 (14) | N1—S1—C3 | 89.86 (10) |
N1—C4—H2A | 109.5 | ||
O1—C1—C2—C3 | 179.8 (2) | O1—C1—N1—S1 | −178.96 (17) |
N1—C1—C2—C3 | −0.5 (3) | C2—C1—N1—S1 | 1.3 (2) |
C1—C2—C3—Cl1 | 179.39 (17) | C1—N1—S1—C3 | −1.33 (17) |
C1—C2—C3—S1 | −0.4 (3) | C4—N1—S1—C3 | −169.62 (18) |
O1—C1—N1—C4 | −11.1 (3) | C2—C3—S1—N1 | 0.99 (19) |
C2—C1—N1—C4 | 169.1 (2) | Cl1—C3—S1—N1 | −178.85 (14) |
Experimental details
Crystal data | |
Chemical formula | C4H4ClNOS |
Mr | 149.59 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 8.0290 (16), 13.978 (3), 5.7375 (11) |
β (°) | 107.812 (4) |
V (Å3) | 613.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.40 × 0.09 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick 1996) |
Tmin, Tmax | 0.726, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4451, 1474, 1157 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.098, 1.00 |
No. of reflections | 1474 |
No. of parameters | 74 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.27 |
Computer programs: SMART-W2K/NT (Bruker, 2003), SAINT-W2K/NT (Bruker, 2003), SAINT-W2K/NT, SHELXTL-NT (Bruker, 2003), SHELXTL-NT, ORTEP-3 for Windows (Farrugia, 1997).
C1—O1 | 1.227 (3) | C3—Cl1 | 1.710 (2) |
C1—N1 | 1.383 (3) | C3—S1 | 1.721 (2) |
C1—C2 | 1.458 (3) | C4—N1 | 1.464 (3) |
C2—C3 | 1.332 (3) | N1—S1 | 1.686 (2) |
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The title compound, 5-Chloro-2-methylisothiazolin-3-one (I) is widely used as a biocide. Some molecular structures which contain (I) as co-crystals have been reported previously (Suzuki et al., 1997; Sekine, Jomoto et al., 2003; Sekine, Mitsumori et al., 2003) but there are no reports on the crystal structure of (I) itself. We are interested in the relationship between the crystal structures of isothiazolines and their biocidal activities (Kato et al., 2007) and report here the crystal structure of (I).
The molecular structure of (I), with the atom-labelling scheme, is shown in Fig. 1. Selected bond lengths and angles are shown in Table 1. The C1—C2 bond length is slightly longer than that previously reported (1.441 (3) Å, Sekine, Mitsumori et al., 2003; 1.438 (4) Å, Sekine, Jomoto et al., 2003; 1.437 Å, Suzuki et al., 1997). The five-membered ring (S1/N1/C1—C3) is planar and the largest deviation from the plane being for atom N1 [0.0086 (12) Å]. The deviation of the C4 atom in the methyl group from the five-membered ring is 0.2214 (36) Å despite the N1 atom with sp3-hybridization state. The planarity around the N1 atom indicates the delocalization of the lone pair of electrons on the N1 atom. An intermolecular interaction between Cl1 and O1 is observed (Fig. 2) and its distance is 2.9811 (19) Å. This distance is the same as reported previously (2.981 (2) Å, Fujii et al., 2005). The Cl1 atom accepts the lone pair electrons of O1 and this intermolecular interaction stabilizes the crystal structure.
We performed the DFT calculations on (I) and 2-methylisothiazolin-3-one (II) by the B3LYP method for elucidating its electronic structure using the Gaussian03 package program (Frisch et al., 2003). The 6–31+G(d,p) basis set was used for all the elements. The optimized geometry shows a good agreement with the crystal structure. The Wiberg bond indices (Wiberg, 1968) were evaluated by natural-bond orbital (NBO) analysis (Glendening et al., 2001) and these values are shown in Fig. 3. The almost Wiberg bond indices, except that of the C1—N1 bond, in (I) tend to be lower than those in (II). This may be due to the electron-withdrawing Cl on the C3 instead of H, and decreases the electron density on the five-membered ring. These results correspond to the higher activity of (I) as a biocide compared to that of (II) since the ease of cleavage of the N1—S1 bond is claimed to give rise to the biocidal activity (Lewis et al., 1973).