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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 62| Part 1| January 2006| Pages o324-o326
doi:10.1107/S1600536805041899

Ethyl 2-({6-amino-2-(benzyl­sulfan­yl)-5-[2-(eth­oxy­carbon­yl)prop-2-en­yl]pyrimidin-4-yl­­oxy}meth­yl)­acrylate

CROSSMARK_Color_square_no_text.svg
Colin L. Gibson,a Judith K. Huggan,a Alan R. Kennedya and Colin J. Sucklinga*

aWestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, Scotland
*Correspondence e-mail: a.r.kennedy@strath.ac.uk

(Received 5 December 2005; accepted 14 December 2005; online 21 December 2005)

A new synthesis of carbon–carbon bonds at the 5-position of 2-thio­substituted pyrimidines via the Claisen rearrangement is reported. A direct route towards the synthesis of carbon bonds at the 5-position of 2-thio­benzyl pyrimidines when reacted with ethyl 2-(bromo­meth­yl)acrylate at 328 K delivered the unexpected title compound, C23H27N3O5S. Structural elucidation showed this compound to have undergone O-allyl­ation followed by ortho-Claisen rearrangement and subsequent secondary O-allyl­ation with excess ethyl 2-(bromo­meth­yl)acrylate. Disorder about the centre of symmetry allows it to exist as two conformers with different orientations of the phenyl group.

Comment

In order to extend and illustrate our endeavours to develop further the C-5 carbon–carbon bond formation of 2-thio­substituted pyrimidines (Huggan et al., 2005[Huggan, J. K., Gibson, C. L., Kiefer, L. & Suckling, C. J. (2005). Chem Biol. Pteridines Folates, 16, 53-57.]; La Rosa et al., 2002[La Rosa, S., Boyle, P. H., Gibson, C. L., Guiney, D. & Suckling, C. J. (2002). Chem. Biol. Pteridines Folates, 11, 25-29.]) we sought to utilize the Claisen rearrangement (Claisen & Tietze, 1925[Claisen, L. & Tietze, E. (1925). Berichte, 58, 275.]) within the context of designing routes towards the synthesis of pyrido[2,3-d]-pyrimidines, (I)[link], and pyrrolo[2,3-d]-pyrimidines, (II)[link], as potential inhibitors of enzymes in the folic acid biosynthesis pathway. When an N atom is present at the 2-position, the formation of C—C bonds at the 5-position is relatively straightforward. However, our solid phase route (Gibson et al., 2003[Gibson, C. L., La Rosa, S. & Suckling, C. J. (2003). Org. Biomol. Chem. pp. 1909-1918.]) utilizes an S atom at the 2-position and previous attempts at C—C bond formation in solution phase with sulfur at the 2-position have proved unsuccessful.

[Scheme 1]

Structurally related folic acid antagonists (Taylor et al., 1983[Taylor, E. C., Palmer, D. C., George, T. J., Fletcher, S. R., Tseng, C. P., Harrington, P. J. & Beardsley, G. P. (1983). J. Org. Chem. 48, 4852-4860.]) have been shown to possess a range of biological properties, such as anti­tumour (Grivsky et al., 1980[Grivsky, E. M., Lee, S., Sigel, C. W., Duch, D. S. & Nichol, C. A. (1980). J. Med. Chem. 23, 327-329.]), anti­bacterial (Matsumoto & Minami, 1975[Matsumoto, J. & Minami, S. (1975). J. Med. Chem. 18, 74-79.]) and anti­fungal (Heckler et al., 1991[Heckler, R. E. & Jourdan, G. P. (1991). European Patent 414 386.]) activity, and hence their efficient synthesis, along with the synthesis of other novel compounds, would be advantageous. The commercially available 6-amino-2-mercaptopyrimidin-4(3H)-one was reacted with benzyl mercaptan to yield 6-amino-2-(benzyl­sulfan­yl)-4(3H)-pyrimidinone, (III)[link] (90%). Compound (III) was then reacted with ethyl 2-(bromo­meth­yl)acrylate to give products, from which the title compound, (IV)[link], was surprisingly isolated and identified.

[Scheme 2]

The mol­ecular structure of (IV)[link] is shown in Fig. 1[link], and selected bond distances and angles are given in Table 1[link]. As can be seen in Fig. 1[link], structural elucidation showed this compound to have been formed through O-allyl­ation followed by ortho-Claisen rearrangement and subsequent secondary O-allyl­ation with excess ethyl 2-(bromo­meth­yl)acrylate.

Disorder about a centre of symmetry allows (IV)[link] to exist as two conformers with different orientations of the phenyl group. An alternative solution in the non-centrosymmetric space group P1 was rejected as the disorder was still present. The two vinyl groups adopt different geometries. The torsion angles C13—C12—C14—O4 and C7—C6—C8—O2 [−13.1 (2) and 176.8 (2)°, respectively] indicate the syn and anti relationship of the vinyl and ketone groups and, whilst the presence of O1 allows the C7-centred group to bo coplanar with the heterocyclic ring, the absence of an equivalent atom forces the C13-centred substituent out of this plane. A search of the Cambridge Structural Database (Version 5 with updates to October 2005; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) found 140 similar non-cyclic vinyl fragments and indicated that the geometric parameters of (IV)[link] (Table 1[link]) are all within normal ranges. A similar search showed that the geometry of the hetrocyclic fragment is also in agreement with the known literature.

In the crystal structure of (IV)[link] both the amine H atoms form hydrogen bonds with atoms O4 and N2 of symmetry-related mol­ecules acting as acceptors (Table 2[link]). This results in the formation of hydrogen-bonded chains of mol­ecules.

[Figure 1]
Figure 1
Mol­ecular structure of (IV)[link], with displacement ellipsoids drawn at the 50% probability level. Only one position of the disordered benzyl unit is shown for clarity.

Experimental

Compound (III) (0.69 g, 2.95 mmol) was dissolved in dimethyl­formamide (12 ml, anhydrous) at room temperature under nitro­gen. Ethyl 2-(bromo­meth­yl)acrylate (610 µl, 4.40 mmol, 1.5 equivalents) and K2CO3 (0.50 g, 3.62 mmol, 1.2 equivalents) were added and the reaction was stirred in an oil bath at 328 K for 24 h. Once the reaction was complete (by thin-layer chromatography) the mixture was cooled to room temperature and the solvent was evaporated under reduced pressure. The residue was dissolved in dichloro­methane, extracted with brine, and then collected, dried (MgSO4) and concentrated under reduced pressure to give a yellow oil. The title compound (IV)[link] was separated by column chromatography using ethyl acetate/hexane (1:1) as eluant, and was isolated as a white solid (0.114 g, 0.25 mmol, 8%). Crystals of (IV)[link] were grown by slow recrystallization from methanol at room temperature (m.p. 383–385 K). IR (KBr): 3407, 3323, 3191, 1707, 1652, 1572, 1555, 1493, 1474, 1444, 1427, 1401, 1376, 1353, 1316, 1280, 1264, 1227, 1158, 1123, 1050, 1027, 855, 776, 708 cm−1; LC–MS: (M+1) = 458.3; 1H NMR (DMSO-d6): δ 7.41–7.39 [2H, m, 2 × C(2)H], 7.31–7.19 [3H, m, 2 × C(3)H, 1 × C(1)H], 6.19 (2H, br s, NH2), 6.19 [1H, s, C(18A)H], 5.99 [1H, s, C(12B)H], 5.75 [1H, s, C(12A)H], 5.14 [1H, s, C(18B)H], 4.98 [2H, s, C(16)H2], 4.29 [2H, s, C(5)H2], 4.20–4.09 [4H, d of q, 1 × 2H, q, C(20)H, 1 × 2H, q, C(14)H], 3.33 [2H, s, C(10)H2], 1.26–1.15 [6H, d of t, 1 × 3H, t, C(21)H, 1 × 3H, t, C(15)H]; 13C NMR (DMSO-d6): δ 166.39 (C-19), 166.18 (C-13), 165.44 (C-7), 164.75 (C-6), 163.39 (C-9), 138.66 (C-4), 137.02 (C-17), 136.31 (C-11), 128.77 (C-2), 128.28 (C-3), 126.82 (C-1), 126.08 (C-12), 123.07 (C-18), 90.74 (C-8), 63.49 (C-16), 60.49 (C-20), 60.34 (C-14), 33.83 (C-5), 24.39 (C-10), 14.04 (C-15), 13.91 (C-21).

Crystal data

  • C23H27N3O5S

  • Mr = 457.54

  • Triclinic, [P \overline 1]

  • a = 7.3668 (2) Å

  • b = 11.5842 (3) Å

  • c = 14.5700 (4) Å

  • α = 111.692 (2)°

  • β = 99.520 (2)°

  • γ = 93.076 (2)°

  • V = 1130.44 (5) Å3

  • Z = 2

  • Dx = 1.344 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 5141 reflections

  • θ = 1.0–27.5°

  • μ = 0.18 mm−1

  • T = 123 (2) K

  • Prism, colourless

  • 0.45 × 0.15 × 0.10 mm
Data collection

  • Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: none

  • 25883 measured reflections

  • 5178 independent reflections

  • 3777 reflections with I > 2σ(I)

  • Rint = 0.044

  • θmax = 27.5°

  • h = −9 → 9

  • k = −15 → 13

  • l = −18 → 18
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.091

  • S = 1.04

  • 5178 reflections

  • 353 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.0315P)2 + 0.4141P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.27 e Å−3

Table 1
Selected geometric parameters (Å, °)[link]

O2—C8 1.2094 (18)
O4—C14 1.2153 (19)
N1—C1 1.3341 (19)
N1—C2 1.3424 (18)
N2—C1 1.3317 (19)
N2—C4 1.3611 (18)
N3—C4 1.347 (2)
C2—C3 1.386 (2)
C3—C4 1.407 (2)
C6—C7 1.313 (2)
C6—C8 1.484 (2)
C12—C13 1.318 (2)
C12—C14 1.496 (2)
C1—N1—C2 113.72 (13)
C1—N2—C4 116.39 (13)
N2—C1—N1 128.05 (13)
N1—C2—C3 125.47 (14)
C2—C3—C4 114.93 (13)
N2—C4—C3 121.35 (14)
C5—O1—C2—N1 −5.5 (2)
C7—C6—C8—O2 176.82 (19)
C4—C3—C11—C12 96.68 (18)
C13—C12—C14—O4 −13.1 (2)
C1—S1—C17—C18 160.97 (14)
C1—S1—C17—C19 −85.22 (17)

Table 2
Hydrogen-bond geometry (Å, °)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N3—H1N⋯O4i 0.872 (18) 2.133 (19) 2.9832 (18) 164.8 (16)
N3—H2N⋯N2ii 0.883 (19) 2.20 (2) 3.0868 (19) 176.8 (17)
Symmetry codes: (i) -x, -y-1, -z; (ii) -x, -y, -z.

After several trial calculations, the disordered CH2Ph group was modelled over two sites each with occupancy 0.5. The methyl­ene H atoms of this group were found in a difference synthesis and then constrained to ride on the parent C atom. The amine H atoms were refined freely, but all other H atoms were positioned geometrically at distances of 0.95 (CH and vinyl CH2), 0.98 (CH3) or 0.99 Å (CH2) from the parent C atoms; a riding model was used [Uiso(H) = 1.5Ueq(C) for CH3 and Uiso(H) = 1.2Ueq(C) for all others] during refinement.

Data collection: COLLECT (Hooft, 1998[Hooft, R. (1998). COLLECT. Nonius BV, Delft, The Netherlands.]) and 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.]); cell refinement: DENZO; data reduction: DENZO; 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: ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks IV, global. DOI: 10.1107/S1600536805041899/su6257sup1.cif

Structure factors: contains datablock IV. DOI: 10.1107/S1600536805041899/su6257IVsup2.hkl


Comment top

In order to extend and illustrate our endeavours to develop further the C-5 carbon–carbon bond formation of 2-thiosubstituted pyrimidines (Huggan et al., 2005; La Rosa et al., 2002) we sought to utilize the Claisen rearrangement (Claisen & Tietze, 1925) within the context of designing routes towards the synthesis of pyrido[2,3-d]-pyrimidines, (I), and pyrrolo[2,3-d]-pyrimidines, (II), as potential inhibitors of enzymes in the folic acid biosynthesis pathway. When an N atom is present at the 2-position, the formation of C—C bonds at the 5-position is relatively straightforward. However, our solid phase route (Gibson et al., 2003) utilizes an S atom at the 2-position and previous attempts at C—C bond formation in solution phase with sulfur at the 2-position have proved unsuccessful.

Structurally related folic acid antagonists (Taylor et al., 1983) have been shown to possess a range of biological properties, such as antitumour (Grivsky et al., 1980), antibacterial (Matsumoto & Minami, 1975) and antifungal (Heckler et al., 1991) activity, and hence their efficient synthesis, along with the synthesis of other novel compounds, would be advantageous. The commercially available 6-amino-2-mercaptopyrimidin-4(3H)-one was reacted with benzyl mercaptan to yield 6-amino-2-(benzylsulfanyl)-4(3H)-pyrimidinone, (III) (90%). Compound (III) was then reacted with ethyl 2-(bromomethyl)acrylate to give products, from which the title compound, (IV), was surprisingly isolated and identified.

The molecular structure of (IV) is shown in Fig. 1, and selected bond distances and angles are given in Table 1. As can be seen in Fig. 1, structural elucidation showed this compound to have been formed through O-allylation followed by ortho Claisen rearrangement and subsequent secondary O-allylation with excess ethyl 2-(bromomethyl)acrylate.

Disorder about the centre of symmetry allows (IV) to exist as two conformers with different orientations of the phenyl group. An alternative solution in the non-centrosymmetric space group P1 was rejected as the disorder was still present. The two vinyl groups adopt different geometries. The torsion angles C13—C12—C14—O4 and C7—C6—C8—O2 [−13.1 (2) and 176.8 (2)°, respectively] indicate the syn and anti relationship of the vinyl and ketone groups and, whilst the presence of O1 allows the C7-centred group to lie in plane with the heterocyclic ring, the absence of an equivalent atom forces the C13-centred substituent out of this plane. A search of the Cambridge Structural Database (Version 5 with updates to October 2005; Allen, 2002) found 140 similar non-cyclic vinyl fragments and indicated that the geometric parameters of (IV) (Table 1) are all within normal ranges. A similar search showed that the geometry of the hetrocyclic fragment is also in agreement with the known literature.

In the crystal structure of (IV) both the amine H atoms form hydrogen bonds with atoms O4 and N2, acting as acceptors, of symmetry-related molecules (Table 2). This results in the formation of hydrogen-bonded chains of molecules.

Experimental top

Compound (III) (0.69 g, 2.95 mmol) was dissolved in dimethylformamide (12 ml, anhydrous) at room temperature under nitrogen. Ethyl 2-(bromomethyl)acrylate (610 µl, 4.40 mmol, 1.5 equivalents) and K2CO3 (0.50 g, 3.62 mmol, 1.2 equivalents) were added and the reaction was stirred in an oil bath at 328 K for 24 h. Once the reaction was complete (by thin-layer chromatography) the mixture was cooled to room temperature and the solvent was evaporated under reduced pressure. The residue was dissolved in dichloromethane, extracted with brine, and then collected, dried (MgSO4) and concentrated under reduced pressure to give a yellow oil. The title compound (IV) was separated by column chromatography using ethyl acetate/hexane (1:1) as eluant and was isolated as a white solid (0.114 g, 0.25 mmol, 8%). Crystals of (IV) were grown by slow recrystallization from methanol at room temperature (m.p. 383–385 K). IR (KBr): 3407, 3323, 3191, 1707, 1652, 1572, 1555, 1493, 1474, 1444, 1427, 1401, 1376, 1353, 1316, 1280, 1264, 1227, 1158, 1123, 1050, 1027, 855, 776, 708 cm−1; LC–MS: (M+1) = 458.3; 1H NMR (DMSO-d6): δ 7.41–7.39 [2H, m, 2 × C(2)H], 7.31–7.19 [3H, m, 2 × C(3)H, 1 × C(1)H], 6.19 (2H, br s, NH2), 6.19 [1H, s, C(18 A)H], 5.99 [1H, s, C(12B)H], 5.75 [1H, s, C(12 A)H], 5.14 [1H, s, C(18B)H], 4.98 [2H, s, C(16)H2], 4.29 [2H, s, C(5)H2], 4.20–4.09 [4H, d of q, 1 × 2H, q, C(20)H, 1 × 2H, q, C(14)H], 3.33 [2H, s, C(10)H2], 1.26–1.15 [6H, d of t, 1 × 3H, t, C(21)H, 1 × 3H, t, C(15)H]; 13C NMR (DMSO-d6): δ 166.39 (C-19), 166.18 (C-13), 165.44 (C-7), 164.75 (C-6), 163.39 (C-9), 138.66 (C-4), 137.02 (C-17), 136.31 (C-11), 128.77 (C-2), 128.28 (C-3), 126.82 (C-1), 126.08 (C-12), 123.07 (C-18), 90.74 (C-8), 63.49 (C-16), 60.49 (C-20), 60.34 (C-14), 33.83 (C-5), 24.39 (C-10), 14.04 (C-15), 13.91 (C-21).

Refinement top

After several trial calculations, the disordered CH2Ph group was modelled over two sites each with occupancy 0.5. The methylene H atoms of this group were found in a difference synthesis and then constrained to ride on the parent C atom. The amine H atoms were refined freely, but all other H atoms were positioned geometrically at distances of 0.95 (CH and vinyl CH2), 0.98 (CH3) or 0.99 Å (CH2) from the parent C atoms; a riding model was used [Uiso(H) = 1.5Ueq(C) for CH3 and Uiso(H) = 1.2Ueq(C) for all others] during refinement.

Computing details top

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: DENZO; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular structure of (IV), with displacement ellipsoids drawn at the 50% probability level. Only one position of the disordered benzyl unit is shown for clarity.
Ethyl 2-({6-amino-2-(benzylsulfanyl)-5-[2-(ethoxycarbonyl)prop-2-enyl]pyrimidin- 4-yloxy}methyl)acrylate top
Crystal data top
C23H27N3O5SZ = 2
Mr = 457.54F(000) = 484
Triclinic, P1Dx = 1.344 Mg m−3
a = 7.3668 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.5842 (3) ÅCell parameters from 5141 reflections
c = 14.5700 (4) Åθ = 1.0–27.5°
α = 111.692 (2)°µ = 0.18 mm−1
β = 99.520 (2)°T = 123 K
γ = 93.076 (2)°Prism, colourless
V = 1130.44 (5) Å30.45 × 0.15 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer		3777 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.044
Graphite monochromatorθmax = 27.5°, θmin = 1.5°
ϕ and ω scansh = −9→9
25883 measured reflectionsk = −15→13
5178 independent reflectionsl = −18→18
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) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0315P)2 + 0.4141P]
where P = (Fo2 + 2Fc2)/3
5178 reflections(Δ/σ)max = 0.001
353 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
Crystal data top
C23H27N3O5Sγ = 93.076 (2)°
Mr = 457.54V = 1130.44 (5) Å3
Triclinic, P1Z = 2
a = 7.3668 (2) ÅMo Kα radiation
b = 11.5842 (3) ŵ = 0.18 mm−1
c = 14.5700 (4) ÅT = 123 K
α = 111.692 (2)°0.45 × 0.15 × 0.10 mm
β = 99.520 (2)°
Data collection top
Nonius KappaCCD
diffractometer		3777 reflections with I > 2σ(I)
25883 measured reflectionsRint = 0.044
5178 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.25 e Å−3
5178 reflectionsΔρmin = −0.27 e Å−3
353 parameters
Special details top

Experimental. Refinement in non-c sp. gr. P1 did NOT give a less disordered structure.

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*/UeqOcc. (<1)
S10.20722 (6)0.26789 (4)0.25469 (3)0.02608 (12)
O10.12101 (15)−0.08791 (9)0.36607 (8)0.0232 (2)
O20.39994 (17)0.10122 (11)0.66437 (9)0.0312 (3)
O30.32728 (16)−0.06824 (11)0.69722 (9)0.0294 (3)
O40.08880 (16)−0.57502 (10)0.08081 (9)0.0311 (3)
O5−0.18394 (15)−0.50840 (9)0.11282 (8)0.0260 (3)
N10.16820 (17)0.07612 (11)0.31459 (10)0.0203 (3)
N20.06085 (17)0.04205 (11)0.14103 (10)0.0204 (3)
N3−0.0786 (2)−0.14863 (13)0.02310 (11)0.0248 (3)
C10.1387 (2)0.11156 (13)0.23660 (12)0.0196 (3)
C20.1026 (2)−0.04373 (14)0.29136 (11)0.0195 (3)
C30.0150 (2)−0.12776 (13)0.19635 (11)0.0194 (3)
C40.0002 (2)−0.07975 (13)0.12009 (12)0.0199 (3)
C50.2241 (2)−0.00740 (14)0.46359 (11)0.0209 (3)
H5A0.16260.06840.49120.025*
H5B0.35110.01890.45880.025*
C60.2317 (2)−0.07954 (15)0.53091 (12)0.0230 (3)
C70.1612 (3)−0.19702 (17)0.50120 (16)0.0488 (6)
H7A0.1706−0.23700.54790.059*
H7B0.1008−0.24200.43300.059*
C80.3274 (2)−0.00539 (15)0.63655 (12)0.0224 (3)
C90.4260 (3)−0.00267 (18)0.80075 (13)0.0335 (4)
H9A0.36920.07350.83410.040*
H9B0.55750.02250.80250.040*
C100.4129 (3)−0.0912 (2)0.85374 (16)0.0488 (6)
H10A0.2841−0.10600.86000.073*
H10B0.4925−0.05450.92100.073*
H10C0.4536−0.17070.81480.073*
C11−0.0638 (2)−0.25956 (13)0.17688 (12)0.0216 (3)
H11A−0.1669−0.28790.11750.026*
H11B−0.1166−0.25810.23550.026*
C120.0730 (2)−0.35458 (14)0.15849 (12)0.0217 (3)
C130.2550 (2)−0.32689 (16)0.18107 (14)0.0345 (4)
H13A0.3320−0.39200.16860.041*
H13B0.3091−0.24180.20990.041*
C14−0.0029 (2)−0.49037 (14)0.11337 (12)0.0229 (3)
C15−0.2680 (2)−0.63874 (15)0.07418 (14)0.0303 (4)
H15A−0.2157−0.68020.11930.036*
H15B−0.2433−0.68500.00610.036*
C16−0.4726 (2)−0.63746 (17)0.06984 (15)0.0358 (4)
H16A−0.4951−0.59250.13770.054*
H16B−0.5341−0.72370.04330.054*
H16C−0.5222−0.59540.02560.054*
C170.3703 (2)0.32554 (15)0.37483 (12)0.0269 (4)
H17A0.45630.26210.37670.032*
H17B0.28370.34320.41410.032*0.50
H17C0.45030.37840.37570.032*0.50
C180.4761 (4)0.4401 (3)0.3713 (2)0.0186 (6)0.50
C190.3027 (4)0.3770 (3)0.4741 (2)0.0206 (7)0.50
C200.1845 (4)0.4685 (3)0.4844 (2)0.0249 (7)0.50
H200.14840.49460.43020.030*0.50
C210.1187 (5)0.5222 (3)0.5721 (3)0.0284 (8)0.50
H210.03650.58380.57740.034*0.50
C220.1722 (8)0.4866 (7)0.6525 (6)0.0311 (15)0.50
H220.12640.52370.71270.037*0.50
C230.2909 (12)0.3982 (6)0.6455 (7)0.0270 (18)0.50
H230.32950.37490.70110.032*0.50
C240.3553 (5)0.3419 (3)0.5556 (3)0.0270 (7)0.50
H240.43570.27930.55020.032*0.50
C250.6559 (4)0.4328 (3)0.3536 (2)0.0232 (7)0.50
H250.70870.35700.34310.028*0.50
C260.7586 (8)0.5350 (8)0.3512 (5)0.0265 (15)0.50
H260.88140.52920.33930.032*0.50
C270.5038 (5)0.6542 (3)0.3830 (2)0.0234 (7)0.50
H270.45140.72990.39260.028*0.50
C280.4009 (4)0.5524 (3)0.3860 (2)0.0221 (7)0.50
H280.27830.55900.39810.027*0.50
C290.6825 (15)0.6457 (6)0.3661 (7)0.0239 (15)0.50
H290.75330.71580.36460.029*0.50
H1N−0.092 (2)−0.2301 (18)0.0018 (13)0.030 (5)*
H2N−0.072 (2)−0.1151 (17)−0.0219 (14)0.035 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0351 (2)0.01458 (19)0.0273 (2)−0.00139 (16)0.00509 (18)0.00771 (17)
O10.0308 (6)0.0174 (5)0.0194 (6)−0.0028 (5)0.0024 (5)0.0066 (5)
O20.0386 (7)0.0261 (6)0.0263 (7)−0.0032 (5)−0.0007 (5)0.0111 (5)
O30.0319 (7)0.0344 (7)0.0296 (7)0.0050 (5)0.0060 (5)0.0209 (6)
O40.0286 (7)0.0180 (6)0.0398 (7)0.0020 (5)0.0037 (5)0.0049 (5)
O50.0263 (6)0.0163 (5)0.0322 (7)−0.0027 (5)0.0064 (5)0.0063 (5)
N10.0226 (7)0.0158 (6)0.0212 (7)−0.0001 (5)0.0048 (5)0.0060 (6)
N20.0222 (7)0.0154 (6)0.0220 (7)0.0007 (5)0.0029 (6)0.0062 (6)
N30.0340 (8)0.0153 (7)0.0219 (8)−0.0033 (6)0.0008 (6)0.0062 (6)
C10.0183 (8)0.0152 (7)0.0248 (9)0.0016 (6)0.0070 (7)0.0061 (7)
C20.0197 (8)0.0170 (7)0.0223 (8)0.0010 (6)0.0063 (6)0.0075 (7)
C30.0195 (8)0.0153 (7)0.0228 (8)0.0006 (6)0.0043 (6)0.0068 (7)
C40.0174 (8)0.0166 (7)0.0235 (8)0.0004 (6)0.0030 (6)0.0060 (7)
C50.0216 (8)0.0181 (7)0.0201 (8)−0.0016 (6)0.0028 (6)0.0051 (7)
C60.0187 (8)0.0231 (8)0.0286 (9)0.0024 (6)0.0015 (7)0.0127 (7)
C70.0598 (14)0.0305 (10)0.0489 (13)−0.0166 (9)−0.0254 (10)0.0252 (10)
C80.0186 (8)0.0265 (9)0.0271 (9)0.0050 (7)0.0067 (7)0.0149 (7)
C90.0342 (10)0.0468 (11)0.0250 (10)0.0140 (9)0.0073 (8)0.0182 (9)
C100.0592 (14)0.0665 (14)0.0414 (12)0.0312 (12)0.0206 (11)0.0366 (11)
C110.0236 (8)0.0173 (7)0.0222 (8)−0.0026 (6)0.0030 (7)0.0068 (7)
C120.0260 (9)0.0163 (7)0.0203 (8)−0.0010 (6)0.0016 (7)0.0058 (6)
C130.0274 (10)0.0199 (8)0.0479 (12)0.0012 (7)0.0011 (8)0.0065 (8)
C140.0253 (8)0.0204 (8)0.0217 (8)−0.0002 (7)0.0004 (7)0.0087 (7)
C150.0326 (10)0.0159 (8)0.0372 (10)−0.0053 (7)0.0042 (8)0.0065 (7)
C160.0305 (10)0.0305 (9)0.0461 (12)−0.0052 (8)0.0010 (9)0.0182 (9)
C170.0308 (9)0.0184 (8)0.0258 (9)−0.0060 (7)0.0074 (7)0.0025 (7)
C180.0257 (16)0.0178 (15)0.0098 (14)−0.0041 (12)−0.0032 (12)0.0061 (12)
C190.0170 (15)0.0149 (14)0.0249 (17)−0.0045 (12)0.0003 (13)0.0046 (13)
C200.0272 (18)0.0212 (16)0.0239 (17)−0.0001 (14)0.0018 (14)0.0079 (14)
C210.0301 (19)0.0216 (16)0.032 (2)0.0027 (14)0.0091 (15)0.0076 (15)
C220.037 (4)0.026 (3)0.028 (2)−0.004 (3)0.013 (3)0.005 (2)
C230.025 (4)0.032 (5)0.021 (3)−0.006 (4)0.000 (2)0.010 (5)
C240.0248 (18)0.0201 (16)0.033 (2)−0.0002 (13)0.0006 (15)0.0091 (15)
C250.0266 (17)0.0201 (16)0.0203 (17)0.0014 (13)−0.0001 (13)0.0070 (13)
C260.024 (4)0.034 (4)0.021 (2)0.002 (3)0.001 (3)0.012 (3)
C270.0332 (19)0.0173 (15)0.0184 (16)0.0017 (14)0.0021 (14)0.0068 (13)
C280.0230 (16)0.0218 (16)0.0215 (17)−0.0015 (13)0.0027 (13)0.0096 (14)
C290.032 (3)0.019 (3)0.017 (3)−0.006 (3)0.004 (2)0.003 (3)
Geometric parameters (Å, º) top
S1—C11.7632 (15)C13—H13A0.9500
S1—C171.8187 (17)C13—H13B0.9500
O1—C21.3549 (18)C15—C161.499 (2)
O1—C51.4327 (18)C15—H15A0.9900
O2—C81.2094 (18)C15—H15B0.9900
O3—C81.3369 (18)C16—H16A0.9800
O3—C91.453 (2)C16—H16B0.9800
O4—C141.2153 (19)C16—H16C0.9800
O5—C141.3367 (19)C17—C181.524 (3)
O5—C151.4615 (18)C17—C191.525 (3)
N1—C11.3341 (19)C17—H17A1.0000
N1—C21.3424 (18)C17—H17B0.9080
N2—C11.3317 (19)C17—H17C0.8220
N2—C41.3611 (18)C18—C251.392 (4)
N3—C41.347 (2)C18—C281.399 (4)
N3—H1N0.872 (18)C18—H17C0.7576
N3—H2N0.883 (19)C19—C201.389 (4)
C2—C31.386 (2)C19—C241.396 (5)
C3—C41.407 (2)C19—H17B0.7979
C3—C111.510 (2)C20—C211.380 (5)
C5—C61.502 (2)C20—H200.9500
C5—H5A0.9900C21—C221.385 (9)
C5—H5B0.9900C21—H210.9500
C6—C71.313 (2)C22—C231.369 (8)
C6—C81.484 (2)C22—H220.9500
C7—H7A0.9500C23—C241.405 (9)
C7—H7B0.9500C23—H230.9500
C9—C101.502 (3)C24—H240.9500
C9—H9A0.9900C25—C261.386 (9)
C9—H9B0.9900C25—H250.9500
C10—H10A0.9800C26—C291.384 (7)
C10—H10B0.9800C26—H260.9500
C10—H10C0.9800C27—C291.381 (11)
C11—C121.513 (2)C27—C281.385 (4)
C11—H11A0.9900C27—H270.9500
C11—H11B0.9900C28—H280.9500
C12—C131.318 (2)C29—H290.9500
C12—C141.496 (2)
C1—S1—C17102.74 (7)O5—C15—H15A110.3
C2—O1—C5118.00 (11)C16—C15—H15A110.3
C8—O3—C9116.27 (13)O5—C15—H15B110.3
C14—O5—C15116.03 (12)C16—C15—H15B110.3
C1—N1—C2113.72 (13)H15A—C15—H15B108.5
C1—N2—C4116.39 (13)C15—C16—H16A109.5
C4—N3—H1N119.5 (12)C15—C16—H16B109.5
C4—N3—H2N118.1 (12)H16A—C16—H16B109.5
H1N—N3—H2N117.4 (17)C15—C16—H16C109.5
N2—C1—N1128.05 (13)H16A—C16—H16C109.5
N2—C1—S1112.15 (11)H16B—C16—H16C109.5
N1—C1—S1119.80 (11)C18—C17—C19103.65 (18)
N1—C2—O1118.31 (13)C18—C17—S1101.61 (14)
N1—C2—C3125.47 (14)C19—C17—S1120.89 (15)
O1—C2—C3116.22 (13)C18—C17—H17A110.0
C2—C3—C4114.93 (13)C19—C17—H17A109.8
C2—C3—C11122.49 (14)S1—C17—H17A110.0
C4—C3—C11122.56 (13)C18—C17—H17B114.5
N3—C4—N2115.60 (14)S1—C17—H17B96.2
N3—C4—C3123.02 (14)H17A—C17—H17B121.5
N2—C4—C3121.35 (14)C19—C17—H17C107.7
O1—C5—C6107.65 (12)S1—C17—H17C109.8
O1—C5—H5A110.2H17A—C17—H17C95.6
C6—C5—H5A110.2H17B—C17—H17C123.7
O1—C5—H5B110.2C25—C18—C28118.7 (3)
C6—C5—H5B110.2C25—C18—C17118.5 (2)
H5A—C5—H5B108.5C28—C18—C17122.8 (3)
C7—C6—C8121.96 (16)C25—C18—H17C103.5
C7—C6—C5124.34 (16)C28—C18—H17C137.4
C8—C6—C5113.70 (13)C20—C19—C24118.0 (3)
C6—C7—H7A120.0C20—C19—C17117.0 (3)
C6—C7—H7B120.0C24—C19—C17124.9 (3)
H7A—C7—H7B120.0C20—C19—H17B100.1
O2—C8—O3123.51 (15)C24—C19—H17B136.2
O2—C8—C6122.92 (14)C21—C20—C19121.2 (3)
O3—C8—C6113.56 (13)C21—C20—H20119.4
O3—C9—C10107.21 (16)C19—C20—H20119.4
O3—C9—H9A110.3C20—C21—C22120.2 (4)
C10—C9—H9A110.3C20—C21—H21119.9
O3—C9—H9B110.3C22—C21—H21119.9
C10—C9—H9B110.3C23—C22—C21120.2 (7)
H9A—C9—H9B108.5C23—C22—H22119.9
C9—C10—H10A109.5C21—C22—H22119.9
C9—C10—H10B109.5C22—C23—C24119.6 (7)
H10A—C10—H10B109.5C22—C23—H23120.2
C9—C10—H10C109.5C24—C23—H23120.2
H10A—C10—H10C109.5C19—C24—C23120.8 (4)
H10B—C10—H10C109.5C19—C24—H24119.6
C3—C11—C12115.26 (13)C23—C24—H24119.6
C3—C11—H11A108.5C26—C25—C18120.6 (4)
C12—C11—H11A108.5C26—C25—H25119.7
C3—C11—H11B108.5C18—C25—H25119.7
C12—C11—H11B108.5C29—C26—C25120.1 (7)
H11A—C11—H11B107.5C29—C26—H26120.0
C13—C12—C14117.25 (15)C25—C26—H26120.0
C13—C12—C11124.92 (14)C29—C27—C28120.1 (4)
C14—C12—C11117.82 (13)C29—C27—H27119.9
C12—C13—H13A120.0C28—C27—H27119.9
C12—C13—H13B120.0C27—C28—C18120.5 (3)
H13A—C13—H13B120.0C27—C28—H28119.8
O4—C14—O5123.58 (14)C18—C28—H28119.8
O4—C14—C12124.08 (15)C27—C29—C26120.0 (8)
O5—C14—C12112.34 (13)C27—C29—H29120.0
O5—C15—C16107.13 (13)C26—C29—H29120.0
C4—N2—C1—N11.5 (2)C15—O5—C14—O42.7 (2)
C4—N2—C1—S1−178.81 (11)C15—O5—C14—C12−177.32 (13)
C2—N1—C1—N2−2.9 (2)C13—C12—C14—O4−13.1 (2)
C2—N1—C1—S1177.38 (11)C11—C12—C14—O4168.24 (15)
C17—S1—C1—N2−162.15 (11)C13—C12—C14—O5166.93 (15)
C17—S1—C1—N117.62 (14)C11—C12—C14—O5−11.8 (2)
C1—N1—C2—O1−178.17 (13)C14—O5—C15—C16−174.00 (14)
C1—N1—C2—C31.3 (2)C1—S1—C17—C18160.97 (14)
C5—O1—C2—N1−5.5 (2)C1—S1—C17—C19−85.22 (17)
C5—O1—C2—C3174.97 (13)C19—C17—C18—C25128.3 (3)
N1—C2—C3—C41.3 (2)S1—C17—C18—C25−105.6 (2)
O1—C2—C3—C4−179.17 (13)C19—C17—C18—C28−51.1 (3)
N1—C2—C3—C11−176.88 (14)S1—C17—C18—C2875.0 (3)
O1—C2—C3—C112.6 (2)C18—C17—C19—C2061.2 (3)
C1—N2—C4—N3179.86 (13)S1—C17—C19—C20−51.6 (3)
C1—N2—C4—C31.7 (2)C18—C17—C19—C24−116.7 (3)
C2—C3—C4—N3179.07 (14)S1—C17—C19—C24130.6 (3)
C11—C3—C4—N3−2.7 (2)C24—C19—C20—C21−0.9 (5)
C2—C3—C4—N2−2.9 (2)C17—C19—C20—C21−178.9 (3)
C11—C3—C4—N2175.33 (14)C19—C20—C21—C221.0 (6)
C2—O1—C5—C6−177.40 (12)C20—C21—C22—C230.1 (9)
O1—C5—C6—C72.6 (2)C21—C22—C23—C24−1.2 (11)
O1—C5—C6—C8−177.24 (12)C20—C19—C24—C23−0.3 (6)
C9—O3—C8—O2−1.9 (2)C17—C19—C24—C23177.6 (4)
C9—O3—C8—C6177.35 (13)C22—C23—C24—C191.3 (9)
C7—C6—C8—O2176.82 (19)C28—C18—C25—C260.4 (5)
C5—C6—C8—O2−3.3 (2)C17—C18—C25—C26−179.1 (4)
C7—C6—C8—O3−2.4 (2)C18—C25—C26—C29−0.3 (9)
C5—C6—C8—O3177.41 (13)C29—C27—C28—C18−0.4 (6)
C8—O3—C9—C10−178.31 (14)C25—C18—C28—C27−0.1 (4)
C2—C3—C11—C12−85.26 (19)C17—C18—C28—C27179.3 (3)
C4—C3—C11—C1296.68 (18)C28—C27—C29—C260.5 (11)
C3—C11—C12—C1316.7 (2)C25—C26—C29—C27−0.2 (12)
C3—C11—C12—C14−164.74 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N···O4i0.872 (18)2.133 (19)2.9832 (18)164.8 (16)
N3—H2N···N2ii0.883 (19)2.20 (2)3.0868 (19)176.8 (17)
Symmetry codes: (i) −x, −y−1, −z; (ii) −x, −y, −z.

Experimental details

Crystal data
Chemical formulaC23H27N3O5S
Mr457.54
Crystal system, space groupTriclinic, P1
Temperature (K)123
a, b, c (Å)7.3668 (2), 11.5842 (3), 14.5700 (4)
α, β, γ (°)111.692 (2), 99.520 (2), 93.076 (2)
V (Å3)1130.44 (5)
Z2
Radiation typeMo Kα
µ (mm−1)0.18
Crystal size (mm)0.45 × 0.15 × 0.10
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction–
No. of measured, independent and
observed [I > 2σ(I)] reflections		25883, 5178, 3777
Rint0.044
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.091, 1.04
No. of reflections5178
No. of parameters353
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.25, −0.27

Computer programs: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
O2—C81.2094 (18)C2—C31.386 (2)
O4—C141.2153 (19)C3—C41.407 (2)
N1—C11.3341 (19)C6—C71.313 (2)
N1—C21.3424 (18)C6—C81.484 (2)
N2—C11.3317 (19)C12—C131.318 (2)
N2—C41.3611 (18)C12—C141.496 (2)
N3—C41.347 (2)
C1—N1—C2113.72 (13)N1—C2—C3125.47 (14)
C1—N2—C4116.39 (13)C2—C3—C4114.93 (13)
N2—C1—N1128.05 (13)N2—C4—C3121.35 (14)
C5—O1—C2—N1−5.5 (2)C13—C12—C14—O4−13.1 (2)
C7—C6—C8—O2176.82 (19)C1—S1—C17—C18160.97 (14)
C4—C3—C11—C1296.68 (18)C1—S1—C17—C19−85.22 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1N···O4i0.872 (18)2.133 (19)2.9832 (18)164.8 (16)
N3—H2N···N2ii0.883 (19)2.20 (2)3.0868 (19)176.8 (17)
Symmetry codes: (i) −x, −y−1, −z; (ii) −x, −y, −z.
 

Acknowledgements

The authors are grateful to the University of Strathclyde for the award of a Postgraduate Scholarship (JKH).

References

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ISSN: 2056-9890
Volume 62| Part 1| January 2006| Pages o324-o326
doi:10.1107/S1600536805041899
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