Crystal structure of diethyl 2-amino-6-[(thio­phen-3-yl)ethyn­yl]azulene-1,3-di­carboxyl­ate

Förster, S.; Seichter, W.; Weber, E.

doi:10.1107/S2056989015003898

organic compounds

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ISSN: 2056-9890

Volume 71| Part 3| March 2015| Pages o212-o213

doi:10.1107/S2056989015003898

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Crystal structure of diethyl 2-amino-6-[(thiophen-3-yl)ethynyl]azulene-1,3-dicarboxylate

Sebastian Förster,^a Wilhelm Seichter ^a and Edwin Weber ^a ^*

^aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
^*Correspondence e-mail: edwin.weber@chemie.tu-freiberg.de

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 19 February 2015; accepted 25 February 2015; online 28 February 2015)

The title compound, C₂₂H₁₉NO₄S, has an almost planar geometry supported by intramolecular N—H⋯O and C—H⋯O hydrogen bonds. The thiophene ring is inclined to the azulene ring by 4.85 (16)°, while the ethoxycarbonyl groups are inclined to the azulene ring by 7.0 (2) and 5.7 (2)°. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R₂²(12) ring motif. The dimers are linked via C—H⋯π interactions, forming sheets parallel to (10-1).

Keywords: crystal structure; azulene; thiophene; 3-thienylethynyl; hydrogen bonds; C—H⋯π interactions.

CCDC reference: 1051132

1. Related literature

For the synthesis of the title compound concerning the azulene-derived starting material, see: McDonald et al. (1976 ). For the background of this work and for the synthesis of related compounds, see: Xia et al. (2014 ); Förster et al. (2012 ). For related structures, see: Förster et al. (2014 ); Shoji et al. (2013 ). For C—H⋯π contacts, see: Nishio et al. (2009 ).

2. Experimental

2.1. Crystal data

C₂₂H₁₉NO₄S
M_r = 393.44
Monoclinic, C 2/c
a = 22.2429 (5) Å
b = 5.5039 (1) Å
c = 32.8340 (8) Å
β = 102.914 (1)°
V = 3917.96 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 296 K
0.50 × 0.14 × 0.04 mm

2.2. Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.909, T_max = 0.992
18444 measured reflections
3679 independent reflections
2441 reflections with I > 2σ(I)
R_int = 0.032

2.3. Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.242
S = 1.04
3679 reflections
255 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the thiophene ring S1/C19–C22.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3	0.86	2.16	2.765 (4)	127
N1—H1A⋯O1	0.86	2.15	2.757 (4)	127
C5—H5⋯O4	0.93	2.22	2.878 (4)	127
C9—H9⋯O2	0.93	2.23	2.897 (4)	128
N1—H1B⋯O3ⁱ	0.86	2.21	2.959 (4)	146
C8—H8⋯Cg1ⁱⁱ	0.93	2.92	3.714 (4)	144
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{5\over 2}}, -z+1]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

CCDC reference: 1051132

Crystal structure: contains datablocks I, Global. DOI: 10.1107/S2056989015003898/su5088sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015003898/su5088Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015003898/su5088Isup3.cml

checkCIF report

Synthesis and crystallization top

The synthesis of the title compound was done starting from the literature known azulene derivative diethyl 2-amino-6-bromoazulene-1,3-dicarboxylate (McDonald et al., 1976). This compound (1.0 g, 2.73 mmol) together with 3-ethynylthiophene (0.33 g, 3.05 mmol) was dissolved in a mixture of 25 ml diisopropylamine and 25 ml tetrahydrofuran. After degassing of the solution, bis(triphenylphosphane)palladium(II) chloride (32 mg, 0.045 mmol), copper(I) iodide (17 mg, 0.09 mmol) and triphenylphosphane (39 mg, 0.15 mmol) were added. The mixture was stirred for 10 h under reflux and an argon atmosphere. After evaporation of the solvent, the residue was purified by column chromatography on SiO₂ [60 F₂₅₄ Merck, eluent: hexane/ethyl acetate (100:1)] to yield 0.81 g (75%) of the title compound as a red solid. Analytical data: mp = 148-149°C; ¹H-NMR: (CDCl₃) δ/ppm = 9.02 (d, 2H, ArH, ³J_HH = 11.5 Hz), 7.86 (s, 2H, NH₂), 7.73 (d, 2H, ArH, ³J_HH = 11.5 Hz), 7.59 (dd, 1H, ArH, ⁴J_HH = 2.9 Hz, ⁵J_HH = 1.1 Hz), 7.34 (dd, 1H, ArH, ³J_HH = 5.0 Hz, ⁴J_HH = 3.0 Hz), 7.23 (dd, 1H, ArH, ³J_HH = 5.0 Hz, ⁵J_HH = 1.1 Hz), 4.47 (q, 4H, CH₂, ³J_HH = 7.2 Hz), 1.48 (t, 6H, CH₃, ³J_HH = 7.2 Hz); ¹³C-NMR: (CDCl₃) δ/ppm = 166.40 (CO), 162.53 (ArC), 145.55 (ArC), 135.24 (ArC), 129.83 (ArC), 129.82 (ArC), 129.40 (ArC), 127.81 (ArC), 125.65 (ArC), 121.92 (ArC), 100.62 (C≡C), 92.47 (C≡C), 59.98 (CH₂), 14.63 (CH₃); GC/MS calc.: 393.5; found: 393 [M]⁺.;EA calc.: C: 67.16 %, H: 4.87 %, N: 3.56 %, S: 8.15 %; found C: 67.10 %, H: 4.75 %, N: 3.51 %, S: 7.97 %; Crystallization by slow solvent evaporation from dichloromethane solution yielded suitable crystals.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The C- and N-bound H atoms were fixed geometrically and treated as riding: N—H = 0.86 Å, C—H = 0.93 - 0.97 Å, with U_iso(H) =1.5U_eq(C) for methyl H atoms and = 1.2U_eq(N,C) for other H atoms.

Comment top

Due to the special physical properties including redox behavior, azulene is an interesting structure building block for electronic materials design (Förster et al., 2012; Shoji et al., 2013; Xia et al., 2014). In this regard, the present tetrasubstituted azulene derivative, as the title compound, represents a promising intermediate.

The title compound has an almost planar overall geometry with maximum deviations of 0.166 (1) Å for C20 and 0.267 (4) Å for C6 (Fig. 1). In contrast to previously published related compounds (Förster et al., 2014), here the amine group gives rise to the formation of two intramolecular N—H···O hydrogen bonds to the neighbouring carbonyl O atoms O1 and O3 (Table 1 and Fig. 1). Furthermore, atoms O2 and O4 establish two weaker intramolecular C—H···O hydrogen bonds to azulene hydrogen atoms (Table 1 and Fig. 1).

In the crystal, an R₂²(12) hydrogen bonded inversion dimer motif is formed (Table 1 and Fig. 2). Along the crystallographic b-axis, the corresponding dimers are arranged in stacks (Fig. 2). Despite a plane to plane distance of 3.15 Å between the azulene units of consecutive molecules, no arene···arene interactions can be observed due to the lateral displacement. In direction of the crystallographic a- and c-axes, these stacks are connected via C—H···π contacts [Table 1; Nishio et al., 2009] and weak van der Waals forces, forming a sheets parallel to (10\1).. The absence of arene···arene interactions is a rather rare phenomenon for this class of azulenes, and is probably due to packing effects (Förster et al., 2014).

Related literature top

For the synthesis of the title compound concerning the azulene-derived starting material, see: McDonald et al. (1976). For the background of this work and for the synthesis of related compounds, see: Xia et al. (2014); Förster et al. (2012). For related structures, see: Förster et al. (2014); Shoji et al. (2013). For C—H···π contacts, see: Nishio et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bonds are shown as dashed lines (see Table 1 for details).
	Fig. 2. Crystal packing of the title compound viewed along the b-axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

Diethyl 2-amino-6-[(thiophen-3-yl)ethynyl]azulene-1,3-dicarboxylate top

Crystal data top

C₂₂H₁₉NO₄S	F(000) = 1648
M_r = 393.44	D_x = 1.334 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.2429 (5) Å	Cell parameters from 4036 reflections
b = 5.5039 (1) Å	θ = 2.5–23.9°
c = 32.8340 (8) Å	µ = 0.19 mm⁻¹
β = 102.914 (1)°	T = 296 K
V = 3917.96 (15) Å³	Rod, red
Z = 8	0.50 × 0.14 × 0.04 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3679 independent reflections
Radiation source: fine-focus sealed tube	2441 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.032
phi and ω scans	θ_max = 25.6°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −24→26
T_min = 0.909, T_max = 0.992	k = −6→6
18444 measured reflections	l = −39→39

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.067	H-atom parameters constrained
wR(F²) = 0.242	w = 1/[σ²(F_o²) + (0.1341P)² + 7.3721P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3679 reflections	Δρ_max = 0.68 e Å⁻³
255 parameters	Δρ_min = −0.69 e Å⁻³

Crystal data top

C₂₂H₁₉NO₄S	V = 3917.96 (15) Å³
M_r = 393.44	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.2429 (5) Å	µ = 0.19 mm⁻¹
b = 5.5039 (1) Å	T = 296 K
c = 32.8340 (8) Å	0.50 × 0.14 × 0.04 mm
β = 102.914 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3679 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2441 reflections with I > 2σ(I)
T_min = 0.909, T_max = 0.992	R_int = 0.032
18444 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.242	H-atom parameters constrained
S = 1.04	Δρ_max = 0.68 e Å⁻³
3679 reflections	Δρ_min = −0.69 e Å⁻³
255 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
S1	0.29785 (6)	−0.1167 (3)	0.23302 (5)	0.0900 (5)
O1	0.85377 (12)	0.5584 (6)	0.43542 (9)	0.0725 (9)
O2	0.80576 (11)	0.3079 (6)	0.38532 (9)	0.0636 (8)
O3	0.68603 (12)	1.1767 (5)	0.47849 (9)	0.0631 (8)
O4	0.59102 (11)	1.0579 (5)	0.44835 (8)	0.0583 (7)
N1	0.78370 (13)	0.9042 (6)	0.46415 (9)	0.0556 (8)
H1A	0.8213	0.8599	0.4661	0.067*
H1B	0.7755	1.0254	0.4785	0.067*
C1	0.74517 (15)	0.5833 (6)	0.41350 (10)	0.0436 (8)
C2	0.73847 (15)	0.7861 (7)	0.43904 (10)	0.0440 (8)
C3	0.67421 (15)	0.8431 (6)	0.43263 (10)	0.0423 (8)
C4	0.64141 (14)	0.6787 (6)	0.40310 (10)	0.0406 (8)
C5	0.57758 (15)	0.6849 (7)	0.38555 (11)	0.0485 (9)
H5	0.5566	0.8141	0.3943	0.058*
C6	0.54133 (15)	0.5301 (7)	0.35757 (11)	0.0496 (9)
H6	0.5001	0.5754	0.3494	0.060*
C7	0.55645 (15)	0.3158 (6)	0.33947 (10)	0.0445 (8)
C8	0.61599 (16)	0.2185 (6)	0.34362 (11)	0.0461 (8)
H8	0.6178	0.0737	0.3294	0.055*
C9	0.67212 (15)	0.3054 (6)	0.36566 (10)	0.0432 (8)
H9	0.7061	0.2140	0.3628	0.052*
C10	0.68606 (14)	0.5089 (6)	0.39161 (10)	0.0399 (8)
C11	0.80595 (16)	0.4849 (7)	0.41321 (11)	0.0522 (9)
C12	0.86442 (18)	0.1954 (10)	0.38488 (16)	0.0778 (14)
H12A	0.8817	0.1216	0.4118	0.093*
H12B	0.8933	0.3163	0.3792	0.093*
C13	0.8535 (2)	0.0097 (10)	0.35201 (16)	0.0811 (14)
H13A	0.8238	−0.1055	0.3573	0.122*
H13B	0.8915	−0.0725	0.3518	0.122*
H13C	0.8381	0.0856	0.3254	0.122*
C14	0.65276 (15)	1.0391 (7)	0.45498 (11)	0.0465 (8)
C15	0.56708 (18)	1.2514 (8)	0.46980 (13)	0.0619 (11)
H15A	0.5837	1.4066	0.4636	0.074*
H15B	0.5781	1.2254	0.4998	0.074*
C16	0.4981 (2)	1.2477 (11)	0.45432 (17)	0.0881 (16)
H16A	0.4879	1.2725	0.4246	0.132*
H16B	0.4801	1.3748	0.4677	0.132*
H16C	0.4823	1.0935	0.4607	0.132*
C17	0.50538 (16)	0.1840 (7)	0.31426 (11)	0.0500 (9)
C18	0.46201 (16)	0.0786 (7)	0.29443 (11)	0.0497 (9)
C19	0.40854 (15)	−0.0390 (6)	0.27000 (11)	0.0430 (8)
C20	0.40753 (18)	−0.2579 (7)	0.24830 (13)	0.0596 (10)
H20	0.4423	−0.3521	0.2484	0.072*
C21	0.34319 (18)	−0.3231 (6)	0.22455 (11)	0.0483 (9)
H21	0.3322	−0.4599	0.2079	0.058*
C22	0.35034 (18)	0.0568 (8)	0.26439 (14)	0.0636 (11)
H22	0.3412	0.2007	0.2765	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0527 (7)	0.0981 (10)	0.1083 (11)	−0.0162 (6)	−0.0053 (7)	−0.0110 (8)
O1	0.0303 (14)	0.104 (2)	0.0759 (19)	−0.0053 (14)	−0.0025 (13)	−0.0228 (17)
O2	0.0318 (13)	0.084 (2)	0.0702 (17)	0.0043 (13)	0.0009 (12)	−0.0169 (15)
O3	0.0433 (15)	0.0706 (18)	0.0707 (17)	−0.0129 (13)	0.0025 (12)	−0.0237 (14)
O4	0.0364 (14)	0.0734 (17)	0.0620 (16)	−0.0051 (12)	0.0043 (11)	−0.0207 (14)
N1	0.0323 (15)	0.073 (2)	0.0567 (18)	−0.0109 (15)	−0.0012 (13)	−0.0119 (16)
C1	0.0308 (17)	0.055 (2)	0.0426 (17)	−0.0058 (15)	0.0028 (13)	0.0032 (16)
C2	0.0357 (17)	0.056 (2)	0.0380 (16)	−0.0117 (15)	0.0027 (13)	0.0022 (15)
C3	0.0331 (17)	0.0487 (18)	0.0414 (17)	−0.0068 (14)	0.0006 (13)	0.0009 (15)
C4	0.0324 (17)	0.0441 (17)	0.0406 (17)	−0.0061 (14)	−0.0013 (13)	0.0040 (14)
C5	0.0342 (18)	0.049 (2)	0.057 (2)	−0.0005 (15)	−0.0005 (15)	−0.0043 (17)
C6	0.0277 (17)	0.056 (2)	0.059 (2)	−0.0017 (15)	−0.0034 (15)	−0.0045 (17)
C7	0.0349 (18)	0.0494 (19)	0.0436 (17)	−0.0083 (15)	−0.0032 (14)	0.0017 (15)
C8	0.0411 (19)	0.0468 (19)	0.0472 (18)	−0.0050 (15)	0.0032 (15)	−0.0038 (15)
C9	0.0321 (17)	0.0488 (18)	0.0463 (18)	0.0002 (14)	0.0036 (14)	0.0026 (15)
C10	0.0313 (17)	0.0461 (18)	0.0398 (16)	−0.0043 (14)	0.0026 (13)	0.0067 (14)
C11	0.0364 (19)	0.069 (2)	0.0487 (19)	−0.0035 (18)	0.0037 (15)	0.0011 (19)
C12	0.035 (2)	0.106 (4)	0.088 (3)	0.013 (2)	0.006 (2)	−0.022 (3)
C13	0.057 (3)	0.095 (4)	0.090 (3)	0.011 (2)	0.014 (2)	−0.017 (3)
C14	0.0368 (18)	0.055 (2)	0.0439 (18)	−0.0084 (16)	0.0010 (14)	0.0020 (16)
C15	0.048 (2)	0.077 (3)	0.059 (2)	0.000 (2)	0.0099 (18)	−0.014 (2)
C16	0.048 (3)	0.120 (4)	0.094 (4)	0.013 (3)	0.012 (2)	−0.023 (3)
C17	0.039 (2)	0.053 (2)	0.054 (2)	−0.0055 (16)	0.0012 (16)	−0.0018 (17)
C18	0.0378 (19)	0.052 (2)	0.055 (2)	−0.0006 (16)	0.0017 (16)	−0.0043 (17)
C19	0.0345 (17)	0.0400 (17)	0.0511 (19)	−0.0072 (14)	0.0027 (14)	−0.0063 (15)
C20	0.050 (2)	0.054 (2)	0.074 (3)	−0.0010 (18)	0.0123 (19)	−0.015 (2)
C21	0.069 (2)	0.0315 (16)	0.0493 (19)	−0.0200 (16)	0.0234 (17)	−0.0221 (15)
C22	0.045 (2)	0.055 (2)	0.085 (3)	−0.0013 (18)	0.000 (2)	−0.018 (2)

Geometric parameters (Å, º) top

S1—C21	1.584 (4)	C8—C9	1.381 (5)
S1—C22	1.673 (4)	C8—H8	0.9300
O1—C11	1.216 (4)	C9—C10	1.400 (5)
O2—C11	1.336 (5)	C9—H9	0.9300
O2—C12	1.447 (5)	C12—C13	1.467 (7)
O3—C14	1.209 (4)	C12—H12A	0.9700
O4—C14	1.345 (4)	C12—H12B	0.9700
O4—C15	1.443 (5)	C13—H13A	0.9600
N1—C2	1.320 (4)	C13—H13B	0.9600
N1—H1A	0.8600	C13—H13C	0.9600
N1—H1B	0.8600	C15—C16	1.504 (6)
C1—C10	1.411 (4)	C15—H15A	0.9700
C1—C2	1.424 (5)	C15—H15B	0.9700
C1—C11	1.459 (5)	C16—H16A	0.9600
C2—C3	1.432 (5)	C16—H16B	0.9600
C3—C4	1.405 (5)	C16—H16C	0.9600
C3—C14	1.445 (5)	C17—C18	1.188 (5)
C4—C5	1.408 (5)	C18—C19	1.432 (5)
C4—C10	1.473 (5)	C19—C22	1.371 (5)
C5—C6	1.374 (5)	C19—C20	1.397 (5)
C5—H5	0.9300	C20—C21	1.512 (5)
C6—C7	1.395 (5)	C20—H20	0.9300
C6—H6	0.9300	C21—H21	0.9300
C7—C8	1.407 (5)	C22—H22	0.9300
C7—C17	1.443 (5)

C21—S1—C22	97.7 (2)	O2—C12—H12A	110.2
C11—O2—C12	117.0 (3)	C13—C12—H12A	110.2
C14—O4—C15	116.9 (3)	O2—C12—H12B	110.2
C2—N1—H1A	120.0	C13—C12—H12B	110.2
C2—N1—H1B	120.0	H12A—C12—H12B	108.5
H1A—N1—H1B	120.0	C12—C13—H13A	109.5
C10—C1—C2	108.6 (3)	C12—C13—H13B	109.5
C10—C1—C11	130.4 (3)	H13A—C13—H13B	109.5
C2—C1—C11	120.9 (3)	C12—C13—H13C	109.5
N1—C2—C1	126.0 (3)	H13A—C13—H13C	109.5
N1—C2—C3	125.5 (3)	H13B—C13—H13C	109.5
C1—C2—C3	108.5 (3)	O3—C14—O4	120.8 (3)
C4—C3—C2	107.9 (3)	O3—C14—C3	124.6 (3)
C4—C3—C14	130.7 (3)	O4—C14—C3	114.6 (3)
C2—C3—C14	121.4 (3)	O4—C15—C16	106.6 (3)
C3—C4—C5	126.0 (3)	O4—C15—H15A	110.4
C3—C4—C10	108.0 (3)	C16—C15—H15A	110.4
C5—C4—C10	125.9 (3)	O4—C15—H15B	110.4
C6—C5—C4	130.2 (3)	C16—C15—H15B	110.4
C6—C5—H5	114.9	H15A—C15—H15B	108.6
C4—C5—H5	114.9	C15—C16—H16A	109.5
C5—C6—C7	130.4 (3)	C15—C16—H16B	109.5
C5—C6—H6	114.8	H16A—C16—H16B	109.5
C7—C6—H6	114.8	C15—C16—H16C	109.5
C6—C7—C8	126.3 (3)	H16A—C16—H16C	109.5
C6—C7—C17	115.8 (3)	H16B—C16—H16C	109.5
C8—C7—C17	117.9 (3)	C18—C17—C7	177.6 (4)
C9—C8—C7	129.8 (3)	C17—C18—C19	177.6 (4)
C9—C8—H8	115.1	C22—C19—C20	110.8 (3)
C7—C8—H8	115.1	C22—C19—C18	122.8 (3)
C8—C9—C10	130.4 (3)	C20—C19—C18	126.3 (3)
C8—C9—H9	114.8	C19—C20—C21	111.9 (3)
C10—C9—H9	114.8	C19—C20—H20	124.0
C9—C10—C1	126.6 (3)	C21—C20—H20	124.0
C9—C10—C4	126.4 (3)	C20—C21—S1	107.8 (2)
C1—C10—C4	106.9 (3)	C20—C21—H21	126.1
O1—C11—O2	121.5 (3)	S1—C21—H21	126.1
O1—C11—C1	124.1 (4)	C19—C22—S1	111.8 (3)
O2—C11—C1	114.5 (3)	C19—C22—H22	124.1
O2—C12—C13	107.7 (3)	S1—C22—H22	124.1

C10—C1—C2—N1	179.6 (3)	C3—C4—C10—C9	174.5 (3)
C11—C1—C2—N1	0.1 (5)	C5—C4—C10—C9	−9.2 (5)
C10—C1—C2—C3	−1.0 (4)	C3—C4—C10—C1	−2.4 (4)
C11—C1—C2—C3	179.5 (3)	C5—C4—C10—C1	173.9 (3)
N1—C2—C3—C4	178.8 (3)	C12—O2—C11—O1	4.5 (6)
C1—C2—C3—C4	−0.6 (4)	C12—O2—C11—C1	−177.3 (4)
N1—C2—C3—C14	−1.7 (5)	C10—C1—C11—O1	−175.9 (4)
C1—C2—C3—C14	178.9 (3)	C2—C1—C11—O1	3.4 (6)
C2—C3—C4—C5	−174.4 (3)	C10—C1—C11—O2	5.9 (6)
C14—C3—C4—C5	6.2 (6)	C2—C1—C11—O2	−174.7 (3)
C2—C3—C4—C10	1.8 (4)	C11—O2—C12—C13	−179.6 (4)
C14—C3—C4—C10	−177.6 (3)	C15—O4—C14—O3	1.3 (5)
C3—C4—C5—C6	−178.0 (4)	C15—O4—C14—C3	−179.8 (3)
C10—C4—C5—C6	6.4 (6)	C4—C3—C14—O3	−176.4 (4)
C4—C5—C6—C7	2.8 (7)	C2—C3—C14—O3	4.2 (6)
C5—C6—C7—C8	−5.8 (7)	C4—C3—C14—O4	4.7 (5)
C5—C6—C7—C17	174.0 (4)	C2—C3—C14—O4	−174.7 (3)
C6—C7—C8—C9	0.1 (6)	C14—O4—C15—C16	174.9 (4)
C17—C7—C8—C9	−179.7 (4)	C22—C19—C20—C21	0.9 (5)
C7—C8—C9—C10	3.0 (6)	C18—C19—C20—C21	−177.9 (3)
C8—C9—C10—C1	179.2 (4)	C19—C20—C21—S1	−0.5 (4)
C8—C9—C10—C4	2.8 (6)	C22—S1—C21—C20	0.0 (3)
C2—C1—C10—C9	−174.9 (3)	C20—C19—C22—S1	−0.9 (5)
C11—C1—C10—C9	4.6 (6)	C18—C19—C22—S1	177.9 (3)
C2—C1—C10—C4	2.0 (4)	C21—S1—C22—C19	0.5 (4)
C11—C1—C10—C4	−178.5 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the thiophene ring S1/C19–C22.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.86	2.16	2.765 (4)	127
N1—H1A···O1	0.86	2.15	2.757 (4)	127
C5—H5···O4	0.93	2.22	2.878 (4)	127
C9—H9···O2	0.93	2.23	2.897 (4)	128
N1—H1B···O3ⁱ	0.86	2.21	2.959 (4)	146
C8—H8···Cg1ⁱⁱ	0.93	2.92	3.714 (4)	144

Symmetry codes: (i) −x+3/2, −y+5/2, −z+1; (ii) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the thiophene ring S1/C19–C22.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.86	2.16	2.765 (4)	127
N1—H1A···O1	0.86	2.15	2.757 (4)	127
C5—H5···O4	0.93	2.22	2.878 (4)	127
C9—H9···O2	0.93	2.23	2.897 (4)	128
N1—H1B···O3ⁱ	0.86	2.21	2.959 (4)	146
C8—H8···Cg1ⁱⁱ	0.93	2.92	3.714 (4)	144

Symmetry codes: (i) −x+3/2, −y+5/2, −z+1; (ii) −x+1, y, −z+1/2.

Acknowledgements

This work has been performed within the `Cluster of Excellence Structure Design of Novel High-Performance Materials via Atomic Design and Defect Engineering' (ADDE), which was supported financially by the European Union (European Regional Development Fund) and by the Ministry of Science and Art of Saxony (SMWK).

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Volume 71| Part 3| March 2015| Pages o212-o213

doi:10.1107/S2056989015003898

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

Crystal structure of di­ethyl 2-amino-6-[(thio­phen-3-yl)ethyn­yl]azulene-1,3-di­carboxyl­ate

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of diethyl 2-amino-6-[(thiophen-3-yl)ethynyl]azulene-1,3-dicarboxylate