Thio­phene-2-carbonyl azide

Hsu, G.C.; Singer, L.M.; Cordes, D.B.; Findlater, M.

doi:10.1107/S1600536813019740

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1298

doi:10.1107/S1600536813019740

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Thiophene-2-carbonyl azide

Gene C. Hsu,^a Laci M. Singer,^a David B. Cordes ^a and Michael Findlater ^a ^*

^aDepartment of Chemistry & Biochemistry, Texas Tech University, Memorial Circle & Boston, Lubbock, TX 79409, USA
^*Correspondence e-mail: michael.findlater@ttu.edu

(Received 15 July 2013; accepted 16 July 2013; online 24 July 2013)

The title compound, C₅H₃N₃OS, is almost planar (r.m.s. deviation for the ten non-H atoms = 0.018 Å) and forms an extended layer structure in the (100) plane, held together via hydrogen-bonding interactions between adjacent molecules. Of particular note is the occurrence of RC—H⋯N⁻=N⁺=NR interactions between an aromatic C—H group and an azide moiety which, in conjunction with a complementary C—H⋯O=C interaction, forms a nine-membered ring.

Related literature

For a previous preparation of the title compound, see: Binder et al. (1977 ). For the synthesis of the starting material, 2-thiophenecarbonyl chloride, see: Kruse et al. (1989 ). For related structures, see: Arsenyan et al. (2008 ); Elshaarawy & Janiak (2011 ); Low et al. (2009 ).

Experimental

Crystal data

C₅H₃N₃OS
M_r = 153.16
Monoclinic, C 2/c
a = 12.668 (3) Å
b = 6.2153 (12) Å
c = 16.400 (3) Å
β = 95.91 (3)°
V = 1284.4 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 153 K
0.20 × 0.16 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.920, T_max = 0.939
2728 measured reflections
1459 independent reflections
1152 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.154
S = 1.13
1459 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N1ⁱ	0.95	2.63	3.512 (4)	155
C3—H3⋯N3ⁱⁱ	0.95	2.66	3.396 (4)	135
C4—H4⋯O1ⁱⁱ	0.95	2.47	3.415 (4)	173
Symmetry codes: (i) x, y-1, z; (ii) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: COLLECT; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013 ); molecular graphics: SHELXTL (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL, enCIFer (Allen et al., 2004 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813019740/tk5242sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019740/tk5242Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019740/tk5242Isup3.cml

checkCIF report

Comment top

The title compound (Fig. 1) displays a different organization in the solid state to that seen in related compounds. It forms one-dimensional hydrogen-bonded chains through the formation of C—H···N/O hydrogen bonds (Table 1 and Fig. 2), that are then linked into two-dimensional sheets in the (1 0 0) plane by further C—H···N interactions. This results in utilization of all the H atoms in the molecule for hydrogen-bonding. All three related structures (Arsenyan et al., 2008; Elshaarawy & Janiak, 2011; Low et al., 2009) are, in contrast, dominated by N—H···O/N hydrogen bonding, resulting in two different one-dimensional chains (Arsenyan et al., 2008; Low et al., 2009), and a two-dimensional sheet (Elshaarawy & Janiak, 2011).

Related literature top

For a previous preparation of the title compound, see: Binder et al. (1977). For the synthesis of the starting material, 2-thiophenecarbonyl chloride, see: Kruse et al. (1989). For related structures, see: Arsenyan et al. (2008); Elshaarawy & Janiak (2011); Low et al. (2009).

Experimental top

The title compound was prepared by the method of Binder et al. (1977), from 2-thiophenecarbonyl chloride (Kruse et al., 1989). Crystals suitable for X-ray structure determination were obtained by cooling a toluene solution of the title compound to -30°C.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT (Nonius, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. View of one of the hydrogen-bonded sheets in the (1 0 0) plane.

Thiophene-2-carbonyl azide top

Crystal data top

C₅H₃N₃OS	F(000) = 624
M_r = 153.16	D_x = 1.584 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.668 (3) Å	Cell parameters from 1494 reflections
b = 6.2153 (12) Å	θ = 1.0–27.5°
c = 16.400 (3) Å	µ = 0.43 mm⁻¹
β = 95.91 (3)°	T = 153 K
V = 1284.4 (4) Å³	Block, colourless
Z = 8	0.20 × 0.16 × 0.15 mm

Data collection top

Nonius KappaCCD diffractometer	1152 reflections with I > 2σ(I)
Radiation source: fine focus sealed tube	R_int = 0.025
ϕ and ω scans	θ_max = 27.4°, θ_min = 2.5°
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)	h = −15→16
T_min = 0.920, T_max = 0.939	k = −7→8
2728 measured reflections	l = −21→21
1459 independent reflections

Refinement top

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0659P)² + 3.253P] where P = (F_o² + 2F_c²)/3
1459 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₅H₃N₃OS	V = 1284.4 (4) Å³
M_r = 153.16	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 12.668 (3) Å	µ = 0.43 mm⁻¹
b = 6.2153 (12) Å	T = 153 K
c = 16.400 (3) Å	0.20 × 0.16 × 0.15 mm
β = 95.91 (3)°

Data collection top

Nonius KappaCCD diffractometer	1459 independent reflections
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)	1152 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.939	R_int = 0.025
2728 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.13	Δρ_max = 0.59 e Å⁻³
1459 reflections	Δρ_min = −0.49 e Å⁻³
91 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3676 (2)	0.0373 (4)	0.57926 (15)	0.0260 (6)
C2	0.3494 (2)	−0.1827 (4)	0.59864 (15)	0.0238 (6)
H2	0.3401	−0.2988	0.5609	0.029*
C3	0.3478 (2)	−0.1956 (5)	0.68730 (18)	0.0334 (7)
H3	0.3368	−0.3267	0.7150	0.040*
C4	0.3632 (2)	−0.0048 (5)	0.72675 (17)	0.0347 (7)
H4	0.3647	0.0105	0.7845	0.042*
C5	0.3763 (2)	0.1133 (5)	0.49575 (15)	0.0271 (6)
N1	0.3946 (2)	0.3386 (4)	0.49385 (13)	0.0323 (6)
N2	0.39920 (19)	0.4093 (4)	0.42227 (13)	0.0308 (6)
N3	0.4044 (2)	0.4879 (5)	0.36125 (15)	0.0401 (7)
O1	0.36928 (17)	−0.0003 (4)	0.43538 (12)	0.0382 (5)
S1	0.37950 (6)	0.20165 (12)	0.66320 (4)	0.0360 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0249 (13)	0.0295 (14)	0.0237 (12)	−0.0011 (11)	0.0039 (10)	−0.0039 (10)
C2	0.0247 (13)	0.0226 (13)	0.0248 (12)	0.0005 (10)	0.0062 (10)	0.0053 (10)
C3	0.0358 (16)	0.0308 (16)	0.0340 (15)	−0.0005 (12)	0.0055 (12)	0.0079 (12)
C4	0.0364 (16)	0.0438 (18)	0.0240 (13)	0.0034 (14)	0.0035 (11)	0.0026 (12)
C5	0.0251 (13)	0.0311 (15)	0.0255 (13)	−0.0021 (11)	0.0045 (10)	−0.0028 (11)
N1	0.0438 (14)	0.0336 (13)	0.0196 (11)	−0.0007 (11)	0.0028 (9)	−0.0002 (9)
N2	0.0317 (13)	0.0335 (14)	0.0266 (12)	−0.0035 (10)	0.0002 (9)	−0.0026 (10)
N3	0.0461 (16)	0.0450 (16)	0.0286 (13)	−0.0109 (13)	0.0005 (10)	0.0039 (12)
O1	0.0519 (14)	0.0382 (12)	0.0255 (10)	−0.0086 (10)	0.0080 (8)	−0.0072 (9)
S1	0.0487 (5)	0.0318 (4)	0.0275 (4)	−0.0028 (3)	0.0036 (3)	−0.0018 (3)

Geometric parameters (Å, º) top

C1—C2	1.428 (4)	C4—S1	1.679 (3)
C1—C5	1.464 (4)	C4—H4	0.9500
C1—S1	1.708 (3)	C5—O1	1.212 (3)
C2—C3	1.459 (4)	C5—N1	1.420 (4)
C2—H2	0.9500	N1—N2	1.260 (3)
C3—C4	1.355 (4)	N2—N3	1.122 (3)
C3—H3	0.9500

C2—C1—C5	123.1 (2)	C3—C4—S1	113.2 (2)
C2—C1—S1	113.34 (19)	C3—C4—H4	123.4
C5—C1—S1	123.5 (2)	S1—C4—H4	123.4
C1—C2—C3	107.1 (2)	O1—C5—N1	123.7 (2)
C1—C2—H2	126.5	O1—C5—C1	124.8 (3)
C3—C2—H2	126.5	N1—C5—C1	111.5 (2)
C4—C3—C2	114.3 (3)	N2—N1—C5	112.8 (2)
C4—C3—H3	122.8	N3—N2—N1	174.5 (3)
C2—C3—H3	122.8	C4—S1—C1	92.11 (14)

C5—C1—C2—C3	178.9 (2)	S1—C1—C5—N1	−0.6 (3)
S1—C1—C2—C3	−0.5 (3)	O1—C5—N1—N2	2.1 (4)
C1—C2—C3—C4	0.0 (3)	C1—C5—N1—N2	−178.0 (2)
C2—C3—C4—S1	0.5 (4)	C3—C4—S1—C1	−0.7 (3)
C2—C1—C5—O1	−0.1 (4)	C2—C1—S1—C4	0.7 (2)
S1—C1—C5—O1	179.2 (2)	C5—C1—S1—C4	−178.7 (2)
C2—C1—C5—N1	−179.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.95	2.63	3.512 (4)	155
C3—H3···N3ⁱⁱ	0.95	2.66	3.396 (4)	135
C4—H4···O1ⁱⁱ	0.95	2.47	3.415 (4)	173

Symmetry codes: (i) x, y−1, z; (ii) x, −y, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N1ⁱ	0.95	2.63	3.512 (4)	155
C3—H3···N3ⁱⁱ	0.95	2.66	3.396 (4)	135
C4—H4···O1ⁱⁱ	0.95	2.47	3.415 (4)	173

Symmetry codes: (i) x, y−1, z; (ii) x, −y, z+1/2.

Acknowledgements

The authors gratefully acknowledge the Robert A. Welch Foundation for their support of GCH via the Welch Summer Scholars Program, and Texas Tech University for start-up funds.

References

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