2-Diazo-1-(1,1-dioxothio­morpholin-4-yl)ethanone

Åsmund Kaupang; Carl Henrik Görbitz; Tore Hansen

doi:10.1107/S1600536811023774

. 2011 Jun 30;67(Pt 7):o1844–o1845. doi: 10.1107/S1600536811023774

2-Diazo-1-(1,1-dioxothiomorpholin-4-yl)ethanone

Åsmund Kaupang ^a, Carl Henrik Görbitz ^a,^*, Tore Hansen ^a

PMCID: PMC3151793 PMID: 21837210

Abstract

In the molecule of the title compound, C₆H₉N₃O₃S, at 105 K, the six-membered ring is predominantly found in the chair conformation, with 1.89 (14)% in the boat conformation. In the crystal structure, there are five intermolecular C—H⋯O=C and C—H⋯O=S contacts less than 2.6 Å, as well as a weak C—H⋯N=N interaction to the diazo group.

Related literature

For related structures found in the Cambridge Structural Database (Version 5.32 of November 2010; Allen, 2002 ▶), see: Fenlon et al. (2007 ▶); Haynes et al. (2006 ▶); Wang et al. (2006 ▶); Miller et al. (1991 ▶); Foces-Foces et al. (1988 ▶); Ganguly et al. (1980 ▶); Herdklotz & Sass (1969 ▶). For details of the synthesis, see: Kaupang (2010 ▶); Toma et al. (2007 ▶) and for the synthesis of related diazoacetamides, see: Kaupang et al. (2010 ▶); Kaupang (2010 ▶); Ouihia et al. (1993 ▶). For quantum chemical calculations involving the acetamide analogue of the title compound, see: Fraenkel et al. (1992 ▶). For the Chemical Abstracts Service, see: American Chemical Society (2008 ▶). For hydrogen-bond graph-set notation, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C₆H₉N₃O₃S
M _r = 203.22
Monoclinic,
a = 5.2729 (3) Å
b = 20.1349 (11) Å
c = 7.8683 (4) Å
β = 95.171 (2)°
V = 831.97 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 105 K
0.80 × 0.30 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.849, T _max = 0.929
14742 measured reflections
3951 independent reflections
3029 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.165
S = 1.11
3951 reflections
138 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.24 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811023774/si2361sup1.cif

e-67-o1844-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023774/si2361Isup2.hkl

e-67-o1844-Isup2.hkl^{(193.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811023774/si2361Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.94 (2)	2.42 (2)	3.326 (2)	163 (2)
C3—H32⋯O1ⁱⁱ	0.99	2.47	3.372 (2)	152
C5—H52⋯O1ⁱⁱⁱ	0.99	2.36	3.022 (2)	123
C5—H51⋯O3^iv	0.99	2.56	3.445 (2)	149
C5—H52⋯N3^v	0.99	2.59	3.417 (3)	141
C6—H61⋯O2^vi	0.99	2.45	3.168 (2)	129

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

supplementary crystallographic information

Comment

2-Diazo-1-(1,1-dioxido-4-thiomorpholinyl)ethanone (I) was prepared as part of a series of diazoacetamides used in the intramolecular C—H insertion reactions taking place upon thermolysis of their corresponding α-bromodiazoacetamides (Kaupang, 2010). The title compound was synthesized from 2-bromo-1-(1,1-dioxido-4-thiomorpholinyl)ethanone following a procedure reported by Toma et al. (2007), modified to employ 1,1,3,3-tetramethylguanidine as the base instead of 1,8-diazabicyclo[5.4.0]undec-7-ene. No previous reports of this compound were found in the Chemical Abstracts Service (CAS, American Chemical Society, 2008).

In the crystal (I) occurs in the expected chair conformation, with a very minor fraction [occupancy 0.0189 (14)] in a boat conformation as shown in Fig. 1. The unit cell and crystal packing are depicted in Fig. 2, while a list of six C—H···O/N interactions with H···O distance shorter than 2.60 Å are given in Table 1. The two shortest interactions, with C2—H2 and C5—H52 donors, form C(8) chains along the a axis and dimeric R₂²(12) ring motifs, respectively (Etter et al., 1990). H52 is also close to the diazo N3 atom and thus participates in a three-center interaction. The interactions of (I) are different from those observed in our previous, related structure of tert-butyl 4-(2-diazoacetyl)piperazine-1-carboxylate (Kaupang et al., 2010) where the H of the diazoacetyl group was accepted by the O atom of the same group.

Experimental

A solution of 4.0 mg of the title compound in 500 µL of CH₂Cl₂ was placed in a 2.5 ml vial which was capped and a pinhole (0.5 mm) made in the cap to allow for slow evaporation in darkness at ambient temperature. A single cluster of pale yellow needles appeared after approximately 48 h.