A non-linear optical chromophore: 2-[3-cyano-4-((E)-{5-[4-(diethyl­amino)styr­yl]thio­phen-2-yl}vin­yl)-5,5-dimethyl­furan-2-(5H)-yl­idene]propane­dinitrile

The title compound, C₂₈H₂₆N₄OS, is an efficient non-linear optical (NLO) material and features a transoid configuration in contrast to the results of quantum chemical calculations. Mol­ecules associate into layers via C—H...N inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.054
• wR factor = 0.128
• Data-to-parameter ratio = 21.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.42 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C25    ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C4     -   C26    ...       1.43 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

2-[3-cyano-4-((E)-{5-[4-(diethylamino)styryl]thiophen-2-yl}vinyl)-5,5- dimethylfuran-2-(5H)-ylidene]propanedinitrile

Crystal data

C28H26N4OS	F(000) = 984
Mr = 466.59	Dx = 1.266 Mg m^−3
Monoclinic, P21/n	Melting point: 502 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.0896 (13) Å	Cell parameters from 9516 reflections
b = 17.421 (2) Å	θ = 2.2–29.1°
c = 12.7970 (15) Å	µ = 0.16 mm^−1
β = 98.141 (2)°	T = 100 K
V = 2447.3 (5) Å^3	Prism, colourless
Z = 4	0.50 × 0.30 × 0.24 mm

Data collection

Bruker SMART APEX-II CCD area-detector diffractometer	6473 independent reflections
Radiation source: fine-focus sealed tube	4431 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
φ and ω scans	θmax = 29.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −15→15
Tmin = 0.895, Tmax = 0.963	k = −23→23
23182 measured reflections	l = −12→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.04P)^2 + 1.9P] where P = (Fo^2 + 2Fc^2)/3
6473 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.42123 (5)	0.24976 (3)	0.69027 (4)	0.02204 (12)
O1	0.28787 (13)	0.22812 (7)	0.15051 (11)	0.0222 (3)
N1	0.67124 (17)	0.44740 (9)	1.31736 (14)	0.0260 (4)
N2	0.26017 (18)	0.44392 (10)	0.37548 (15)	0.0329 (4)
N3	0.17089 (19)	0.49093 (10)	0.09586 (15)	0.0347 (5)
N4	0.21537 (19)	0.30399 (11)	−0.10712 (16)	0.0361 (5)
C1	0.22372 (19)	0.32249 (11)	−0.02142 (17)	0.0244 (4)
C2	0.23231 (18)	0.34965 (11)	0.08439 (16)	0.0223 (4)
C3	0.26535 (18)	0.30166 (11)	0.16819 (16)	0.0216 (4)
C4	0.27978 (18)	0.31592 (11)	0.27952 (16)	0.0216 (4)
C5	0.30866 (16)	0.24828 (11)	0.33222 (15)	0.0198 (4)
C6	0.31001 (18)	0.18524 (11)	0.25144 (15)	0.0210 (4)
C7	0.33555 (17)	0.24124 (11)	0.44330 (16)	0.0211 (4)
H7A	0.3346	0.2871	0.4834	0.025*
C8	0.36261 (18)	0.17508 (11)	0.49787 (16)	0.0217 (4)
H8A	0.3569	0.1285	0.4588	0.026*
C9	0.39874 (17)	0.16995 (11)	0.60858 (16)	0.0206 (4)
C10	0.42509 (18)	0.10391 (11)	0.66657 (16)	0.0235 (4)
H10A	0.4178	0.0540	0.6365	0.028*
C11	0.46315 (18)	0.11728 (11)	0.77281 (17)	0.0249 (4)
H11A	0.4842	0.0771	0.8223	0.030*
C12	0.46794 (18)	0.19395 (11)	0.80078 (16)	0.0226 (4)
C13	0.50885 (18)	0.22619 (12)	0.90229 (16)	0.0242 (4)
H13A	0.5318	0.1913	0.9586	0.029*
C14	0.51772 (18)	0.30151 (12)	0.92522 (16)	0.0236 (4)
H14A	0.4933	0.3355	0.8681	0.028*
C15	0.55970 (17)	0.33751 (11)	1.02568 (16)	0.0221 (4)
C16	0.58032 (19)	0.41671 (12)	1.03246 (17)	0.0254 (4)
H16A	0.5678	0.4463	0.9695	0.031*
C17	0.61811 (19)	0.45344 (12)	1.12684 (17)	0.0264 (4)
H17A	0.6314	0.5073	1.1275	0.032*
C18	0.63710 (18)	0.41225 (11)	1.22192 (16)	0.0231 (4)
C19	0.62133 (18)	0.33184 (11)	1.21494 (16)	0.0236 (4)
H19A	0.6366	0.3016	1.2772	0.028*
C20	0.58446 (18)	0.29660 (12)	1.12016 (16)	0.0241 (4)
H20A	0.5754	0.2424	1.1186	0.029*
C21	0.6683 (2)	0.53031 (12)	1.32973 (18)	0.0291 (5)
H21A	0.6419	0.5425	1.3986	0.035*
H21B	0.6072	0.5520	1.2736	0.035*
C22	0.7903 (2)	0.56830 (13)	1.3244 (2)	0.0378 (6)
H22A	0.7826	0.6239	1.3332	0.057*
H22B	0.8163	0.5575	1.2558	0.057*
H22C	0.8509	0.5481	1.3809	0.057*
C23	0.69657 (19)	0.40325 (12)	1.41483 (16)	0.0262 (4)
H23A	0.7497	0.4339	1.4679	0.031*
H23B	0.7413	0.3560	1.4010	0.031*
C24	0.5821 (2)	0.38129 (14)	1.45967 (17)	0.0317 (5)
H24A	0.6041	0.3519	1.5248	0.048*
H24B	0.5299	0.3499	1.4082	0.048*
H24C	0.5383	0.4279	1.4750	0.048*
C25	0.20033 (19)	0.42849 (12)	0.09502 (16)	0.0252 (4)
C26	0.26761 (19)	0.38822 (11)	0.32994 (16)	0.0245 (4)
C27	0.20560 (18)	0.12899 (11)	0.24942 (16)	0.0234 (4)
H27C	0.1289	0.1573	0.2476	0.035*
H27D	0.2186	0.0968	0.3128	0.035*
H27B	0.2017	0.0965	0.1866	0.035*
C28	0.43179 (18)	0.14523 (11)	0.25444 (17)	0.0245 (4)
H28D	0.4964	0.1837	0.2556	0.037*
H28C	0.4304	0.1128	0.1917	0.037*
H28B	0.4473	0.1133	0.3180	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0257 (2)	0.0207 (2)	0.0192 (2)	−0.00098 (19)	0.00239 (18)	−0.00006 (19)
O1	0.0281 (8)	0.0194 (6)	0.0191 (7)	0.0035 (5)	0.0047 (6)	0.0007 (5)
N1	0.0325 (10)	0.0247 (9)	0.0211 (9)	−0.0013 (7)	0.0055 (7)	−0.0011 (7)
N2	0.0433 (12)	0.0239 (9)	0.0309 (11)	0.0022 (8)	0.0036 (8)	−0.0030 (8)
N3	0.0506 (13)	0.0221 (9)	0.0309 (11)	0.0007 (8)	0.0052 (9)	0.0023 (8)
N4	0.0417 (12)	0.0380 (11)	0.0277 (11)	0.0082 (9)	0.0032 (9)	−0.0017 (9)
C1	0.0252 (10)	0.0232 (9)	0.0243 (11)	0.0029 (8)	0.0026 (8)	0.0015 (8)
C2	0.0239 (10)	0.0210 (9)	0.0218 (10)	0.0002 (8)	0.0038 (8)	0.0006 (8)
C3	0.0193 (9)	0.0201 (9)	0.0259 (11)	−0.0010 (7)	0.0054 (8)	−0.0010 (8)
C4	0.0227 (10)	0.0207 (9)	0.0214 (10)	−0.0020 (7)	0.0036 (8)	0.0007 (8)
C5	0.0168 (9)	0.0207 (8)	0.0223 (10)	−0.0016 (7)	0.0045 (7)	−0.0004 (8)
C6	0.0259 (10)	0.0194 (9)	0.0176 (10)	0.0006 (7)	0.0033 (8)	0.0019 (7)
C7	0.0226 (10)	0.0202 (9)	0.0210 (10)	−0.0022 (7)	0.0056 (7)	−0.0029 (7)
C8	0.0213 (10)	0.0221 (9)	0.0222 (10)	−0.0035 (8)	0.0055 (8)	−0.0026 (8)
C9	0.0180 (9)	0.0216 (9)	0.0224 (10)	−0.0014 (7)	0.0040 (7)	−0.0009 (8)
C10	0.0251 (10)	0.0198 (9)	0.0261 (11)	−0.0013 (8)	0.0063 (8)	−0.0001 (8)
C11	0.0252 (10)	0.0229 (9)	0.0264 (11)	0.0007 (8)	0.0042 (8)	0.0054 (8)
C12	0.0211 (10)	0.0265 (10)	0.0205 (10)	−0.0012 (8)	0.0051 (8)	0.0029 (8)
C13	0.0222 (10)	0.0313 (10)	0.0192 (10)	−0.0002 (8)	0.0038 (8)	0.0018 (8)
C14	0.0226 (10)	0.0310 (10)	0.0178 (10)	0.0017 (8)	0.0057 (8)	0.0029 (8)
C15	0.0188 (9)	0.0249 (10)	0.0233 (11)	0.0021 (7)	0.0065 (8)	0.0005 (8)
C16	0.0288 (11)	0.0275 (10)	0.0203 (11)	0.0049 (8)	0.0051 (8)	0.0042 (8)
C17	0.0296 (11)	0.0217 (10)	0.0279 (12)	0.0020 (8)	0.0050 (9)	0.0012 (8)
C18	0.0208 (10)	0.0259 (10)	0.0235 (11)	0.0007 (8)	0.0073 (8)	−0.0014 (8)
C19	0.0267 (10)	0.0247 (10)	0.0201 (10)	0.0000 (8)	0.0062 (8)	0.0013 (8)
C20	0.0257 (11)	0.0228 (9)	0.0246 (11)	−0.0016 (8)	0.0074 (8)	−0.0005 (8)
C21	0.0345 (12)	0.0251 (10)	0.0282 (12)	0.0019 (9)	0.0073 (9)	−0.0036 (9)
C22	0.0396 (14)	0.0226 (11)	0.0522 (16)	−0.0049 (9)	0.0108 (11)	−0.0007 (10)
C23	0.0268 (11)	0.0304 (11)	0.0209 (11)	−0.0021 (8)	0.0027 (8)	−0.0016 (8)
C24	0.0306 (12)	0.0427 (13)	0.0228 (11)	−0.0027 (10)	0.0079 (9)	0.0005 (9)
C25	0.0295 (11)	0.0244 (10)	0.0218 (11)	−0.0027 (8)	0.0047 (8)	0.0010 (8)
C26	0.0263 (11)	0.0245 (10)	0.0224 (11)	−0.0007 (8)	0.0030 (8)	0.0019 (8)
C27	0.0257 (11)	0.0201 (9)	0.0240 (11)	−0.0010 (8)	0.0027 (8)	−0.0009 (8)
C28	0.0250 (10)	0.0243 (10)	0.0251 (11)	0.0031 (8)	0.0070 (8)	0.0029 (8)

Geometric parameters (Å, º)

S1—C12	1.734 (2)	C13—H13A	0.9500
S1—C9	1.736 (2)	C14—C15	1.447 (3)
O1—C3	1.331 (2)	C14—H14A	0.9500
O1—C6	1.482 (2)	C15—C20	1.397 (3)
N1—C18	1.371 (3)	C15—C16	1.399 (3)
N1—C21	1.454 (3)	C16—C17	1.378 (3)
N1—C23	1.459 (3)	C16—H16A	0.9500
N2—C26	1.141 (3)	C17—C18	1.403 (3)
N3—C25	1.136 (3)	C17—H17A	0.9500
N4—C1	1.134 (3)	C18—C19	1.413 (3)
C1—C2	1.425 (3)	C19—C20	1.369 (3)
C2—C3	1.368 (3)	C19—H19A	0.9500
C2—C25	1.430 (3)	C20—H20A	0.9500
C3—C4	1.433 (3)	C21—C22	1.516 (3)
C4—C5	1.373 (3)	C21—H21A	0.9900
C4—C26	1.430 (3)	C21—H21B	0.9900
C5—C7	1.416 (3)	C22—H22A	0.9800
C5—C6	1.510 (3)	C22—H22B	0.9800
C6—C27	1.514 (3)	C22—H22C	0.9800
C6—C28	1.515 (3)	C23—C24	1.514 (3)
C7—C8	1.359 (3)	C23—H23A	0.9900
C7—H7A	0.9500	C23—H23B	0.9900
C8—C9	1.420 (3)	C24—H24A	0.9800
C8—H8A	0.9500	C24—H24B	0.9800
C9—C10	1.378 (3)	C24—H24C	0.9800
C10—C11	1.385 (3)	C27—H27C	0.9800
C10—H10A	0.9500	C27—H27D	0.9800
C11—C12	1.382 (3)	C27—H27B	0.9800
C11—H11A	0.9500	C28—H28D	0.9800
C12—C13	1.429 (3)	C28—H28C	0.9800
C13—C14	1.345 (3)	C28—H28B	0.9800
C12—S1—C9	92.46 (10)	C17—C16—H16A	118.7
C3—O1—C6	110.43 (15)	C15—C16—H16A	118.7
C18—N1—C21	122.22 (17)	C16—C17—C18	120.82 (19)
C18—N1—C23	121.47 (17)	C16—C17—H17A	119.6
C21—N1—C23	115.80 (17)	C18—C17—H17A	119.6
N4—C1—C2	177.0 (2)	N1—C18—C17	122.22 (18)
C3—C2—C1	121.09 (18)	N1—C18—C19	121.01 (18)
C3—C2—C25	123.71 (19)	C17—C18—C19	116.76 (19)
C1—C2—C25	115.17 (18)	C20—C19—C18	121.28 (19)
O1—C3—C2	119.41 (18)	C20—C19—H19A	119.4
O1—C3—C4	109.80 (17)	C18—C19—H19A	119.4
C2—C3—C4	130.78 (18)	C19—C20—C15	122.38 (19)
C5—C4—C26	124.37 (18)	C19—C20—H20A	118.8
C5—C4—C3	108.97 (17)	C15—C20—H20A	118.8
C26—C4—C3	126.66 (18)	N1—C21—C22	113.27 (18)
C4—C5—C7	124.67 (18)	N1—C21—H21A	108.9
C4—C5—C6	108.19 (17)	C22—C21—H21A	108.9
C7—C5—C6	127.11 (17)	N1—C21—H21B	108.9
O1—C6—C5	102.34 (14)	C22—C21—H21B	108.9
O1—C6—C27	106.22 (15)	H21A—C21—H21B	107.7
C5—C6—C27	113.62 (16)	C21—C22—H22A	109.5
O1—C6—C28	106.92 (15)	C21—C22—H22B	109.5
C5—C6—C28	114.36 (16)	H22A—C22—H22B	109.5
C27—C6—C28	112.29 (16)	C21—C22—H22C	109.5
C8—C7—C5	126.10 (18)	H22A—C22—H22C	109.5
C8—C7—H7A	116.9	H22B—C22—H22C	109.5
C5—C7—H7A	116.9	N1—C23—C24	112.77 (18)
C7—C8—C9	125.23 (18)	N1—C23—H23A	109.0
C7—C8—H8A	117.4	C24—C23—H23A	109.0
C9—C8—H8A	117.4	N1—C23—H23B	109.0
C10—C9—C8	126.77 (18)	C24—C23—H23B	109.0
C10—C9—S1	110.05 (15)	H23A—C23—H23B	107.8
C8—C9—S1	123.14 (15)	C23—C24—H24A	109.5
C9—C10—C11	113.59 (18)	C23—C24—H24B	109.5
C9—C10—H10A	123.2	H24A—C24—H24B	109.5
C11—C10—H10A	123.2	C23—C24—H24C	109.5
C12—C11—C10	114.33 (18)	H24A—C24—H24C	109.5
C12—C11—H11A	122.8	H24B—C24—H24C	109.5
C10—C11—H11A	122.8	N3—C25—C2	174.9 (2)
C11—C12—C13	127.66 (19)	N2—C26—C4	176.1 (2)
C11—C12—S1	109.55 (15)	C6—C27—H27C	109.5
C13—C12—S1	122.74 (15)	C6—C27—H27D	109.5
C14—C13—C12	125.86 (19)	H27C—C27—H27D	109.5
C14—C13—H13A	117.1	C6—C27—H27B	109.5
C12—C13—H13A	117.1	H27C—C27—H27B	109.5
C13—C14—C15	128.40 (19)	H27D—C27—H27B	109.5
C13—C14—H14A	115.8	C6—C28—H28D	109.5
C15—C14—H14A	115.8	C6—C28—H28C	109.5
C20—C15—C16	116.04 (19)	H28D—C28—H28C	109.5
C20—C15—C14	123.16 (18)	C6—C28—H28B	109.5
C16—C15—C14	120.79 (18)	H28D—C28—H28B	109.5
C17—C16—C15	122.60 (19)	H28C—C28—H28B	109.5
C6—O1—C3—C2	−174.47 (17)	C8—C9—C10—C11	177.27 (19)
C6—O1—C3—C4	4.6 (2)	S1—C9—C10—C11	−0.6 (2)
C1—C2—C3—O1	−1.1 (3)	C9—C10—C11—C12	−0.2 (3)
C25—C2—C3—O1	176.75 (18)	C10—C11—C12—C13	−176.72 (19)
C1—C2—C3—C4	180.0 (2)	C10—C11—C12—S1	0.8 (2)
C25—C2—C3—C4	−2.1 (3)	C9—S1—C12—C11	−0.97 (16)
O1—C3—C4—C5	−1.8 (2)	C9—S1—C12—C13	176.72 (17)
C2—C3—C4—C5	177.1 (2)	C11—C12—C13—C14	176.5 (2)
O1—C3—C4—C26	177.73 (19)	S1—C12—C13—C14	−0.7 (3)
C2—C3—C4—C26	−3.3 (4)	C12—C13—C14—C15	−179.17 (19)
C26—C4—C5—C7	−2.9 (3)	C13—C14—C15—C20	−8.3 (3)
C3—C4—C5—C7	176.69 (18)	C13—C14—C15—C16	170.4 (2)
C26—C4—C5—C6	178.77 (18)	C20—C15—C16—C17	−2.5 (3)
C3—C4—C5—C6	−1.6 (2)	C14—C15—C16—C17	178.76 (19)
C3—O1—C6—C5	−5.33 (19)	C15—C16—C17—C18	−0.4 (3)
C3—O1—C6—C27	114.07 (17)	C21—N1—C18—C17	11.7 (3)
C3—O1—C6—C28	−125.85 (17)	C23—N1—C18—C17	−176.87 (19)
C4—C5—C6—O1	4.09 (19)	C21—N1—C18—C19	−169.39 (19)
C7—C5—C6—O1	−174.20 (17)	C23—N1—C18—C19	2.1 (3)
C4—C5—C6—C27	−109.97 (19)	C16—C17—C18—N1	−178.08 (19)
C7—C5—C6—C27	71.7 (2)	C16—C17—C18—C19	2.9 (3)
C4—C5—C6—C28	119.31 (18)	N1—C18—C19—C20	178.43 (19)
C7—C5—C6—C28	−59.0 (3)	C17—C18—C19—C20	−2.6 (3)
C4—C5—C7—C8	178.93 (19)	C18—C19—C20—C15	−0.4 (3)
C6—C5—C7—C8	−3.0 (3)	C16—C15—C20—C19	2.9 (3)
C5—C7—C8—C9	174.70 (18)	C14—C15—C20—C19	−178.40 (19)
C7—C8—C9—C10	179.0 (2)	C18—N1—C21—C22	−95.9 (2)
C7—C8—C9—S1	−3.4 (3)	C23—N1—C21—C22	92.2 (2)
C12—S1—C9—C10	0.89 (16)	C18—N1—C23—C24	−81.4 (2)
C12—S1—C9—C8	−177.06 (17)	C21—N1—C23—C24	90.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···N3^i	0.95	2.50	3.427 (3)	164
C19—H19A···N4^ii	0.95	2.44	3.347 (3)	159
C27—H27D···N3^i	0.98	2.42	3.288 (3)	147
C27—H27C···S1^iii	0.98	2.83	3.782 (2)	165

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