Crystal structure of diethyl 2-amino-6-[(thio-phen-3-yl)ethyn-yl]azulene-1,3-di-carboxyl-ate.

The title compound, C22H19NO4S, has an almost planar geometry supported by intra-molecular N-H⋯O and C-H⋯O hydrogen bonds. The thio-phene ring is inclined to the azulene ring by 4.85 (16)°, while the eth-oxy-carbonyl groups are inclined to the azulene ring by 7.0 (2) and 5.7 (2)°. In the crystal, mol-ecules are linked by pairs of N-H⋯O hydrogen bonds, forming inversion dimers with an R 2 (2)(12) ring motif. The dimers are linked via C-H⋯π inter-actions, forming sheets parallel to (10-1).

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 ▸).

Experimental

Crystal data

C22H19NO4S

M = 393.44

Monoclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.242

S = 1.04

3679 reflections

255 parameters

H-atom parameters constrained

Δρmax = 0.68 e Å−3

Δρmin = −0.69 e Å−3

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 ▸).

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015003898/su5088sup1.cif

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

Click here for additional data file.

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

Click here for additional data file.

. DOI: 10.1107/S2056989015003898/su5088fig1.tif

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).

Click here for additional data file.

b . DOI: 10.1107/S2056989015003898/su5088fig2.tif

Crystal packing of the title compound viewed along the b-axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1051132

Additional supporting information: crystallographic information; 3D view; checkCIF report

C22H19NO4S	F(000) = 1648
Mr = 393.44	Dx = 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

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

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(Fo2) + (0.1341P)2 + 7.3721P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3679 reflections	Δρmax = 0.68 e Å−3
255 parameters	Δρmin = −0.69 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

Table 1

Hydrogen-bond geometry (, )

Cg1 is the centroid of the thiophene ring S1/C19C22.

DHA	DH	HA	D A	DHA
N1H1BO3	0.86	2.16	2.765(4)	127
N1H1AO1	0.86	2.15	2.757(4)	127
C5H5O4	0.93	2.22	2.878(4)	127
C9H9O2	0.93	2.23	2.897(4)	128
N1H1BO3i	0.86	2.21	2.959(4)	146
C8H8Cg1ii	0.93	2.92	3.714(4)	144

Symmetry codes: (i) ; (ii) .