Crystal structure of 1,3-bis-{[4-(acetyl-sulfanyl)phenyl]ethynyl}azulene.

In the title compound, C30H20O2S2, the dihedral angles between the central azulene ring system (r.m.s. deviation = 0.039 Å) and the pendant benzene rings are 28.96 (7) and 55.15 (7)°. The dihedral angles between the benzene rings and their attached acetyl-sulfanyl groups are 59.60 (10) and 84.79 (10)°. The expected π-π stacking inter-actions are not observed in the crystal structure; instead, the packing features C-H⋯O hydrogen bonds, which link the mol-ecules into C(12) [010] chains, which are supported by weak C-H⋯π contacts.

Related literature

For background to this work, see: Wang et al. (2009 ▸); Puodziukynaite et al. (2014 ▸); Xia et al. (2014 ▸). For the synthesis and related structures, see: Förster et al. (2012 ▸, 2014 ▸).

Experimental

Crystal data

C30H20O2S2

M = 476.58

Monoclinic,

a = 13.7674 (3) Å

b = 8.9849 (2) Å

c = 19.7586 (4) Å

β = 104.022 (1)°

V = 2371.28 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.25 mm−1

T = 100 K

0.24 × 0.23 × 0.15 mm

Data collection

Bruker Kappa APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.942, T max = 0.963

36340 measured reflections

5898 independent reflections

4422 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.130

S = 1.03

5898 reflections

309 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker AXS); cell refinement: SAINT (Sheldrick, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2015 (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, publication_text. DOI: 10.1107/S2056989016000323/hb7546sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016000323/hb7546Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989016000323/hb7546Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989016000323/hb7546fig1.tif

Ellipsoid plot.

Click here for additional data file.

. DOI: 10.1107/S2056989016000323/hb7546fig2.tif

Packing diagram.

CCDC reference: 1445850

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

C30H20O2S2	F(000) = 992
Mr = 476.58	Dx = 1.335 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.7674 (3) Å	Cell parameters from 8057 reflections
b = 8.9849 (2) Å	θ = 2.5–28.0°
c = 19.7586 (4) Å	µ = 0.25 mm−1
β = 104.022 (1)°	T = 100 K
V = 2371.28 (9) Å3	Irregular, green
Z = 4	0.24 × 0.23 × 0.15 mm

Bruker Kappa APEX CCD diffractometer	4422 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.039
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 28.3°, θmin = 2.5°
Tmin = 0.942, Tmax = 0.963	h = −18→18
36340 measured reflections	k = −12→11
5898 independent reflections	l = −26→26

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H-atom parameters constrained
wR(F2) = 0.130	w = 1/[σ2(Fo2) + (0.0658P)2 + 1.347P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
5898 reflections	Δρmax = 0.44 e Å−3
309 parameters	Δρmin = −0.27 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	1.37569 (4)	0.11544 (6)	0.58441 (3)	0.03405 (15)
S2	0.55913 (4)	−0.42293 (6)	1.10153 (3)	0.03144 (14)
O1	1.43557 (12)	0.39449 (19)	0.60090 (9)	0.0418 (4)
O2	0.52513 (12)	−0.17076 (16)	1.16136 (8)	0.0361 (4)
C1	0.93413 (13)	0.2985 (2)	0.81129 (9)	0.0229 (4)
C2	0.91025 (14)	0.1731 (2)	0.84616 (10)	0.0248 (4)
H2	0.9425	0.0791	0.8485	0.030*
C3	0.83172 (14)	0.2075 (2)	0.87699 (10)	0.0235 (4)
C4	0.80547 (13)	0.3585 (2)	0.86356 (9)	0.0224 (4)
C5	0.73471 (14)	0.4346 (2)	0.88954 (10)	0.0258 (4)
H5	0.7021	0.3782	0.9182	0.031*
C6	0.70505 (15)	0.5828 (2)	0.87924 (11)	0.0286 (4)
H6	0.6574	0.6156	0.9036	0.034*
C7	0.73635 (14)	0.6887 (2)	0.83792 (10)	0.0281 (4)
H7	0.7048	0.7831	0.8366	0.034*
C8	0.80679 (15)	0.6777 (2)	0.79820 (10)	0.0279 (4)
H8	0.8147	0.7643	0.7725	0.033*
C9	0.86748 (14)	0.5575 (2)	0.79079 (10)	0.0244 (4)
H9	0.9129	0.5744	0.7623	0.029*
C10	0.86986 (13)	0.4173 (2)	0.81964 (9)	0.0217 (4)
C11	1.01077 (14)	0.2995 (2)	0.77358 (10)	0.0235 (4)
C12	1.07506 (14)	0.2876 (2)	0.74377 (10)	0.0252 (4)
C13	1.15323 (13)	0.2606 (2)	0.70827 (10)	0.0222 (4)
C14	1.15694 (14)	0.3358 (2)	0.64730 (10)	0.0261 (4)
H14	1.1120	0.4155	0.6312	0.031*
C15	1.22577 (14)	0.2948 (2)	0.61000 (10)	0.0272 (4)
H15	1.2263	0.3440	0.5675	0.033*
C16	1.29404 (13)	0.1821 (2)	0.63447 (10)	0.0242 (4)
C17	1.29573 (14)	0.1142 (2)	0.69783 (10)	0.0270 (4)
H17	1.3454	0.0420	0.7163	0.032*
C18	1.22522 (14)	0.1517 (2)	0.73400 (10)	0.0269 (4)
H18	1.2256	0.1031	0.7768	0.032*
C19	1.44675 (15)	0.2760 (3)	0.57564 (11)	0.0328 (5)
C20	1.52157 (17)	0.2459 (3)	0.53316 (12)	0.0483 (7)
H20A	1.4865	0.2112	0.4866	0.072*
H20B	1.5688	0.1692	0.5562	0.072*
H20C	1.5582	0.3375	0.5289	0.072*
C21	0.78423 (15)	0.1054 (2)	0.91530 (9)	0.0243 (4)
C22	0.74797 (15)	0.0199 (2)	0.94649 (10)	0.0275 (4)
C23	0.70236 (14)	−0.0862 (2)	0.98362 (10)	0.0246 (4)
C24	0.76034 (15)	−0.1665 (2)	1.03950 (10)	0.0284 (4)
H24	0.8306	−0.1504	1.0535	0.034*
C25	0.71595 (15)	−0.2691 (2)	1.07442 (11)	0.0289 (4)
H25	0.7557	−0.3248	1.1119	0.035*
C26	0.61271 (15)	−0.2908 (2)	1.05464 (10)	0.0268 (4)
C27	0.55486 (15)	−0.2111 (2)	1.00026 (11)	0.0318 (5)
H27	0.4845	−0.2261	0.9870	0.038*
C28	0.59931 (15)	−0.1085 (2)	0.96468 (11)	0.0308 (4)
H28	0.5592	−0.0532	0.9272	0.037*
C29	0.52713 (14)	−0.3041 (2)	1.16535 (10)	0.0261 (4)
C30	0.50479 (17)	−0.3905 (2)	1.22472 (11)	0.0341 (5)
H30A	0.5636	−0.3895	1.2643	0.051*
H30B	0.4883	−0.4935	1.2100	0.051*
H30C	0.4479	−0.3451	1.2387	0.051*

	U11	U22	U33	U12	U13	U23
S1	0.0321 (3)	0.0331 (3)	0.0435 (3)	0.0021 (2)	0.0220 (2)	−0.0023 (2)
S2	0.0425 (3)	0.0203 (2)	0.0379 (3)	−0.0023 (2)	0.0221 (2)	0.0025 (2)
O1	0.0341 (8)	0.0477 (10)	0.0446 (9)	−0.0138 (7)	0.0117 (7)	−0.0013 (8)
O2	0.0478 (9)	0.0248 (8)	0.0381 (8)	0.0010 (7)	0.0152 (7)	0.0001 (6)
C1	0.0234 (9)	0.0222 (9)	0.0244 (9)	−0.0025 (7)	0.0085 (7)	−0.0004 (7)
C2	0.0276 (9)	0.0225 (9)	0.0260 (9)	−0.0003 (7)	0.0097 (7)	−0.0001 (8)
C3	0.0246 (9)	0.0238 (9)	0.0233 (9)	−0.0034 (7)	0.0083 (7)	0.0004 (7)
C4	0.0224 (8)	0.0239 (9)	0.0217 (9)	−0.0023 (7)	0.0069 (7)	−0.0007 (7)
C5	0.0232 (9)	0.0301 (10)	0.0266 (9)	−0.0025 (8)	0.0108 (7)	−0.0010 (8)
C6	0.0259 (9)	0.0312 (11)	0.0309 (10)	0.0015 (8)	0.0114 (8)	−0.0043 (8)
C7	0.0273 (9)	0.0266 (10)	0.0293 (10)	0.0039 (8)	0.0048 (8)	−0.0027 (8)
C8	0.0314 (10)	0.0241 (10)	0.0277 (10)	0.0006 (8)	0.0062 (8)	0.0041 (8)
C9	0.0259 (9)	0.0261 (10)	0.0224 (9)	−0.0024 (7)	0.0082 (7)	0.0002 (7)
C10	0.0208 (8)	0.0237 (9)	0.0213 (8)	−0.0023 (7)	0.0067 (7)	−0.0012 (7)
C11	0.0265 (9)	0.0180 (9)	0.0269 (9)	−0.0045 (7)	0.0083 (7)	−0.0018 (7)
C12	0.0272 (9)	0.0179 (9)	0.0309 (10)	−0.0011 (7)	0.0078 (8)	−0.0020 (7)
C13	0.0222 (8)	0.0193 (9)	0.0267 (9)	−0.0021 (7)	0.0093 (7)	−0.0034 (7)
C14	0.0234 (9)	0.0230 (10)	0.0331 (10)	0.0033 (7)	0.0093 (8)	0.0033 (8)
C15	0.0283 (9)	0.0271 (10)	0.0284 (10)	0.0010 (8)	0.0111 (8)	0.0059 (8)
C16	0.0217 (8)	0.0241 (10)	0.0293 (9)	−0.0010 (7)	0.0113 (7)	−0.0016 (8)
C17	0.0244 (9)	0.0240 (10)	0.0335 (10)	0.0033 (7)	0.0085 (8)	0.0027 (8)
C18	0.0293 (10)	0.0256 (10)	0.0279 (10)	0.0009 (8)	0.0108 (8)	0.0023 (8)
C19	0.0232 (9)	0.0482 (14)	0.0265 (10)	−0.0047 (9)	0.0051 (8)	0.0029 (9)
C20	0.0271 (11)	0.084 (2)	0.0374 (12)	−0.0038 (12)	0.0152 (9)	0.0081 (13)
C21	0.0329 (10)	0.0213 (9)	0.0204 (9)	0.0035 (8)	0.0095 (7)	−0.0006 (7)
C22	0.0301 (10)	0.0246 (10)	0.0304 (10)	0.0002 (8)	0.0126 (8)	−0.0050 (8)
C23	0.0321 (10)	0.0181 (9)	0.0284 (9)	−0.0015 (7)	0.0169 (8)	−0.0030 (7)
C24	0.0273 (9)	0.0285 (10)	0.0318 (10)	−0.0006 (8)	0.0115 (8)	0.0010 (8)
C25	0.0325 (10)	0.0262 (10)	0.0304 (10)	0.0028 (8)	0.0124 (8)	0.0046 (8)
C26	0.0357 (10)	0.0184 (9)	0.0314 (10)	−0.0013 (8)	0.0181 (8)	0.0002 (8)
C27	0.0253 (9)	0.0294 (11)	0.0424 (12)	−0.0021 (8)	0.0117 (8)	0.0057 (9)
C28	0.0309 (10)	0.0271 (10)	0.0358 (11)	0.0019 (8)	0.0110 (8)	0.0096 (9)
C29	0.0248 (9)	0.0233 (10)	0.0311 (10)	−0.0001 (7)	0.0085 (8)	0.0012 (8)
C30	0.0416 (12)	0.0305 (11)	0.0355 (11)	0.0012 (9)	0.0195 (9)	0.0028 (9)

S1—C16	1.7716 (19)	C14—C15	1.384 (3)
S1—C19	1.775 (2)	C14—H14	0.9500
S2—C26	1.7727 (19)	C15—C16	1.387 (3)
S2—C29	1.787 (2)	C15—H15	0.9500
O1—C19	1.201 (3)	C16—C17	1.387 (3)
O2—C29	1.201 (2)	C17—C18	1.380 (3)
C1—C2	1.401 (3)	C17—H17	0.9500
C1—C10	1.421 (3)	C18—H18	0.9500
C1—C11	1.432 (2)	C19—C20	1.503 (3)
C2—C3	1.398 (3)	C20—H20A	0.9800
C2—H2	0.9500	C20—H20B	0.9800
C3—C4	1.413 (3)	C20—H20C	0.9800
C3—C21	1.443 (3)	C21—C22	1.170 (3)
C4—C5	1.386 (3)	C22—C23	1.437 (3)
C4—C10	1.480 (2)	C23—C28	1.391 (3)
C5—C6	1.393 (3)	C23—C24	1.396 (3)
C5—H5	0.9500	C24—C25	1.380 (3)
C6—C7	1.388 (3)	C24—H24	0.9500
C6—H6	0.9500	C25—C26	1.394 (3)
C7—C8	1.391 (3)	C25—H25	0.9500
C7—H7	0.9500	C26—C27	1.374 (3)
C8—C9	1.394 (3)	C27—C28	1.388 (3)
C8—H8	0.9500	C27—H27	0.9500
C9—C10	1.380 (3)	C28—H28	0.9500
C9—H9	0.9500	C29—C30	1.500 (3)
C11—C12	1.181 (3)	C30—H30A	0.9800
C12—C13	1.440 (3)	C30—H30B	0.9800
C13—C14	1.393 (3)	C30—H30C	0.9800
C13—C18	1.398 (3)
C16—S1—C19	102.66 (10)	C17—C16—S1	118.76 (15)
C26—S2—C29	100.01 (9)	C18—C17—C16	120.01 (18)
C2—C1—C10	108.67 (16)	C18—C17—H17	120.0
C2—C1—C11	123.48 (17)	C16—C17—H17	120.0
C10—C1—C11	127.85 (17)	C17—C18—C13	120.56 (18)
C3—C2—C1	109.57 (17)	C17—C18—H18	119.7
C3—C2—H2	125.2	C13—C18—H18	119.7
C1—C2—H2	125.2	O1—C19—C20	124.5 (2)
C2—C3—C4	108.68 (16)	O1—C19—S1	123.40 (16)
C2—C3—C21	125.77 (18)	C20—C19—S1	112.13 (18)
C4—C3—C21	125.55 (17)	C19—C20—H20A	109.5
C5—C4—C3	125.09 (17)	C19—C20—H20B	109.5
C5—C4—C10	128.00 (18)	H20A—C20—H20B	109.5
C3—C4—C10	106.88 (16)	C19—C20—H20C	109.5
C4—C5—C6	128.65 (18)	H20A—C20—H20C	109.5
C4—C5—H5	115.7	H20B—C20—H20C	109.5
C6—C5—H5	115.7	C22—C21—C3	178.1 (2)
C7—C6—C5	128.24 (18)	C21—C22—C23	178.9 (2)
C7—C6—H6	115.9	C28—C23—C24	119.25 (17)
C5—C6—H6	115.9	C28—C23—C22	120.10 (18)
C6—C7—C8	129.88 (19)	C24—C23—C22	120.64 (18)
C6—C7—H7	115.1	C25—C24—C23	120.20 (18)
C8—C7—H7	115.1	C25—C24—H24	119.9
C7—C8—C9	129.18 (19)	C23—C24—H24	119.9
C7—C8—H8	115.4	C24—C25—C26	119.92 (19)
C9—C8—H8	115.4	C24—C25—H25	120.0
C10—C9—C8	128.20 (18)	C26—C25—H25	120.0
C10—C9—H9	115.9	C27—C26—C25	120.30 (18)
C8—C9—H9	115.9	C27—C26—S2	121.48 (15)
C9—C10—C1	126.22 (17)	C25—C26—S2	118.21 (15)
C9—C10—C4	127.60 (17)	C26—C27—C28	119.96 (19)
C1—C10—C4	106.17 (16)	C26—C27—H27	120.0
C12—C11—C1	174.3 (2)	C28—C27—H27	120.0
C11—C12—C13	175.5 (2)	C27—C28—C23	120.36 (19)
C14—C13—C18	118.85 (17)	C27—C28—H28	119.8
C14—C13—C12	121.86 (17)	C23—C28—H28	119.8
C18—C13—C12	119.23 (17)	O2—C29—C30	124.21 (19)
C15—C14—C13	120.34 (18)	O2—C29—S2	123.75 (16)
C15—C14—H14	119.8	C30—C29—S2	112.03 (14)
C13—C14—H14	119.8	C29—C30—H30A	109.5
C14—C15—C16	120.16 (17)	C29—C30—H30B	109.5
C14—C15—H15	119.9	H30A—C30—H30B	109.5
C16—C15—H15	119.9	C29—C30—H30C	109.5
C15—C16—C17	119.82 (17)	H30A—C30—H30C	109.5
C15—C16—S1	121.35 (15)	H30B—C30—H30C	109.5
C10—C1—C2—C3	0.1 (2)	C13—C14—C15—C16	−2.4 (3)
C11—C1—C2—C3	−179.26 (17)	C14—C15—C16—C17	−2.5 (3)
C1—C2—C3—C4	−1.4 (2)	C14—C15—C16—S1	174.31 (15)
C1—C2—C3—C21	177.71 (18)	C19—S1—C16—C15	61.42 (18)
C2—C3—C4—C5	−175.89 (18)	C19—S1—C16—C17	−121.78 (17)
C21—C3—C4—C5	5.0 (3)	C15—C16—C17—C18	4.4 (3)
C2—C3—C4—C10	2.2 (2)	S1—C16—C17—C18	−172.40 (15)
C21—C3—C4—C10	−176.99 (17)	C16—C17—C18—C13	−1.6 (3)
C3—C4—C5—C6	179.6 (2)	C14—C13—C18—C17	−3.1 (3)
C10—C4—C5—C6	1.9 (3)	C12—C13—C18—C17	174.31 (18)
C4—C5—C6—C7	3.0 (4)	C16—S1—C19—O1	0.8 (2)
C5—C6—C7—C8	−2.4 (4)	C16—S1—C19—C20	−179.13 (15)
C6—C7—C8—C9	−2.1 (4)	C28—C23—C24—C25	1.4 (3)
C7—C8—C9—C10	2.4 (4)	C22—C23—C24—C25	−179.43 (18)
C8—C9—C10—C1	−179.16 (19)	C23—C24—C25—C26	−1.1 (3)
C8—C9—C10—C4	2.5 (3)	C24—C25—C26—C27	0.3 (3)
C2—C1—C10—C9	−177.39 (18)	C24—C25—C26—S2	−179.55 (15)
C11—C1—C10—C9	1.9 (3)	C29—S2—C26—C27	−86.86 (18)
C2—C1—C10—C4	1.2 (2)	C29—S2—C26—C25	92.98 (17)
C11—C1—C10—C4	−179.46 (18)	C25—C26—C27—C28	0.1 (3)
C5—C4—C10—C9	−5.5 (3)	S2—C26—C27—C28	179.98 (16)
C3—C4—C10—C9	176.53 (18)	C26—C27—C28—C23	0.2 (3)
C5—C4—C10—C1	175.89 (19)	C24—C23—C28—C27	−1.0 (3)
C3—C4—C10—C1	−2.1 (2)	C22—C23—C28—C27	179.86 (19)
C18—C13—C14—C15	5.1 (3)	C26—S2—C29—O2	14.4 (2)
C12—C13—C14—C15	−172.25 (18)	C26—S2—C29—C30	−164.72 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.95	2.40	3.285 (3)	155
C17—H1···Cg1	0.95	2.69	3.612 (3)	165
C20—H20A···Cg2ii	0.98	2.89	3.835 (2)	162

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the mid-point of the C11—C12 bond and Cg2 is the centroid of the C1–C4/C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.95	2.40	3.285 (3)	155
C17—H1⋯Cg1	0.95	2.69	3.612 (3)	165
C20—H20A⋯Cg2ii	0.98	2.89	3.835 (2)	162

Symmetry code: (i) ; (ii) .