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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Ethyl 2-amino-4-tert-butyl-1,3-thiazole-5-carboxyl­ate and 6-methylimidazo­[2,1-b]­thia­zole–2-amino-1,3-thia­zole (1/1)

CROSSMARK_Color_square_no_text.svg

aSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, England, and bKey Organics Ltd, Highfield Industrial Estate, Camelford, Cornwall PL32 9QZ, England
*Correspondence e-mail: apx106@coventry.ac.uk

(Received 17 June 2004; accepted 24 June 2004; online 21 July 2004)

The structure of ethyl 2-amino-4-tert-butyl-1,3-thia­zole-5-carboxyl­ate, C10H16N2O2S, (I[link]), and the structure of the 1:1 adduct 6-methyl­imidazo­[2,1-b]­thia­zole–2-amino-1,3-thia­zole (1/1), C6H6N2S·C3H4N2S, (II[link]), have been determined. The mol­ecules in (I[link]) associate via a hydrogen-bonded R[{_2^2}](8) dimer consisting of N—H⋯N interactions, with the hydrogen-bonding array additionally involving N—H⋯O interactions to one of the carboxyl­ate O atoms. The 2-amino­thia­zole mol­ecules in (II[link]) also associate via an N—H⋯N hydrogen-bonded R[{_2^2}](8) dimer, with an additional N—H⋯N interaction to the Nsp2 atom of the imidazo­thia­zole moiety, creating hydrogen-bonded quartets.

Comment

Amino­thia­zoles have been extensively studied for a range of biological and industrial applications (Lynch et al., 1999[Lynch, D. E., Nicholls, L. J., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1999). Acta Cryst. B55, 758-766.]; Toplak et al., 2003[Toplak, R., Lah, N., Volmajer, J., Leban, I. & Le Maréchal, A. M. (2003). Acta Cryst. C59, o502-o505.]). 2-Amino-1,3-thia­zole, the structure of which was reported in 1982 (Caranoni & Reboul, 1982[Caranoni, P. C. & Reboul, J. P. (1982). Acta Cryst. B38, 1255-1259.]), is itself listed as a thyroid inhibitor (Merck, 2001[Merck (2001). The Merck Index, 13th ed. New York: John Wiley & Sons.]). A search of the Cambridge Structural Database (CSD, Version 5.25 of April 2004; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) reveals that there are 73 crystal structures containing the 2-amino­thia­zole moiety, with 51 of those being pure organics. The present authors have recently published a paper on the packing modes of 2-amino-4-phenyl-1,3-thia­zole derivatives (Lynch et al., 2002[Lynch, D. E., McClenaghan, I., Light, M. E. & Coles, S. J. (2002). Cryst. Eng. 5, 123-136.]) and have been investigating the structural aspects of 2-amino­thia­zole derivatives for the last six years. One such compound reported during this time was ethyl 4-tert-butyl-2-(3-phenyl­ureido)-1,3-thia­zole-5-carboxyl­ate (Lynch & McClenaghan, 2002[Lynch, D. E. & McClenaghan, I. (2002). Acta Cryst. E58, o733-o734.]), which is currently the only structure of a 4-tert-butyl-5-ester derivative of an amino­thia­zole. However, we have recently determined the structure of ethyl 2-amino-4-tert-butyl-1,3-thia­zole-5-carboxyl­ate, (I[link]), and report it here.

Another amino­thia­zole derivative is imidazo­[2,1-b]­thia­zole, which has 11 analogues whose structures have previously been reported in the CSD. This bicyclic ring system can be prepared by refluxing a halo­methyl ketone with 2-amino­thia­zole in ethanol. In an attempt to do so, using chloro­acetone, an incomplete reaction yielded a mixture of the imidazo­[2,1-b]­thia­zole derivative with the starting thia­zole. The crystals that formed from the impure product were subsequently found to contain the 1:1 adduct of 6-methyl­imidazo­[2,1-b]­thia­zole with 2-amino­thia­zole, (II[link]), the structure of which is also reported here.

[Scheme 1]

The structure of (I[link]) consists of a single mol­ecule (Fig. 1[link]) which associates, via hydrogen-bonding interactions, to three symmetry-equivalent mol­ecules (Fig. 2[link]). One symmetry-equivalent mol­ecule forms a hydrogen-bonded R[{_2^2}](8) graph-set dimer (Etter, 1990[Etter, M. C. (1990). Acc. Chem. Res. 23, 120-126.]) with (I[link]) through an N—H⋯N interaction (Table 1[link]), a feature common for 2-amino­thia­zole derivatives, while the other two associate to and from (I[link]) through an N—H⋯O interaction. A similar packing mode has previously been observed in the structure of ethyl 2-amino-4-phenyl-1,3-thia­zole-5-carboxyl­ate (Lynch et al., 2002[Lynch, D. E., McClenaghan, I., Light, M. E. & Coles, S. J. (2002). Cryst. Eng. 5, 123-136.]), but is not observed in any other 5-ester-substituted 2-amino­thia­zole. This is probably due to the fact that, in each of these other structures, there are alternative exocyclic hydrogen-bonding acceptor atoms in addition to the two carboxyl­ate O atoms. The ethyl chain twists out of the plane of the thia­zole ring, with the C51—O52—C53—C54 torsion angle being 85.5 (2)°, compared with −168.5 (3)° in ethyl 4-tert-butyl-2-(3-phenyl­ureido)-1,3-thia­zole-5-carboxyl­ate (Lynch & McClenaghan, 2002[Lynch, D. E. & McClenaghan, I. (2002). Acta Cryst. E58, o733-o734.]). One of the methyl groups in the tert-butyl moiety is aligned with the thia­zole ring, with the N3—C4—C41—C42 torsion angle being −1.8 (2)°, similar to what was observed in ethyl 4-tert-butyl-2-(3-phenyl­ureido)-1,3-thia­zole-5-carboxyl­ate [comparative torsion angle = 7.2 (5)°].

The structure of (II[link]) comprises two adduct mol­ecules associated by a single hydrogen-bonding interaction from one of the 2-amino H atoms to the Nsp2 atom in the imidazo­thia­zole system (Fig. 3[link]). Although one of the present authors (DEL) has determined 16 co-crystal structures containing 2-­amino­thia­zole derivatives, there are only two previously reported co-crystals containing 2-amino­thia­zole itself (Kuz'mina & Struchkov, 1984[Kuz'mina, L. G. & Struchkov, Y. T. (1984). Zh. Strukt. Khim. 25, 88-92. (In Russian.)]; Moers et al., 2000[Moers, O., Wijaya, K., Lange, I., Blaschette, A. & Jones, P. G. (2000). Z. Naturforsch. Teil B, 55, 738-752.]), and both of these are organic salts. The structure of (II[link]) is unique in that it is the first adduct (not an organic salt) of 2-amino­thia­zole. The mol­ecules in (II[link]) pack across an inversion centre to construct an associated quartet, with the 2-amino­thia­zoles forming a hydrogen-bonded R[{_2^2}](8) graph-set dimer (Fig. 4[link]). Hydro­gen-bonding associations are listed in Table 2[link]. A C—H⋯N close contact is also observed between atom C2A and the 2-amino N atom. The distance between atoms N7A and S1B is 3.294 (3) Å.

The determination of the structure of (II[link]) and examination of the packing associations may now lead to a series of adducts containing 2-amino­thia­zole and heterocyclic bases, as opposed to continuing to try to obtain co-crystals (either adducts or organic salts) with organic acids.

[Figure 1]
Figure 1
The molecular configuration and atom-numbering scheme for (I[link]). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2]
Figure 2
A packing diagram for (I[link]). [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) [{3 \over 2}] − x, y + [{1 \over 2}], [{3 \over 2}] − z.]
[Figure 3]
Figure 3
The molecular configuration and atom-numbering scheme for (II[link]). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4]
Figure 4
A packing diagram for (II[link]). [Symmetry code: (i) −x, 1 − y, 1 − z.]

Experimental

Compound (I[link]) was obtained from Key Organics Ltd and was crystallized from ethanol. Compound (II[link]) was prepared by refluxing equimolar amounts of 2-amino-1,3-thia­zole and chloro­acetone in ethanol for 16 h. Upon removal of the reaction solvent, the product was washed with aqueous NaOH and then extracted into di­chloro­methane. Crystals of (II[link]) grew from the resultant liquid after removal of the extraction solvent.

Compound (I)[link]

Crystal data
  • C10H16N2O2S

  • Mr = 228.31

  • Monoclinic, P21/n

  • a = 10.6248 (8) Å

  • b = 8.6055 (5) Å

  • c = 13.0135 (9) Å

  • β = 92.977 (4)°

  • V = 1188.24 (14) Å3

  • Z = 4

  • Dx = 1.276 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3289 reflections

  • θ = 2.9–27.5°

  • μ = 0.26 mm−1

  • T = 120 (2) K

  • Prism, colourless

  • 0.42 × 0.32 × 0.08 mm

Data collection
  • Bruker–Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SORTAV; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-37.]) Tmin = 0.913, Tmax = 0.977

  • 9227 measured reflections

  • 2093 independent reflections

  • 1668 reflections with I > 2σ(I)

  • Rint = 0.082

  • θmax = 25.0°

  • h = −12 → 12

  • k = −10 → 10

  • l = −15 → 15

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.106

  • S = 1.08

  • 2093 reflections

  • 140 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0601P)2 + 0.0328P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.34 e Å−3

Table 1
Hydrogen-bonding geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N21—H21⋯N3i 0.88 2.14 3.016 (2) 173
N21—H22⋯O51ii 0.88 2.02 2.858 (2) 158
Symmetry codes: (i) 1-x,1-y,1-z; (ii) [{\script{3\over 2}}-x,{\script{1\over 2}}+y,{\script{3\over 2}}-z].

Compound (II)[link]

Crystal data
  • C6H6N2S·C3H4N2S

  • Mr = 238.33

  • Triclinic, [P\overline 1]

  • a = 6.9195 (2) Å

  • b = 9.1860 (2) Å

  • c = 9.6953 (3) Å

  • α = 69.5204 (17)°

  • β = 71.4823 (16)°

  • γ = 74.2770 (17)°

  • V = 538.48 (3) Å3

  • Z = 2

  • Dx = 1.470 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 9410 reflections

  • θ = 2.9–27.5°

  • μ = 0.47 mm−1

  • T = 120 (2) K

  • Plate, colourless

  • 0.26 × 0.08 × 0.04 mm

Data collection
  • Bruker–Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SORTAV; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-37.]) Tmin = 0.885, Tmax = 0.982

  • 12 593 measured reflections

  • 2472 independent reflections

  • 2224 reflections with I > 2σ(I)

  • Rint = 0.072

  • θmax = 27.6°

  • h = −8 → 9

  • k = −11 → 11

  • l = −12 → 12

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.105

  • S = 1.05

  • 2472 reflections

  • 137 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0468P)2 + 0.3904P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.44 e Å−3

Table 2
Hydrogen-bonding geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N21B—H21B⋯N3Bi 0.88 2.14 3.010 (2) 170
N21B—H22B⋯N7A 0.88 2.10 2.933 (2) 159
C2A—H2A⋯N21Bii 0.95 2.59 3.531 (2) 174
Symmetry codes: (i) -x,1-y,1-z; (ii) x,y-1,z.

All H atoms were included in the refinement at calculated positions in the riding-model approximation, with N—H distances of 0.88 Å, and C—H distances of 0.95 (aromatic H atoms), 0.98 (CH3 H atoms) and 0.99 Å (CH2 H atoms), and with Uiso(H) = 1.25Ueq(C,N).

For both compounds, data collection: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO and COLLECT; data reduction: DENZO, SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLUTON94 (Spek, 1994[Spek, A. L. (1994). PLUTON94. University of Utrecht, The Netherlands.]) and PLATON97 (Spek, 1997[Spek, A. L. (1997). PLATON97. University of Utrecht, The Netherlands.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Aminothiazoles have been extensively studied for a range of biological and industrial applications (Lynch et al., 1999; Toplak et al., 2003). 2-Amino-1,3-thiazole, the structure of which was reported in 1982 (Caranoni & Reboul, 1982), is itself listed as a thyroid inhibitor (Merck Index, 2001). A search of the Cambridge Structural Database (CSD, Version?; Allen, 2002) reveals that there are 73 crystal structures containing the 2-aminothiazole moiety, with 51 of those being pure organics. The present authors have recently published a paper on the packing modes of 2-amino-4-phenyl-1,3-thiazole derivatives (Lynch et al., 2002) and have been investigating the structural aspects of 2-aminothiazole derivatives for the last six years. One such compound reported during this time was ethyl 4-tert-butyl-2-(3-phenylureido)-1,3-thiazole-5-carboxylate (Lynch & McClenaghan, 2002), which is currently the only structure of a 4-tert-butyl-5-ester derivative of an aminothiazole. However, we have recently determined the structure of ethyl 2-amino-4-tert-butyl-1,3-thiazole-5-carboxylate, (I), and report it here.

Another aminothiazole derivative is imidazo[2,1-b]thiazole, which has 11 analogues whose structures have been previously reported in the CSD. This bicyclic ring system can be prepared by refluxing a halomethylketone with 2-aminothiazole in ethanol. In an attempt to do so, using chloroacetone, an incomplete reaction yielded a mixture of the imidazo[2,1-b]thiazole derivative with the starting thiazole. The crystals that formed from the impure product were subsequently found to contain the 1:1 adduct of 6-methylimidazo[2,1-b]thiazole with 2-aminothiazole, (II), the structure of which is also reported here. \sch

The structure of (I) consists of a single molecule (Fig. 1) which associates, via hydrogen-bonding interactions, to three symmetry-equivalent molecules (Fig. 2). One symmetry-equivalent molecule forms a hydrogen-bonded R22(8) graph-set dimer (Etter, 1990) with (I) through an N—H···N interaction (Table 1), a feature common for 2-aminothiazole derivatives, while the other two associate to and from (I) through an N—H···O interaction. A similar packing mode has previously been observed in the structure of ethyl 2-amino-4-phenyl-1,3-thiazole-5-carboxylate (Lynch et al., 2002), but is not observed in any other 5-ester substituted 2-aminothiazole. This is probably due to the fact that, in each of these other structures, there are alternative exocyclic hydrogen-bonding acceptor atoms in addition to the two carboxylate O atoms. The ethyl chain twists out of the plane of the thiazole ring, with the C51—O52—C53—C54 torsion angle being 85.5 (2)°, compared with −168.5 (3)° in ethyl 4-tert-butyl-2-(3-phenylureido)-1,3-thiazole-5-carboxylate (Lynch & McClenaghan, 2002). One of the methyl groups in the tert-butyl moiety is aligned with the thiazole ring, with the N3—C4—C41—C42 torsion angle being −1.8 (2)°, similar to what was observed in ethyl 4-tert-butyl-2-(3-phenylureido)-1,3-thiazole-5-carboxylate [comparative torsion angle 7.2 (5)°].

The structure of (II) comprises two adduct molecules associated by a single hydrogen-bonding interaction from one of the 2-amino H atoms to the Nsp2 atom in the imidazothiazole (Fig. 3). Although one of the present authors (DEL) has determined 16 co-crystal structures containing 2-aminothiazole derivatives, there are only two previously reported co-crystals containing 2-aminothiazole itself (Kuz'mina & Struchkov, 1984; Moers et al., 2000), and both of these are organic salts. The structure of (II) is unique in that it is the first adduct (not an organic salt) of 2-aminothiazole. The molecules in (II) pack across an inversion centre to construct an associated quartet, with the 2-aminothiazoles forming a hydrogen-bonded R22(8) graph-set dimer (Fig. 4). Hydrogen-bonding associations are listed in Table 2. A C—H···N close contact is also observed between atom C2A and the 2-amino N atom. The distance between atoms N7A and S1B is 3.294 (3) Å.

The determination of the structure of (II), and examination of the packing associations, may now lead to a series of adducts containing 2-aminothiazole and heterocyclic bases, as opposed to continuing to try to obtain co-crystals (either adducts or organic salts) with organic acids.

Experimental top

Compound (I) was obtained from Key Organics Ltd. and was crystallized from ethanol. Compound (II) was prepared by refluxing equimolar amounts of 2-amino-1,3-thiazole and chloroacetone in ethanol for 16 h. Upon removal of the reaction solvent, the product was washed with aqueous NaOH and then extracted into dichloromethane. Crystals of (II) grew from the resultant liquid after removal of the extraction solvent.

Refinement top

All H atoms were included in the refinement at calculated positions, in the riding-model approximation, with N—H distances of 0.88 Å, and C—H distances of 0.95 (aromatic H atoms), 0.98 (CH3 H atoms) and 0.99 Å (CH2 H atoms), and with Uiso(H) = 1.25Ueq(C,N).

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for (I); DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998) for (II). For both compounds, cell refinement: DENZO and COLLECT; data reduction: DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-numbering scheme for (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (I). [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 3/2 − x, y + 1/2, 3/2 − z.]
[Figure 3] Fig. 3. The molecular configuration and atom-numbering scheme for (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. A packing diagram for (II). [Symmetry code: (i) −x, 1 − y, 1 − z.]
(I) Ethyl 2-amino-4-tert-butyl-1,3-thiazole-5-carboxylate top
Crystal data top
C10H16N2O2SF(000) = 488
Mr = 228.31Dx = 1.276 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3289 reflections
a = 10.6248 (8) Åθ = 2.9–27.5°
b = 8.6055 (5) ŵ = 0.26 mm1
c = 13.0135 (9) ÅT = 120 K
β = 92.977 (4)°Prism, colourless
V = 1188.24 (14) Å30.42 × 0.32 × 0.08 mm
Z = 4
Data collection top
Bruker-Nonius KappaCCD area-detector
diffractometer
2093 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1668 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.082
Detector resolution: 9.091 pixels mm-1θmax = 25.0°, θmin = 3.1°
ϕ and ω scansh = 1212
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 1010
Tmin = 0.913, Tmax = 0.977l = 1515
9227 measured reflections
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0601P)2 + 0.0328P]
where P = (Fo2 + 2Fc2)/3
2093 reflections(Δ/σ)max < 0.001
140 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C10H16N2O2SV = 1188.24 (14) Å3
Mr = 228.31Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.6248 (8) ŵ = 0.26 mm1
b = 8.6055 (5) ÅT = 120 K
c = 13.0135 (9) Å0.42 × 0.32 × 0.08 mm
β = 92.977 (4)°
Data collection top
Bruker-Nonius KappaCCD area-detector
diffractometer
2093 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1668 reflections with I > 2σ(I)
Tmin = 0.913, Tmax = 0.977Rint = 0.082
9227 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 1.08Δρmax = 0.20 e Å3
2093 reflectionsΔρmin = 0.34 e Å3
140 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.73102 (5)0.23587 (6)0.65724 (3)0.02690 (19)
C20.62597 (18)0.3504 (2)0.58627 (14)0.0256 (5)
N210.57163 (16)0.47329 (19)0.62767 (12)0.0318 (4)
H210.51860.53090.59000.040*
H220.58870.49690.69270.040*
N30.60506 (15)0.30740 (18)0.48900 (11)0.0242 (4)
C40.67079 (18)0.1747 (2)0.46746 (14)0.0233 (4)
C410.64797 (18)0.1044 (2)0.35997 (14)0.0260 (5)
C420.5490 (2)0.1988 (3)0.29758 (15)0.0366 (5)
H410.47130.20360.33480.046*
H420.53160.14910.23060.046*
H430.58070.30430.28730.046*
C430.7696 (2)0.1048 (2)0.30173 (15)0.0326 (5)
H440.80070.21160.29640.041*
H450.75260.06220.23260.041*
H460.83330.04110.33890.041*
C440.5958 (2)0.0610 (2)0.37003 (15)0.0306 (5)
H470.65900.12660.40640.038*
H480.57590.10390.30130.038*
H490.51910.05810.40880.038*
C50.74610 (18)0.1188 (2)0.54923 (14)0.0249 (4)
C510.83058 (18)0.0117 (2)0.56901 (14)0.0261 (5)
O510.87845 (14)0.03732 (17)0.65452 (10)0.0345 (4)
O520.85479 (13)0.09931 (15)0.48804 (9)0.0288 (3)
C530.9321 (2)0.2367 (2)0.50785 (16)0.0312 (5)
H510.99640.21440.56370.039*
H520.97640.26400.44520.039*
C540.8522 (3)0.3706 (2)0.5382 (2)0.0484 (6)
H530.80940.34400.60080.060*
H540.90550.46210.55120.060*
H550.78930.39330.48250.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0291 (3)0.0302 (3)0.0211 (3)0.0021 (2)0.0018 (2)0.0009 (2)
C20.0268 (11)0.0267 (10)0.0232 (10)0.0036 (8)0.0002 (8)0.0000 (8)
N210.0404 (11)0.0325 (9)0.0220 (8)0.0094 (8)0.0049 (7)0.0022 (8)
N30.0277 (9)0.0246 (8)0.0203 (8)0.0001 (7)0.0004 (7)0.0006 (7)
C40.0235 (10)0.0247 (10)0.0219 (9)0.0045 (8)0.0031 (8)0.0015 (8)
C410.0264 (11)0.0305 (11)0.0213 (9)0.0015 (8)0.0012 (8)0.0005 (8)
C420.0438 (14)0.0413 (12)0.0237 (10)0.0090 (10)0.0068 (9)0.0071 (9)
C430.0385 (13)0.0374 (12)0.0225 (10)0.0001 (10)0.0071 (9)0.0011 (9)
C440.0306 (12)0.0337 (11)0.0276 (10)0.0024 (9)0.0029 (9)0.0067 (9)
C50.0272 (11)0.0270 (10)0.0208 (9)0.0024 (8)0.0030 (8)0.0006 (8)
C510.0255 (11)0.0292 (11)0.0239 (10)0.0035 (8)0.0039 (8)0.0021 (9)
O510.0395 (9)0.0393 (9)0.0241 (7)0.0101 (7)0.0042 (6)0.0016 (6)
O520.0315 (8)0.0315 (8)0.0233 (7)0.0067 (6)0.0017 (6)0.0011 (6)
C530.0293 (12)0.0332 (11)0.0315 (11)0.0087 (9)0.0046 (9)0.0010 (9)
C540.0551 (16)0.0331 (12)0.0583 (15)0.0020 (11)0.0163 (13)0.0017 (12)
Geometric parameters (Å, º) top
S1—C21.7214 (19)C43—H450.98
S1—C51.7434 (18)C43—H460.98
C2—N31.327 (2)C44—H470.98
C2—N211.332 (2)C44—H480.98
N21—H210.88C44—H490.98
N21—H220.88C5—C511.452 (3)
N3—C41.375 (2)C51—O511.219 (2)
C4—C51.384 (3)C51—O521.332 (2)
C4—C411.532 (2)O52—C531.455 (2)
C41—C421.529 (3)C53—C541.496 (3)
C41—C431.532 (3)C53—H510.99
C41—C441.535 (3)C53—H520.99
C42—H410.98C54—H530.98
C42—H420.98C54—H540.98
C42—H430.98C54—H550.98
C43—H440.98
C2—S1—C588.99 (9)H44—C43—H46109.5
N3—C2—N21123.57 (17)H45—C43—H46109.5
N3—C2—S1115.09 (14)C41—C44—H47109.5
N21—C2—S1121.34 (14)C41—C44—H48109.5
C2—N21—H21120.0H47—C44—H48109.5
C2—N21—H22120.0C41—C44—H49109.5
H21—N21—H22120.0H47—C44—H49109.5
C2—N3—C4111.38 (15)H48—C44—H49109.5
N3—C4—C5114.28 (16)C4—C5—C51137.07 (18)
N3—C4—C41117.14 (15)C4—C5—S1110.22 (14)
C5—C4—C41128.52 (17)C51—C5—S1112.69 (13)
C42—C41—C4110.29 (16)O51—C51—O52122.07 (17)
C42—C41—C43108.08 (16)O51—C51—C5121.76 (18)
C4—C41—C43110.68 (16)O52—C51—C5116.15 (16)
C42—C41—C44107.26 (17)C51—O52—C53116.77 (14)
C4—C41—C44109.21 (15)O52—C53—C54110.44 (17)
C43—C41—C44111.25 (16)O52—C53—H51109.6
C41—C42—H41109.5C54—C53—H51109.6
C41—C42—H42109.5O52—C53—H52109.6
H41—C42—H42109.5C54—C53—H52109.6
C41—C42—H43109.5H51—C53—H52108.1
H41—C42—H43109.5C53—C54—H53109.5
H42—C42—H43109.5C53—C54—H54109.5
C41—C43—H44109.5H53—C54—H54109.5
C41—C43—H45109.5C53—C54—H55109.5
H44—C43—H45109.5H53—C54—H55109.5
C41—C43—H46109.5H54—C54—H55109.5
C5—S1—C2—N31.16 (16)C41—C4—C5—C512.1 (4)
C5—S1—C2—N21179.29 (17)N3—C4—C5—S11.1 (2)
N21—C2—N3—C4178.48 (18)C41—C4—C5—S1176.03 (16)
S1—C2—N3—C42.0 (2)C2—S1—C5—C40.00 (15)
C2—N3—C4—C52.0 (2)C2—S1—C5—C51178.60 (15)
C2—N3—C4—C41175.51 (16)C4—C5—C51—O51174.3 (2)
N3—C4—C41—C421.8 (2)S1—C5—C51—O513.8 (2)
C5—C4—C41—C42175.29 (19)C4—C5—C51—O527.1 (3)
N3—C4—C41—C43117.77 (19)S1—C5—C51—O52174.81 (13)
C5—C4—C41—C4365.2 (3)O51—C51—O52—C535.6 (3)
N3—C4—C41—C44119.42 (18)C5—C51—O52—C53175.82 (16)
C5—C4—C41—C4457.7 (3)C51—O52—C53—C5485.5 (2)
N3—C4—C5—C51179.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···N3i0.882.143.016 (2)173
N21—H22···O51ii0.882.022.858 (2)158
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+3/2, y+1/2, z+3/2.
(II) 6-Methylimidazo[2,1-b]thiazole 2-amino-1,3-thiazole top
Crystal data top
C6H6N2S·C3H4N2SZ = 2
Mr = 238.33F(000) = 248
Triclinic, P1Dx = 1.470 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9195 (2) ÅCell parameters from 9410 reflections
b = 9.1860 (2) Åθ = 2.9–27.5°
c = 9.6953 (3) ŵ = 0.47 mm1
α = 69.5204 (17)°T = 120 K
β = 71.4823 (16)°Plate, colourless
γ = 74.2770 (17)°0.26 × 0.08 × 0.04 mm
V = 538.48 (3) Å3
Data collection top
Bruker-Nonius KappaCCD area-detector
diffractometer
2472 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2224 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.072
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 3.2°
ϕ and ω scansh = 89
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 1111
Tmin = 0.885, Tmax = 0.982l = 1212
12593 measured reflections
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0468P)2 + 0.3904P]
where P = (Fo2 + 2Fc2)/3
2472 reflections(Δ/σ)max < 0.001
137 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
C6H6N2S·C3H4N2Sγ = 74.2770 (17)°
Mr = 238.33V = 538.48 (3) Å3
Triclinic, P1Z = 2
a = 6.9195 (2) ÅMo Kα radiation
b = 9.1860 (2) ŵ = 0.47 mm1
c = 9.6953 (3) ÅT = 120 K
α = 69.5204 (17)°0.26 × 0.08 × 0.04 mm
β = 71.4823 (16)°
Data collection top
Bruker-Nonius KappaCCD area-detector
diffractometer
2472 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
2224 reflections with I > 2σ(I)
Tmin = 0.885, Tmax = 0.982Rint = 0.072
12593 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.05Δρmax = 0.26 e Å3
2472 reflectionsΔρmin = 0.44 e Å3
137 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1A0.00960 (8)0.08327 (6)0.30204 (5)0.03224 (15)
C2A0.1187 (3)0.2132 (2)0.1913 (2)0.0286 (4)
H2A0.10300.32070.22630.036*
C3A0.2265 (3)0.1461 (2)0.0524 (2)0.0243 (4)
H3A0.29550.19990.02250.030*
N4A0.2258 (2)0.01230 (17)0.03015 (16)0.0202 (3)
C5A0.3102 (3)0.1371 (2)0.0801 (2)0.0233 (4)
H5A0.39490.13790.17900.029*
C6A0.2462 (3)0.2595 (2)0.0171 (2)0.0226 (4)
C61A0.2951 (3)0.4226 (2)0.0846 (2)0.0301 (4)
H61A0.36030.44350.01900.038*
H62A0.16700.49960.09370.038*
H63A0.39020.43160.18550.038*
N7A0.1235 (2)0.21473 (18)0.12958 (17)0.0249 (3)
C8A0.1169 (3)0.0656 (2)0.15266 (19)0.0226 (4)
S1B0.43793 (7)0.20121 (5)0.32915 (5)0.02753 (15)
C2B0.2352 (3)0.3412 (2)0.39595 (19)0.0214 (3)
N21B0.0592 (2)0.38726 (19)0.34887 (18)0.0271 (3)
H21B0.04150.45740.38370.034*
H22B0.04480.34730.28320.034*
N3B0.2716 (2)0.39372 (18)0.49329 (17)0.0240 (3)
C4B0.4678 (3)0.3223 (2)0.5168 (2)0.0256 (4)
H4B0.52060.34620.58410.032*
C5B0.5789 (3)0.2182 (2)0.4401 (2)0.0294 (4)
H5B0.71480.16210.44570.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0402 (3)0.0267 (3)0.0227 (2)0.0067 (2)0.0004 (2)0.00468 (19)
C2A0.0265 (9)0.0212 (9)0.0359 (10)0.0024 (7)0.0074 (8)0.0073 (8)
C3A0.0220 (8)0.0198 (8)0.0329 (10)0.0007 (7)0.0073 (7)0.0115 (7)
N4A0.0189 (7)0.0199 (7)0.0216 (7)0.0012 (5)0.0053 (5)0.0073 (6)
C5A0.0209 (8)0.0242 (9)0.0224 (8)0.0043 (7)0.0031 (6)0.0058 (7)
C6A0.0225 (8)0.0205 (8)0.0257 (9)0.0028 (6)0.0098 (7)0.0051 (7)
C61A0.0314 (10)0.0210 (9)0.0369 (11)0.0039 (7)0.0116 (8)0.0052 (8)
N7A0.0302 (8)0.0223 (7)0.0232 (7)0.0025 (6)0.0080 (6)0.0082 (6)
C8A0.0244 (8)0.0230 (8)0.0198 (8)0.0021 (7)0.0059 (7)0.0069 (7)
S1B0.0291 (3)0.0251 (3)0.0274 (3)0.00164 (18)0.00392 (18)0.01401 (19)
C2B0.0247 (8)0.0162 (8)0.0204 (8)0.0027 (6)0.0013 (6)0.0065 (6)
N21B0.0271 (8)0.0276 (8)0.0316 (8)0.0007 (6)0.0084 (6)0.0176 (7)
N3B0.0262 (8)0.0217 (7)0.0246 (8)0.0019 (6)0.0052 (6)0.0102 (6)
C4B0.0294 (9)0.0230 (9)0.0238 (9)0.0054 (7)0.0069 (7)0.0052 (7)
C5B0.0272 (9)0.0271 (9)0.0308 (10)0.0011 (7)0.0069 (7)0.0077 (8)
Geometric parameters (Å, º) top
S1A—C8A1.7324 (18)C61A—H62A0.98
S1A—C2A1.743 (2)C61A—H63A0.98
C2A—C3A1.334 (3)N7A—C8A1.319 (2)
C2A—H2A0.95S1B—C5B1.732 (2)
C3A—N4A1.393 (2)S1B—C2B1.7518 (17)
C3A—H3A0.95C2B—N3B1.312 (2)
N4A—C8A1.363 (2)C2B—N21B1.345 (2)
N4A—C5A1.381 (2)N21B—H21B0.88
C5A—C6A1.368 (3)N21B—H22B0.88
C5A—H5A0.95N3B—C4B1.391 (2)
C6A—N7A1.388 (2)C4B—C5B1.340 (3)
C6A—C61A1.495 (3)C4B—H4B0.95
C61A—H61A0.98C5B—H5B0.95
C8A—S1A—C2A89.74 (9)H61A—C61A—H63A109.5
C3A—C2A—S1A113.09 (14)H62A—C61A—H63A109.5
C3A—C2A—H2A123.5C8A—N7A—C6A104.09 (14)
S1A—C2A—H2A123.5N7A—C8A—N4A112.88 (15)
C2A—C3A—N4A111.98 (16)N7A—C8A—S1A136.17 (14)
C2A—C3A—H3A124.0N4A—C8A—S1A110.93 (13)
N4A—C3A—H3A124.0C5B—S1B—C2B89.06 (9)
C8A—N4A—C5A106.52 (14)N3B—C2B—N21B124.61 (16)
C8A—N4A—C3A114.26 (15)N3B—C2B—S1B114.35 (13)
C5A—N4A—C3A139.17 (15)N21B—C2B—S1B121.04 (13)
C6A—C5A—N4A105.51 (15)C2B—N21B—H21B120.0
C6A—C5A—H5A127.2C2B—N21B—H22B120.0
N4A—C5A—H5A127.2H21B—N21B—H22B120.0
C5A—C6A—N7A110.99 (16)C2B—N3B—C4B109.87 (15)
C5A—C6A—C61A128.64 (17)C5B—C4B—N3B116.87 (17)
N7A—C6A—C61A120.35 (16)C5B—C4B—H4B121.6
C6A—C61A—H61A109.5N3B—C4B—H4B121.6
C6A—C61A—H62A109.5C4B—C5B—S1B109.85 (15)
H61A—C61A—H62A109.5C4B—C5B—H5B125.1
C6A—C61A—H63A109.5S1B—C5B—H5B125.1
C8A—S1A—C2A—C3A0.24 (15)C3A—N4A—C8A—N7A178.36 (14)
S1A—C2A—C3A—N4A0.2 (2)C5A—N4A—C8A—S1A178.08 (11)
C2A—C3A—N4A—C8A0.0 (2)C3A—N4A—C8A—S1A0.15 (19)
C2A—C3A—N4A—C5A176.93 (19)C2A—S1A—C8A—N7A177.8 (2)
C8A—N4A—C5A—C6A0.15 (18)C2A—S1A—C8A—N4A0.22 (14)
C3A—N4A—C5A—C6A177.26 (19)C5B—S1B—C2B—N3B0.48 (14)
N4A—C5A—C6A—N7A0.16 (19)C5B—S1B—C2B—N21B179.75 (16)
N4A—C5A—C6A—C61A178.67 (17)N21B—C2B—N3B—C4B179.87 (17)
C5A—C6A—N7A—C8A0.4 (2)S1B—C2B—N3B—C4B0.36 (19)
C61A—C6A—N7A—C8A178.53 (16)C2B—N3B—C4B—C5B0.0 (2)
C6A—N7A—C8A—N4A0.5 (2)N3B—C4B—C5B—S1B0.4 (2)
C6A—N7A—C8A—S1A177.48 (16)C2B—S1B—C5B—C4B0.45 (15)
C5A—N4A—C8A—N7A0.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21B—H21B···N3Bi0.882.143.010 (2)170
N21B—H22B···N7A0.882.102.933 (2)159
C2A—H2A···N21Bii0.952.593.531 (2)174
Symmetry codes: (i) x, y+1, z+1; (ii) x, y1, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC10H16N2O2SC6H6N2S·C3H4N2S
Mr228.31238.33
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)120120
a, b, c (Å)10.6248 (8), 8.6055 (5), 13.0135 (9)6.9195 (2), 9.1860 (2), 9.6953 (3)
α, β, γ (°)90, 92.977 (4), 9069.5204 (17), 71.4823 (16), 74.2770 (17)
V3)1188.24 (14)538.48 (3)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.260.47
Crystal size (mm)0.42 × 0.32 × 0.080.26 × 0.08 × 0.04
Data collection
DiffractometerBruker-Nonius KappaCCD area-detector
diffractometer
Bruker-Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Multi-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.913, 0.9770.885, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
9227, 2093, 1668 12593, 2472, 2224
Rint0.0820.072
(sin θ/λ)max1)0.5950.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.106, 1.08 0.040, 0.105, 1.05
No. of reflections20932472
No. of parameters140137
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.340.26, 0.44

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N21—H21···N3i0.882.143.016 (2)173
N21—H22···O51ii0.882.022.858 (2)158
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+3/2, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N21B—H21B···N3Bi0.882.143.010 (2)170
N21B—H22B···N7A0.882.102.933 (2)159
C2A—H2A···N21Bii0.952.593.531 (2)174
Symmetry codes: (i) x, y+1, z+1; (ii) x, y1, z.
 

Acknowledgements

The authors thank the EPSRC National Crystallography Service, Southampton, England.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–37.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationCaranoni, P. C. & Reboul, J. P. (1982). Acta Cryst. B38, 1255–1259.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationEtter, M. C. (1990). Acc. Chem. Res. 23, 120–126.  CrossRef CAS Web of Science Google Scholar
First citationKuz'mina, L. G. & Struchkov, Y. T. (1984). Zh. Strukt. Khim. 25, 88–92. (In Russian.)  CAS Google Scholar
First citationLynch, D. E. & McClenaghan, I. (2002). Acta Cryst. E58, o733–o734.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLynch, D. E., McClenaghan, I., Light, M. E. & Coles, S. J. (2002). Cryst. Eng. 5, 123–136.  Web of Science CSD CrossRef CAS Google Scholar
First citationLynch, D. E., Nicholls, L. J., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1999). Acta Cryst. B55, 758–766.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationMerck (2001). The Merck Index, 13th ed. New York: John Wiley & Sons.  Google Scholar
First citationMoers, O., Wijaya, K., Lange, I., Blaschette, A. & Jones, P. G. (2000). Z. Naturforsch. Teil B, 55, 738–752.  CAS Google Scholar
First citationNonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSpek, A. L. (1994). PLUTON94. University of Utrecht, The Netherlands.  Google Scholar
First citationSpek, A. L. (1997). PLATON97. University of Utrecht, The Netherlands.  Google Scholar
First citationToplak, R., Lah, N., Volmajer, J., Leban, I. & Le Maréchal, A. M. (2003). Acta Cryst. C59, o502–o505.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds