(Z)-2-(4-Nitro­phen­yl)-3-[4-(pyridin-4-ylmeth­oxy)phen­yl]acrylo­nitrile

Rao, Q.; Wang, Z.; Yang, M.; Wu, Z.

doi:10.1107/S2414314618013287

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 9| September 2018| x181328

https://doi.org/10.1107/S2414314618013287

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(Z)-2-(4-Nitrophenyl)-3-[4-(pyridin-4-ylmethoxy)phenyl]acrylonitrile

Qingpeng Rao,^a Zepeng Wang,^a Mingdi Yang ^b and Zhichao Wu ^a,^c ^*

^aDepartment of Chemistry, Anhui University, Hefei 230601, People's Republic of China, ^bCollege of Chemistry and Chemical Engineering, Anhui University, and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Hefei, 230601, People's Republic of China, and ^cKey Laboratory of Functional Inorganic Materials Chemistry, Hefei 230601, People's Republic of China
^*Correspondence e-mail: wu_zhichao63@sina.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 15 August 2018; accepted 18 September 2018; online 28 September 2018)

The title compound, C₂₁H₁₅N₃O₃, features an essentially planar molecule (r.m.s. deviation for all non-H atoms = 0.090 Å). An intramolecular C—H⋯N hydrogen bond occurs. In the crystal, the molecules are connected by C—H⋯N and C—H⋯O hydrogen bonds into layers parallel to (102).

Keywords: crystal structure; two-dimensional layer structure; C—H⋯N hydrogen bonds; C—H⋯O hydrogen bonds.

CCDC reference: 1868352

Structure description

We are interested in the title compound as it is a potential aggregation-induced emission (AIE) material (Liu & Fujiki, 2016 ). The molecule (Fig. 1) is almost planar (r.m.s. deviation for all non-H atoms = 0.090 Å). An intramolecular C—H⋯N hydrogen bond occurs (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯N2	0.93	2.58	3.417 (2)	149
C1—H1⋯N3ⁱ	0.93	2.97	3.468 (2)	115
C16—H16A⋯N2ⁱⁱ	0.97	2.83	3.261 (2)	107
C4—H4⋯O2ⁱⁱⁱ	0.93	2.63	3.502 (3)	156
C18—H18⋯O1^iv	0.93	2.47	3.362 (2)	162
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x, -y+1, -z+2; (iii) -x+2, -y+1, -z+1; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
The structure of title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular hydrogen bond is indicated by a dashed line.

In the crystal, the molecules are connected by C—H⋯O and C—H⋯N hydrogen bonds into layers parallel to (102) (Table 1, Fig. 2).

Figure 2
C—H⋯N and C—H⋯O hydrogen bonds connect the molecules into layers parallel to (102).

Synthesis and crystallization

Firstly, 1.24 g (4.90 mmol) of 4-(bromomethyl)pyridine hydrobromide and 0.50 g (4.10 mmol) of 4-hydroxybenzaldehyde were added to a flask equipped with 50 ml acetonitrile. And then anhydrous potassium carbonate (3.24 g, 23.44 mmol) and 18-crown-6 (1 g) were added and refluxed at 353 K overnight. Subsequently, the mixture was filtered and the solvent was removed under reduced pressure. Finally, the white product was obtained by column chromatography with petroleum petroleum ether/ethyl acetate (2:1, v/v). Then, the white product (0.20 g, 0.94 mmol) of the previous step and 0.15 g (0.95 mmol) of 2-(4-nitrophenyl)acetonitrile were dissolved in 20 ml ethanol into a flask equipped with a magnetic stirrer for 5 h. Subsequently, the yellow solid was filtered. Yellow crystals suitable for X-ray analysis were obtained by recrystallization from ethanol solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₁₅N₃O₃
M_r	357.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.1759 (15), 23.521 (4), 7.4038 (11)
β (°)	95.674 (2)
V (Å³)	1763.4 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.21 × 0.20 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area detector
No. of measured, independent and observed [I > 2σ(I)] reflections	12823, 3270, 2621
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.113, 1.01
No. of reflections	3270
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.18
Computer programs: SMART (Bruker, 2004 ), SAINT (Bruker, 2004), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Structural data

CCDC reference: 1868352

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618013287/bt4072sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618013287/bt4072Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618013287/bt4072Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(Z)-2-(4-Nitrophenyl)-3-[4-(pyridin-4-ylmethoxy)phenyl]acrylonitrile top

Crystal data top

C₂₁H₁₅N₃O₃	F(000) = 744
M_r = 357.36	D_x = 1.346 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1759 (15) Å	Cell parameters from 4694 reflections
b = 23.521 (4) Å	θ = 2.2–27.0°
c = 7.4038 (11) Å	µ = 0.09 mm⁻¹
β = 95.674 (2)°	T = 296 K
V = 1763.4 (5) Å³	Block, yellow
Z = 4	0.21 × 0.20 × 0.19 mm

Data collection top

Bruker SMART CCD area detector diffractometer	2621 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 25.5°, θ_min = 1.7°
phi and ω scans	h = −12→12
12823 measured reflections	k = −28→28
3270 independent reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0544P)² + 0.3275P] where P = (F_o² + 2F_c²)/3
3270 reflections	(Δ/σ)_max < 0.001
244 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

All H atoms were placed in geometrically calculated positions and refined using a riding model with C–H distances of 0.93 Å for all H atoms bound to C(sp²) atoms and 0.97 Å for H atoms bound to secondary C(sp³) atoms. Isotropic displacement parameters for H atoms were calculated as U_iso(H) = 1.2U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.90163 (15)	0.59837 (8)	0.5910 (2)	0.0760 (5)
N2	0.26154 (15)	0.56478 (6)	0.8779 (2)	0.0798 (5)
N3	−0.40049 (15)	0.17881 (7)	1.0732 (2)	0.0745 (4)
O1	0.90200 (15)	0.65022 (7)	0.5838 (2)	0.1062 (5)
O2	0.99589 (15)	0.56935 (8)	0.5654 (3)	0.1137 (6)
O3	−0.00447 (10)	0.29351 (4)	0.96989 (17)	0.0635 (3)
C1	0.55913 (15)	0.57655 (6)	0.7070 (2)	0.0533 (4)
H1	0.4858	0.5987	0.7251	0.064*
C2	0.67248 (17)	0.60273 (7)	0.6613 (2)	0.0613 (4)
H2	0.6758	0.6420	0.6486	0.074*
C3	0.77981 (15)	0.57002 (7)	0.6351 (2)	0.0567 (4)
C4	0.77684 (15)	0.51182 (7)	0.6501 (2)	0.0604 (4)
H4	0.8504	0.4902	0.6296	0.072*
C5	0.66288 (14)	0.48595 (6)	0.6962 (2)	0.0539 (4)
H5	0.6602	0.4466	0.7070	0.065*
C6	0.55184 (13)	0.51786 (6)	0.72667 (18)	0.0428 (3)
C7	0.42900 (13)	0.49128 (6)	0.78063 (18)	0.0417 (3)
C8	0.33306 (14)	0.53124 (6)	0.8334 (2)	0.0521 (4)
C9	0.40641 (13)	0.43488 (6)	0.78435 (18)	0.0440 (3)
H9	0.4751	0.4128	0.7487	0.053*
C10	0.29350 (13)	0.40227 (6)	0.83428 (18)	0.0440 (3)
C11	0.30583 (15)	0.34322 (6)	0.8376 (2)	0.0597 (4)
H11	0.3842	0.3270	0.8077	0.072*
C12	0.20650 (16)	0.30814 (6)	0.8833 (3)	0.0661 (5)
H12	0.2181	0.2689	0.8843	0.079*
C13	0.08860 (14)	0.33152 (6)	0.9280 (2)	0.0500 (4)
C14	0.07328 (14)	0.38986 (6)	0.9266 (2)	0.0530 (4)
H14	−0.0051	0.4059	0.9573	0.064*
C15	0.17420 (14)	0.42453 (6)	0.8797 (2)	0.0525 (4)
H15	0.1622	0.4637	0.8785	0.063*
C16	−0.12520 (14)	0.31518 (6)	1.0222 (2)	0.0525 (4)
H16A	−0.1632	0.3419	0.9317	0.063*
H16B	−0.1095	0.3350	1.1372	0.063*
C17	−0.21847 (13)	0.26665 (6)	1.03973 (19)	0.0446 (3)
C18	−0.18182 (15)	0.21070 (6)	1.0301 (2)	0.0548 (4)
H18	−0.0952	0.2010	1.0136	0.066*
C19	−0.27535 (18)	0.16909 (7)	1.0453 (3)	0.0700 (5)
H19	−0.2491	0.1314	1.0354	0.084*
C20	−0.43400 (16)	0.23323 (8)	1.0816 (2)	0.0667 (5)
H20	−0.5211	0.2417	1.0994	0.080*
C21	−0.34893 (15)	0.27792 (7)	1.0658 (2)	0.0560 (4)
H21	−0.3785	0.3152	1.0724	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0579 (10)	0.0991 (13)	0.0716 (10)	−0.0312 (9)	0.0090 (7)	0.0036 (9)
N2	0.0692 (9)	0.0503 (8)	0.1253 (14)	0.0098 (7)	0.0371 (9)	0.0006 (8)
N3	0.0680 (9)	0.0672 (10)	0.0908 (11)	−0.0271 (7)	0.0199 (8)	−0.0032 (8)
O1	0.0915 (11)	0.0937 (11)	0.1359 (14)	−0.0495 (9)	0.0244 (9)	0.0119 (10)
O2	0.0546 (8)	0.1344 (14)	0.1563 (16)	−0.0212 (9)	0.0321 (9)	0.0062 (11)
O3	0.0458 (6)	0.0438 (6)	0.1057 (9)	−0.0047 (4)	0.0305 (6)	−0.0001 (5)
C1	0.0515 (8)	0.0476 (8)	0.0617 (10)	−0.0046 (6)	0.0106 (7)	0.0026 (7)
C2	0.0654 (10)	0.0525 (9)	0.0668 (10)	−0.0167 (8)	0.0099 (8)	0.0045 (7)
C3	0.0476 (8)	0.0713 (11)	0.0513 (9)	−0.0220 (7)	0.0049 (7)	0.0020 (7)
C4	0.0432 (8)	0.0721 (11)	0.0672 (10)	−0.0046 (7)	0.0123 (7)	−0.0011 (8)
C5	0.0475 (8)	0.0493 (8)	0.0667 (10)	−0.0040 (6)	0.0144 (7)	0.0000 (7)
C6	0.0425 (7)	0.0458 (8)	0.0404 (7)	−0.0051 (6)	0.0050 (6)	−0.0008 (6)
C7	0.0398 (7)	0.0436 (7)	0.0422 (7)	−0.0010 (5)	0.0074 (6)	−0.0003 (6)
C8	0.0483 (8)	0.0433 (8)	0.0666 (10)	−0.0030 (6)	0.0148 (7)	0.0022 (7)
C9	0.0400 (7)	0.0446 (7)	0.0488 (8)	−0.0003 (5)	0.0107 (6)	−0.0017 (6)
C10	0.0421 (7)	0.0422 (7)	0.0489 (8)	−0.0028 (6)	0.0099 (6)	−0.0018 (6)
C11	0.0456 (8)	0.0458 (8)	0.0916 (12)	0.0018 (6)	0.0262 (8)	−0.0022 (8)
C12	0.0531 (9)	0.0386 (8)	0.1111 (15)	0.0001 (7)	0.0309 (9)	−0.0004 (8)
C13	0.0418 (7)	0.0450 (8)	0.0650 (9)	−0.0070 (6)	0.0148 (7)	−0.0010 (7)
C14	0.0400 (7)	0.0461 (8)	0.0754 (10)	−0.0004 (6)	0.0186 (7)	−0.0046 (7)
C15	0.0475 (8)	0.0391 (7)	0.0730 (10)	−0.0023 (6)	0.0167 (7)	−0.0030 (7)
C16	0.0434 (8)	0.0466 (8)	0.0698 (10)	−0.0037 (6)	0.0174 (7)	−0.0061 (7)
C17	0.0428 (7)	0.0472 (8)	0.0449 (8)	−0.0078 (6)	0.0094 (6)	−0.0032 (6)
C18	0.0506 (8)	0.0499 (9)	0.0660 (10)	−0.0030 (7)	0.0161 (7)	−0.0026 (7)
C19	0.0784 (12)	0.0450 (9)	0.0894 (13)	−0.0119 (8)	0.0220 (10)	−0.0038 (8)
C20	0.0449 (9)	0.0792 (12)	0.0780 (12)	−0.0130 (8)	0.0167 (8)	0.0004 (9)
C21	0.0486 (8)	0.0541 (9)	0.0671 (10)	−0.0020 (7)	0.0144 (7)	−0.0011 (7)

Geometric parameters (Å, º) top

O3—C13	1.3603 (17)	C17—C18	1.372 (2)
O3—C16	1.4188 (17)	C17—C21	1.386 (2)
C7—C9	1.3472 (19)	C17—C16	1.4983 (19)
C7—C8	1.4370 (19)	C11—C12	1.373 (2)
C7—C6	1.4873 (18)	C11—H11	0.9300
C6—C1	1.391 (2)	C18—C19	1.378 (2)
C6—C5	1.393 (2)	C18—H18	0.9300
C10—C15	1.3935 (19)	C16—H16A	0.9700
C10—C11	1.395 (2)	C16—H16B	0.9700
C10—C9	1.4590 (18)	C2—C1	1.379 (2)
C9—H9	0.9300	C2—H2	0.9300
C14—C13	1.381 (2)	C12—H12	0.9300
C14—C15	1.3822 (19)	C4—H4	0.9300
C14—H14	0.9300	C1—H1	0.9300
C5—C4	1.382 (2)	N1—O2	1.208 (2)
C5—H5	0.9300	N1—O1	1.221 (2)
C8—N2	1.1436 (19)	N3—C20	1.328 (2)
C3—C2	1.366 (2)	N3—C19	1.330 (2)
C3—C4	1.374 (2)	C21—C20	1.374 (2)
C3—N1	1.4723 (19)	C21—H21	0.9300
C15—H15	0.9300	C20—H20	0.9300
C13—C12	1.389 (2)	C19—H19	0.9300

C13—O3—C16	117.86 (11)	C17—C18—C19	118.93 (15)
C9—C7—C8	121.11 (12)	C17—C18—H18	120.5
C9—C7—C6	124.69 (12)	C19—C18—H18	120.5
C8—C7—C6	114.19 (11)	O3—C16—C17	108.85 (11)
C1—C6—C5	117.73 (13)	O3—C16—H16A	109.9
C1—C6—C7	120.02 (13)	C17—C16—H16A	109.9
C5—C6—C7	122.25 (12)	O3—C16—H16B	109.9
C15—C10—C11	116.68 (12)	C17—C16—H16B	109.9
C15—C10—C9	126.19 (13)	H16A—C16—H16B	108.3
C11—C10—C9	117.14 (12)	C3—C2—C1	118.92 (15)
C7—C9—C10	131.53 (12)	C3—C2—H2	120.5
C7—C9—H9	114.2	C1—C2—H2	120.5
C10—C9—H9	114.2	C11—C12—C13	119.67 (14)
C13—C14—C15	120.13 (13)	C11—C12—H12	120.2
C13—C14—H14	119.9	C13—C12—H12	120.2
C15—C14—H14	119.9	C3—C4—C5	118.97 (15)
C4—C5—C6	121.10 (14)	C3—C4—H4	120.5
C4—C5—H5	119.5	C5—C4—H4	120.5
C6—C5—H5	119.5	C2—C1—C6	121.56 (15)
N2—C8—C7	176.74 (17)	C2—C1—H1	119.2
C2—C3—C4	121.71 (14)	C6—C1—H1	119.2
C2—C3—N1	118.63 (16)	O2—N1—O1	123.50 (16)
C4—C3—N1	119.66 (16)	O2—N1—C3	118.56 (18)
C14—C15—C10	121.71 (13)	O1—N1—C3	117.94 (17)
C14—C15—H15	119.1	C20—N3—C19	115.30 (14)
C10—C15—H15	119.1	C20—C21—C17	119.06 (15)
O3—C13—C14	125.04 (13)	C20—C21—H21	120.5
O3—C13—C12	115.55 (13)	C17—C21—H21	120.5
C14—C13—C12	119.41 (13)	N3—C20—C21	124.52 (16)
C18—C17—C21	117.38 (13)	N3—C20—H20	117.7
C18—C17—C16	123.27 (13)	C21—C20—H20	117.7
C21—C17—C16	119.34 (13)	N3—C19—C18	124.79 (16)
C12—C11—C10	122.39 (13)	N3—C19—H19	117.6
C12—C11—H11	118.8	C18—C19—H19	117.6
C10—C11—H11	118.8

C9—C7—C6—C1	172.46 (14)	C18—C17—C16—O3	8.2 (2)
C8—C7—C6—C1	−8.53 (19)	C21—C17—C16—O3	−171.38 (13)
C9—C7—C6—C5	−8.3 (2)	C4—C3—C2—C1	1.1 (2)
C8—C7—C6—C5	170.74 (14)	N1—C3—C2—C1	−178.40 (14)
C8—C7—C9—C10	0.6 (2)	C10—C11—C12—C13	0.1 (3)
C6—C7—C9—C10	179.53 (13)	O3—C13—C12—C11	179.45 (16)
C15—C10—C9—C7	5.0 (3)	C14—C13—C12—C11	−0.3 (3)
C11—C10—C9—C7	−174.82 (16)	C2—C3—C4—C5	−1.2 (3)
C1—C6—C5—C4	0.7 (2)	N1—C3—C4—C5	178.31 (14)
C7—C6—C5—C4	−178.54 (14)	C6—C5—C4—C3	0.2 (2)
C9—C7—C8—N2	152 (3)	C3—C2—C1—C6	−0.1 (2)
C6—C7—C8—N2	−27 (3)	C5—C6—C1—C2	−0.8 (2)
C13—C14—C15—C10	−0.5 (2)	C7—C6—C1—C2	178.46 (13)
C11—C10—C15—C14	0.3 (2)	C2—C3—N1—O2	−178.99 (17)
C9—C10—C15—C14	−179.48 (14)	C4—C3—N1—O2	1.5 (2)
C16—O3—C13—C14	−2.2 (2)	C2—C3—N1—O1	1.5 (2)
C16—O3—C13—C12	178.05 (15)	C4—C3—N1—O1	−177.97 (17)
C15—C14—C13—O3	−179.23 (15)	C18—C17—C21—C20	0.4 (2)
C15—C14—C13—C12	0.5 (3)	C16—C17—C21—C20	179.94 (15)
C15—C10—C11—C12	−0.1 (3)	C19—N3—C20—C21	−0.8 (3)
C9—C10—C11—C12	179.69 (16)	C17—C21—C20—N3	−0.2 (3)
C21—C17—C18—C19	0.4 (2)	C20—N3—C19—C18	1.7 (3)
C16—C17—C18—C19	−179.10 (15)	C17—C18—C19—N3	−1.6 (3)
C13—O3—C16—C17	173.17 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···N2	0.93	2.58	3.417 (2)	149
C1—H1···N3ⁱ	0.93	2.97	3.468 (2)	115
C16—H16A···N2ⁱⁱ	0.97	2.83	3.261 (2)	107
C4—H4···O2ⁱⁱⁱ	0.93	2.63	3.502 (3)	156
C18—H18···O1^iv	0.93	2.47	3.362 (2)	162

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

Funding information

This work was supported by the Undergraduate Research Training Program of Anhui University (KYXL2017019).

References

Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, B. & Fujiki, M. (2016). _Aggregation-Induced Emission: Materials and Applications, Vol. 1, edited by M. Fujiki, B. Liu and B. Z. Tang, ch. 1. ACS Symposium Series. Washington, DC: American Chemical Society. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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