Crystal structure of 1-iodo-3-{[4-(tert-butyl-sulfan-yl)phen-yl]ethyn-yl}azulene.

The title compound, C20H19IS, features a 1,3-disubstituted azulene involving an ethynylene elongated 4-(tert-butyl-sulfanyl)-phenyl sidearm and an iodine atom as the substituents. The azulene ring system is almost planar (r.m.s. deviation = 0.012 Å) and subtends a dihedral angle of 35.7 (1)° with the benzene ring. As a result of the inherent dipole character of the azulene core, a supra-molecular π-π dimer [separation between the centroids of the five- and seven-membered rings = 3.7632 (10) Å] with anti-parallel orientated mol-ecules can be observed in the crystal. The packing is consolidated by an unusual I⋯π(acetyl-ene) contact [I⋯Cg = 3.34 Å, C-I⋯Cg = 173.3°], and a very weak C-H⋯π inter-action is also found in the structure, with the azulene five-membered ring as the acceptor.

Related literature

For background to this work, see: Strachota et al. (2008 ▸); Xia et al. (2014 ▸). For related structures, see: Förster et al. (2012 ▸, 2014 ▸). For the synthesis of the starting compounds 1,3-di­iodo­azulene and 1-(tert-butyl­sulfan­yl)-4-ethynyl­benzene, see: Wakabayashi et al. (1998 ▸); Mayor et al. (2003 ▸). For the Sonogashira–Hagihara cross-coupling reaction, see: Sonogashira et al. (1975 ▸). For I⋯π contacts, see: Forni et al. (2012 ▸). For C—H⋯π inter­actions, see: Nishio et al. (2009 ▸).

Experimental

Crystal data

C22H19IS

M = 442.33

Monoclinic,

a = 12.7222 (2) Å

b = 11.9892 (2) Å

c = 13.7895 (3) Å

β = 113.851 (1)°

V = 1923.68 (6) Å3

Z = 4

Mo Kα radiation

μ = 1.77 mm−1

T = 100 K

0.28 × 0.20 × 0.13 mm

Data collection

Bruker Kappa Apex CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.637, T max = 0.802

23474 measured reflections

5163 independent reflections

4688 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.059

S = 1.04

5163 reflections

220 parameters

H-atom parameters constrained

Δρmax = 1.37 e Å−3

Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2010 ▸); cell refinement: SAINT-NT (Sheldrick, 2008 ▸); data reduction: SAINT-NT; 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, New_Global_Publ_Block. DOI: 10.1107/S2056989015012542/hb7447sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012542/hb7447Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015012542/hb7447Isup3.tif

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015012542/hb7447Isup4.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015012542/hb7447fig1.tif

The mol­ecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

c . DOI: 10.1107/S2056989015012542/hb7447fig2.tif

A view along the c axis of the crystal packing of the title compound.

CCDC reference: 1409619

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

C22H19IS	F(000) = 880
Mr = 442.33	Dx = 1.527 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.7222 (2) Å	Cell parameters from 9945 reflections
b = 11.9892 (2) Å	θ = 2.5–33.1°
c = 13.7895 (3) Å	µ = 1.77 mm−1
β = 113.851 (1)°	T = 100 K
V = 1923.68 (6) Å3	Irregular, violet
Z = 4	0.28 × 0.20 × 0.13 mm

Bruker Kappa Apex CCD diffractometer	4688 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.024
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 29.1°, θmin = 1.8°
Tmin = 0.637, Tmax = 0.802	h = −17→17
23474 measured reflections	k = −16→16
5163 independent reflections	l = −18→18

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021	H-atom parameters constrained
wR(F2) = 0.059	w = 1/[σ2(Fo2) + (0.0333P)2 + 0.9341P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
5163 reflections	Δρmax = 1.37 e Å−3
220 parameters	Δρmin = −0.39 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
I1	0.84013 (2)	0.46782 (2)	0.23899 (2)	0.02206 (5)
S2	0.11506 (4)	−0.30969 (4)	0.07255 (4)	0.02563 (10)
C1	0.69313 (13)	0.37992 (13)	0.14949 (13)	0.0173 (3)
C2	0.64454 (13)	0.29623 (13)	0.18826 (13)	0.0179 (3)
H2	0.6733	0.2710	0.2596	0.022*
C3	0.54571 (13)	0.25519 (13)	0.10422 (13)	0.0173 (3)
C4	0.53172 (13)	0.31415 (13)	0.01096 (13)	0.0163 (3)
C5	0.44468 (14)	0.29644 (14)	−0.08807 (14)	0.0204 (3)
H5	0.3916	0.2391	−0.0919	0.024*
C6	0.42455 (15)	0.35115 (15)	−0.18259 (14)	0.0236 (3)
H6	0.3600	0.3256	−0.2426	0.028*
C7	0.48585 (16)	0.43818 (16)	−0.20148 (14)	0.0238 (3)
H7	0.4551	0.4657	−0.2721	0.029*
C8	0.58518 (16)	0.49110 (16)	−0.13288 (16)	0.0249 (4)
H8	0.6140	0.5480	−0.1634	0.030*
C9	0.64791 (15)	0.47161 (13)	−0.02540 (15)	0.0207 (3)
H9	0.7142	0.5168	0.0076	0.025*
C10	0.62711 (13)	0.39541 (13)	0.04023 (13)	0.0160 (3)
C11	0.47274 (14)	0.16724 (14)	0.10849 (14)	0.0197 (3)
C12	0.41110 (14)	0.09113 (14)	0.10767 (14)	0.0214 (3)
C13	0.34086 (13)	−0.00436 (14)	0.10156 (14)	0.0183 (3)
C14	0.31147 (16)	−0.03408 (14)	0.18573 (15)	0.0230 (4)
H14	0.3377	0.0096	0.2486	0.028*
C15	0.24401 (15)	−0.12745 (15)	0.17689 (14)	0.0219 (3)
H15	0.2249	−0.1478	0.2343	0.026*
C16	0.20377 (14)	−0.19206 (13)	0.08477 (14)	0.0188 (3)
C17	0.23511 (15)	−0.16333 (14)	0.00239 (15)	0.0217 (3)
H17	0.2099	−0.2079	−0.0599	0.026*
C18	0.30281 (15)	−0.07036 (15)	0.01021 (14)	0.0218 (3)
H18	0.3234	−0.0514	−0.0467	0.026*
C19	−0.03091 (15)	−0.24833 (16)	0.01235 (15)	0.0258 (4)
C20	−0.05345 (17)	−0.19664 (19)	−0.09463 (17)	0.0337 (4)
H20A	−0.1330	−0.1700	−0.1272	0.051*
H20B	−0.0411	−0.2527	−0.1407	0.051*
H20C	−0.0008	−0.1339	−0.0851	0.051*
C21	−0.04654 (19)	−0.1617 (2)	0.0863 (2)	0.0435 (6)
H21A	0.0031	−0.0974	0.0917	0.065*
H21B	−0.0259	−0.1946	0.1567	0.065*
H21C	−0.1269	−0.1374	0.0579	0.065*
C22	−0.1104 (2)	−0.3474 (2)	−0.0007 (2)	0.0454 (6)
H22A	−0.1904	−0.3218	−0.0299	0.068*
H22B	−0.0920	−0.3824	0.0684	0.068*
H22C	−0.0999	−0.4018	−0.0491	0.068*

	U11	U22	U33	U12	U13	U23
I1	0.01979 (7)	0.02162 (7)	0.02101 (7)	−0.00596 (4)	0.00437 (5)	−0.00162 (4)
S2	0.0270 (2)	0.01496 (19)	0.0329 (2)	−0.00596 (16)	0.01011 (19)	0.00387 (16)
C1	0.0149 (7)	0.0151 (7)	0.0203 (8)	−0.0020 (6)	0.0054 (6)	−0.0022 (6)
C2	0.0170 (7)	0.0161 (7)	0.0202 (8)	0.0007 (6)	0.0070 (6)	0.0020 (6)
C3	0.0165 (7)	0.0136 (7)	0.0214 (8)	−0.0004 (6)	0.0071 (6)	0.0008 (6)
C4	0.0162 (7)	0.0121 (7)	0.0212 (8)	0.0000 (5)	0.0081 (6)	−0.0007 (6)
C5	0.0202 (7)	0.0167 (7)	0.0229 (8)	−0.0031 (6)	0.0073 (7)	−0.0020 (6)
C6	0.0238 (8)	0.0243 (9)	0.0183 (8)	−0.0017 (7)	0.0040 (7)	−0.0010 (6)
C7	0.0294 (9)	0.0243 (8)	0.0176 (8)	0.0005 (7)	0.0094 (7)	0.0021 (6)
C8	0.0269 (9)	0.0213 (8)	0.0295 (10)	−0.0012 (7)	0.0146 (8)	0.0059 (7)
C9	0.0208 (8)	0.0174 (8)	0.0251 (9)	−0.0047 (6)	0.0106 (7)	−0.0014 (6)
C10	0.0157 (7)	0.0135 (7)	0.0193 (7)	−0.0006 (5)	0.0076 (6)	−0.0016 (6)
C11	0.0178 (7)	0.0171 (7)	0.0225 (8)	0.0009 (6)	0.0064 (6)	0.0035 (6)
C12	0.0168 (7)	0.0203 (8)	0.0244 (8)	0.0003 (6)	0.0057 (6)	0.0055 (6)
C13	0.0141 (7)	0.0153 (7)	0.0239 (8)	−0.0005 (6)	0.0060 (6)	0.0037 (6)
C14	0.0229 (8)	0.0243 (9)	0.0195 (8)	−0.0065 (6)	0.0063 (7)	−0.0008 (6)
C15	0.0231 (8)	0.0238 (8)	0.0190 (8)	−0.0051 (6)	0.0087 (7)	0.0018 (6)
C16	0.0181 (7)	0.0140 (7)	0.0240 (8)	−0.0013 (6)	0.0080 (6)	0.0026 (6)
C17	0.0248 (8)	0.0175 (8)	0.0269 (9)	−0.0028 (6)	0.0147 (7)	−0.0041 (6)
C18	0.0240 (8)	0.0207 (8)	0.0261 (9)	−0.0010 (6)	0.0157 (7)	0.0022 (7)
C19	0.0210 (8)	0.0274 (9)	0.0279 (9)	−0.0097 (7)	0.0087 (7)	0.0018 (7)
C20	0.0284 (9)	0.0367 (11)	0.0314 (10)	−0.0069 (8)	0.0072 (8)	0.0088 (8)
C21	0.0270 (10)	0.0586 (15)	0.0486 (14)	−0.0018 (10)	0.0191 (10)	−0.0132 (11)
C22	0.0338 (11)	0.0454 (13)	0.0482 (14)	−0.0219 (10)	0.0073 (10)	0.0110 (11)

I1—C1	2.0651 (15)	C13—C18	1.398 (3)
S2—C16	1.7712 (16)	C13—C14	1.402 (2)
S2—C19	1.8526 (19)	C14—C15	1.386 (2)
C1—C2	1.394 (2)	C14—H14	0.9500
C1—C10	1.409 (2)	C15—C16	1.396 (2)
C2—C3	1.410 (2)	C15—H15	0.9500
C2—H2	0.9500	C16—C17	1.391 (2)
C3—C4	1.414 (2)	C17—C18	1.386 (2)
C3—C11	1.422 (2)	C17—H17	0.9500
C4—C5	1.383 (2)	C18—H18	0.9500
C4—C10	1.479 (2)	C19—C20	1.517 (3)
C5—C6	1.387 (2)	C19—C22	1.523 (3)
C5—H5	0.9500	C19—C21	1.523 (3)
C6—C7	1.389 (3)	C20—H20A	0.9800
C6—H6	0.9500	C20—H20B	0.9800
C7—C8	1.388 (3)	C20—H20C	0.9800
C7—H7	0.9500	C21—H21A	0.9800
C8—C9	1.390 (3)	C21—H21B	0.9800
C8—H8	0.9500	C21—H21C	0.9800
C9—C10	1.385 (2)	C22—H22A	0.9800
C9—H9	0.9500	C22—H22B	0.9800
C11—C12	1.200 (2)	C22—H22C	0.9800
C12—C13	1.434 (2)
C16—S2—C19	102.19 (8)	C13—C14—H14	120.1
C2—C1—C10	109.87 (14)	C14—C15—C16	120.96 (16)
C2—C1—I1	124.97 (12)	C14—C15—H15	119.5
C10—C1—I1	125.15 (12)	C16—C15—H15	119.5
C1—C2—C3	108.81 (14)	C17—C16—C15	119.00 (15)
C1—C2—H2	125.6	C17—C16—S2	120.11 (13)
C3—C2—H2	125.6	C15—C16—S2	120.89 (13)
C2—C3—C4	108.39 (14)	C18—C17—C16	120.67 (16)
C2—C3—C11	127.23 (15)	C18—C17—H17	119.7
C4—C3—C11	124.35 (15)	C16—C17—H17	119.7
C5—C4—C3	125.25 (15)	C17—C18—C13	120.22 (16)
C5—C4—C10	127.69 (15)	C17—C18—H18	119.9
C3—C4—C10	107.06 (14)	C13—C18—H18	119.9
C4—C5—C6	128.67 (16)	C20—C19—C22	110.38 (17)
C4—C5—H5	115.7	C20—C19—C21	110.34 (19)
C6—C5—H5	115.7	C22—C19—C21	110.54 (18)
C5—C6—C7	128.83 (17)	C20—C19—S2	111.05 (13)
C5—C6—H6	115.6	C22—C19—S2	103.93 (14)
C7—C6—H6	115.6	C21—C19—S2	110.44 (14)
C8—C7—C6	129.86 (17)	C19—C20—H20A	109.5
C8—C7—H7	115.1	C19—C20—H20B	109.5
C6—C7—H7	115.1	H20A—C20—H20B	109.5
C7—C8—C9	128.44 (17)	C19—C20—H20C	109.5
C7—C8—H8	115.8	H20A—C20—H20C	109.5
C9—C8—H8	115.8	H20B—C20—H20C	109.5
C10—C9—C8	128.97 (16)	C19—C21—H21A	109.5
C10—C9—H9	115.5	C19—C21—H21B	109.5
C8—C9—H9	115.5	H21A—C21—H21B	109.5
C9—C10—C1	126.65 (15)	C19—C21—H21C	109.5
C9—C10—C4	127.49 (15)	H21A—C21—H21C	109.5
C1—C10—C4	105.87 (13)	H21B—C21—H21C	109.5
C12—C11—C3	176.91 (19)	C19—C22—H22A	109.5
C11—C12—C13	175.55 (19)	C19—C22—H22B	109.5
C18—C13—C14	119.41 (15)	H22A—C22—H22B	109.5
C18—C13—C12	119.05 (16)	C19—C22—H22C	109.5
C14—C13—C12	121.53 (16)	H22A—C22—H22C	109.5
C15—C14—C13	119.71 (16)	H22B—C22—H22C	109.5
C15—C14—H14	120.1
C10—C1—C2—C3	0.28 (19)	C5—C4—C10—C9	1.0 (3)
I1—C1—C2—C3	−179.64 (11)	C3—C4—C10—C9	−179.53 (16)
C1—C2—C3—C4	−0.09 (18)	C5—C4—C10—C1	−179.21 (16)
C1—C2—C3—C11	177.91 (16)	C3—C4—C10—C1	0.28 (17)
C2—C3—C4—C5	179.39 (15)	C18—C13—C14—C15	−0.8 (3)
C11—C3—C4—C5	1.3 (3)	C12—C13—C14—C15	−179.58 (16)
C2—C3—C4—C10	−0.12 (17)	C13—C14—C15—C16	−0.6 (3)
C11—C3—C4—C10	−178.19 (15)	C14—C15—C16—C17	1.8 (3)
C3—C4—C5—C6	179.33 (17)	C14—C15—C16—S2	−178.67 (14)
C10—C4—C5—C6	−1.3 (3)	C19—S2—C16—C17	−89.74 (15)
C4—C5—C6—C7	−0.8 (3)	C19—S2—C16—C15	90.77 (15)
C5—C6—C7—C8	2.6 (3)	C15—C16—C17—C18	−1.6 (3)
C6—C7—C8—C9	−1.7 (3)	S2—C16—C17—C18	178.85 (14)
C7—C8—C9—C10	−0.4 (3)	C16—C17—C18—C13	0.2 (3)
C8—C9—C10—C1	−179.23 (18)	C14—C13—C18—C17	1.0 (3)
C8—C9—C10—C4	0.5 (3)	C12—C13—C18—C17	179.80 (16)
C2—C1—C10—C9	179.47 (16)	C16—S2—C19—C20	60.73 (15)
I1—C1—C10—C9	−0.6 (2)	C16—S2—C19—C22	179.40 (14)
C2—C1—C10—C4	−0.35 (18)	C16—S2—C19—C21	−62.02 (16)
I1—C1—C10—C4	179.57 (11)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···Cg1i	0.95	2.95	3.471 (2)	116

Table 1

Hydrogen-bond geometry (, )

Cg1 is the centroid of the C1C4/C10 ring.

DHA	DH	HA	D A	DHA
C17H17Cg1i	0.95	2.95	3.471(2)	116

Symmetry code: (i) .