(E)-3-[4-(Benzo[d]oxazol-2-yl)styr­yl]-1-methyl­pyridin-1-ium tri­fluoro­acetate

Xia, Y.; Wang, H.; Yu, J.; Wu, Z.

doi:10.1107/S2414314617017333

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 12| December 2017| x171733

https://doi.org/10.1107/S2414314617017333

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(E)-3-[4-(Benzo[d]oxazol-2-yl)styryl]-1-methylpyridin-1-ium trifluoroacetate

Ying Xia,^a,^b Haiyan Wang,^a,^b ^* Jianhua Yu ^a,^b and Zhichao Wu ^a,^b

^aDepartment of Chemistry, Anhui University, Hefei 230601, People's Republic of China, and ^bKey Laboratory of Functional Inorganic Materials Chemistry, Hefei 230601, People's Republic of China
^*Correspondence e-mail: 24886084@qq.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 4 September 2017; accepted 4 December 2017; online 8 December 2017)

In the title molecular salt, C₂₁H₁₇N₂O⁺·CF₃CO₂⁻, the dihedral angles between the benzene ring and pendant pyridyl and benzoxazole substituents of the cation are 15.35 (10) and 2.55 (9)°, respectively. In the crystal, the components are linked by weak C—H⋯O hydrogen bonds, C—F⋯π interactions and aromatic π–π stacking interactions. The F atoms of the anion are disordered over two set of sites in a 0.536 (6):0.464 (6) ratio.

Keywords: crystal structure; benzoxazole derivative; trifluoroacetate.

CCDC reference: 1588979

Structure description

In the title molecular salt (Fig. 1), the dihedral angles between the benzene ring and pendant pyridyl and benzoxazole substituents of the cation are 15.35 (10) and 2.55 (9)°, respectively. The near co-planarity of the ring systems was also found in a similar structure (Centore et al., 2013 ).

Figure 1
The molecular structure, with displacement ellipsoids drawn at the 50% probability level.

In the crystal (Figs. 2 and 3), the components are linked by weak C—H⋯O hydrogen bonds, C—F⋯π interactions (Table 1) and aromatic π–π stacking interactions [shortest centroid-centroid separation = 3.7709 (11) Å].

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C5/N2 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2ⁱ	0.93	2.49	3.375 (3)	158
C3—H3⋯O2ⁱⁱ	0.93	2.40	3.213 (3)	146
C11—H11A⋯O1ⁱ	0.96	2.34	3.245 (5)	157
C22—F2⋯Cg2ⁱⁱⁱ	1.35 (1)	3.24 (1)	4.072 (4)	120 (1)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) -x+1, -y+1, -z+1.

Figure 2
Hydrogen-bonded chain in the crystal.

Figure 3
The unit-cell packing.

Synthesis and crystallization

Silver trifluoroacetate (0.15 g, 0.68 mmol) was added to a solution of 3-(4-(benzo[d]oxazol-2-yl)styryl)-1-methylpyridin-1-ium iodide (0.3 g, 0.68 mmol) in acetonitrile. The reaction mixture was refluxed for 4 h, then filtered and evaporated, and concentrated in vacuo to give an off-yellow solid. Yellow single crystals were obtained in 15% yield by recrystallization from acetonitrile solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The F atoms of the anion are disordered over two set of sites in a 0.536 (6):0.464 (6) ratio.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₁₇N₂O⁺·C₂F₃O₂⁻
M_r	426.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	19.817 (2), 8.4268 (9), 12.4459 (14)
β (°)	101.220 (1)
V (Å³)	2038.6 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000 )
T_min, T_max	0.950, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	14029, 3593, 2798
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.161, 1.12
No. of reflections	3593
No. of parameters	311
No. of restraints	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.23
Computer programs: SMART and SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1588979

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017333/hb4169sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017333/hb4169Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617017333/hb4169Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(E)-3-[4-(Benzo[d]oxazol-2-yl)styryl]-1-methylpyridin-1-ium trifluoroacetate top

Crystal data top

C₂₁H₁₇N₂O⁺·C₂F₃O₂⁻	F(000) = 880
M_r = 426.39	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.817 (2) Å	Cell parameters from 4829 reflections
b = 8.4268 (9) Å	θ = 2.6–26.7°
c = 12.4459 (14) Å	µ = 0.11 mm⁻¹
β = 101.220 (1)°	T = 296 K
V = 2038.6 (4) Å³	Block, yellow
Z = 4	0.2 × 0.2 × 0.2 mm

Data collection top

Bruker SMART CCD diffractometer	2798 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.037
phi and ω scans	θ_max = 25.0°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −22→23
T_min = 0.950, T_max = 0.966	k = −10→9
14029 measured reflections	l = −14→14
3593 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.0891P)² + 0.3359P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
3593 reflections	Δρ_max = 0.37 e Å⁻³
311 parameters	Δρ_min = −0.23 e Å⁻³
92 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

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. All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å and and U_iso(H) = 1.5U_eq(C) for the methyl H atoms and 1.2U_eq(C) for the others.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O3	0.43709 (6)	0.38309 (16)	0.38049 (9)	0.0493 (4)
C12	0.49287 (9)	0.2408 (2)	0.54155 (13)	0.0443 (4)
C15	0.43415 (9)	0.3313 (2)	0.48389 (14)	0.0462 (4)
N1	0.37833 (8)	0.3688 (2)	0.51762 (13)	0.0555 (4)
C7	0.66050 (10)	−0.0328 (2)	0.71466 (15)	0.0508 (5)
H7	0.6525	−0.0861	0.7764	0.061*
C8	0.60374 (9)	0.0606 (2)	0.65363 (14)	0.0459 (4)
C5	0.77889 (10)	−0.1425 (2)	0.75259 (15)	0.0507 (5)
C10	0.54997 (10)	0.2117 (2)	0.49481 (14)	0.0514 (5)
H10	0.5513	0.2518	0.4256	0.062*
C14	0.54614 (10)	0.0900 (2)	0.69936 (15)	0.0515 (5)
H14	0.5443	0.0482	0.7679	0.062*
C13	0.49192 (10)	0.1796 (2)	0.64546 (14)	0.0507 (5)
H13	0.4545	0.1994	0.6784	0.061*
C6	0.72239 (10)	−0.0490 (2)	0.69052 (16)	0.0538 (5)
H6	0.7306	0.0037	0.6287	0.065*
C16	0.37561 (9)	0.4620 (2)	0.34662 (15)	0.0476 (5)
C9	0.60454 (10)	0.1243 (2)	0.54981 (14)	0.0524 (5)
H9	0.6425	0.1073	0.5177	0.063*
N2	0.89569 (9)	−0.2225 (2)	0.77180 (15)	0.0688 (5)
C1	0.84123 (11)	−0.1384 (3)	0.71989 (17)	0.0597 (5)
H1	0.8459	−0.0759	0.6602	0.072*
C3	0.83135 (13)	−0.3201 (3)	0.89581 (19)	0.0718 (6)
H3	0.8282	−0.3819	0.9565	0.086*
C2	0.89154 (13)	−0.3125 (3)	0.8594 (2)	0.0714 (6)
H2	0.9297	−0.3693	0.8949	0.086*
C20	0.28822 (12)	0.6107 (3)	0.23782 (19)	0.0676 (6)
H20	0.2697	0.6628	0.1729	0.081*
C17	0.33959 (10)	0.4538 (2)	0.43082 (16)	0.0527 (5)
C21	0.35254 (11)	0.5396 (3)	0.24913 (17)	0.0602 (5)
H21	0.3783	0.5442	0.1943	0.072*
C4	0.77489 (12)	−0.2364 (3)	0.84290 (17)	0.0623 (6)
H4	0.7337	−0.2428	0.8679	0.075*
C18	0.27540 (12)	0.5279 (3)	0.4186 (2)	0.0721 (7)
H18	0.2500	0.5251	0.4740	0.087*
C19	0.25131 (12)	0.6053 (3)	0.3212 (2)	0.0723 (7)
H19	0.2088	0.6556	0.3113	0.087*
C11	0.96006 (15)	−0.2176 (5)	0.7288 (3)	0.1203 (13)
H11A	0.9543	−0.1482	0.6666	0.180*
H11B	0.9968	−0.1792	0.7847	0.180*
H11C	0.9710	−0.3225	0.7073	0.180*
O2	0.17618 (10)	0.6468 (2)	−0.02605 (16)	0.0915 (6)
C23	0.11504 (13)	0.6724 (3)	−0.03020 (19)	0.0677 (6)
O1	0.06594 (13)	0.5908 (3)	−0.0700 (2)	0.1265 (9)
C22	0.09873 (16)	0.8216 (4)	0.0293 (3)	0.1014 (10)
F2	0.1534 (4)	0.8663 (7)	0.1057 (5)	0.150 (3)	0.536 (6)
F3	0.0446 (5)	0.8467 (13)	0.0561 (8)	0.167 (3)	0.536 (6)
F1	0.1012 (3)	0.9471 (6)	−0.0515 (7)	0.150 (2)	0.536 (6)
F2'	0.1024 (4)	0.7737 (10)	0.1428 (4)	0.158 (3)	0.464 (6)
F1'	0.1287 (4)	0.9425 (9)	0.0258 (9)	0.155 (3)	0.464 (6)
F3'	0.0297 (4)	0.8498 (11)	0.0030 (8)	0.138 (3)	0.464 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0469 (7)	0.0595 (8)	0.0440 (7)	0.0070 (6)	0.0151 (5)	0.0010 (6)
C12	0.0451 (10)	0.0481 (10)	0.0409 (9)	−0.0034 (8)	0.0114 (8)	−0.0060 (7)
C15	0.0493 (10)	0.0511 (11)	0.0400 (9)	−0.0028 (8)	0.0133 (8)	−0.0052 (8)
N1	0.0509 (9)	0.0703 (11)	0.0496 (9)	0.0083 (8)	0.0209 (7)	−0.0003 (8)
C7	0.0584 (12)	0.0512 (11)	0.0430 (10)	−0.0026 (9)	0.0103 (8)	0.0013 (8)
C8	0.0499 (10)	0.0465 (10)	0.0406 (9)	−0.0037 (8)	0.0076 (8)	−0.0028 (7)
C5	0.0575 (12)	0.0431 (10)	0.0487 (10)	0.0002 (8)	0.0038 (8)	−0.0003 (8)
C10	0.0540 (11)	0.0640 (12)	0.0387 (9)	0.0074 (9)	0.0156 (8)	0.0036 (8)
C14	0.0577 (12)	0.0586 (12)	0.0405 (9)	−0.0042 (9)	0.0151 (8)	0.0030 (8)
C13	0.0501 (11)	0.0607 (12)	0.0450 (9)	−0.0028 (9)	0.0183 (8)	−0.0004 (8)
C6	0.0602 (12)	0.0529 (11)	0.0486 (10)	0.0035 (9)	0.0113 (9)	0.0076 (9)
C16	0.0435 (10)	0.0494 (11)	0.0502 (10)	0.0036 (8)	0.0102 (8)	−0.0068 (8)
C9	0.0497 (11)	0.0667 (13)	0.0440 (10)	0.0066 (9)	0.0166 (8)	−0.0004 (9)
N2	0.0612 (11)	0.0721 (12)	0.0708 (11)	0.0161 (9)	0.0076 (9)	0.0102 (10)
C1	0.0627 (13)	0.0602 (13)	0.0548 (11)	0.0120 (10)	0.0080 (10)	0.0086 (9)
C3	0.0831 (17)	0.0618 (14)	0.0659 (13)	0.0016 (12)	0.0027 (12)	0.0180 (11)
C2	0.0772 (16)	0.0582 (13)	0.0710 (14)	0.0106 (12)	−0.0048 (12)	0.0103 (11)
C20	0.0672 (14)	0.0611 (13)	0.0688 (13)	0.0112 (11)	−0.0008 (11)	−0.0003 (11)
C17	0.0482 (11)	0.0575 (12)	0.0544 (11)	0.0037 (9)	0.0149 (9)	−0.0066 (9)
C21	0.0640 (13)	0.0633 (13)	0.0537 (11)	0.0078 (10)	0.0121 (10)	0.0012 (10)
C4	0.0668 (13)	0.0558 (12)	0.0622 (12)	−0.0027 (10)	0.0074 (10)	0.0080 (10)
C18	0.0557 (13)	0.0858 (17)	0.0798 (15)	0.0149 (12)	0.0252 (11)	−0.0055 (13)
C19	0.0540 (13)	0.0723 (15)	0.0882 (17)	0.0171 (11)	0.0081 (12)	−0.0074 (13)
C11	0.0751 (18)	0.162 (3)	0.131 (3)	0.048 (2)	0.0386 (18)	0.052 (2)
O2	0.0895 (13)	0.0849 (13)	0.1105 (14)	0.0171 (10)	0.0453 (11)	0.0163 (10)
C23	0.0698 (15)	0.0606 (14)	0.0690 (14)	−0.0011 (12)	0.0044 (12)	0.0095 (11)
O1	0.1061 (17)	0.0880 (15)	0.162 (2)	0.0031 (13)	−0.0307 (15)	−0.0219 (15)
C22	0.0757 (18)	0.080 (2)	0.155 (3)	0.0000 (16)	0.039 (2)	−0.0221 (17)
F2	0.181 (5)	0.116 (4)	0.131 (4)	0.011 (3)	−0.021 (4)	−0.066 (3)
F3	0.142 (5)	0.183 (5)	0.206 (7)	0.036 (4)	0.111 (5)	−0.010 (5)
F1	0.159 (5)	0.066 (2)	0.225 (6)	0.027 (3)	0.034 (4)	0.017 (3)
F2'	0.158 (5)	0.226 (6)	0.098 (3)	0.031 (5)	0.044 (3)	−0.031 (4)
F1'	0.152 (6)	0.102 (4)	0.226 (7)	−0.045 (4)	0.068 (5)	−0.065 (5)
F3'	0.096 (3)	0.119 (4)	0.197 (7)	0.036 (3)	0.024 (4)	−0.049 (5)

Geometric parameters (Å, º) top

O3—C15	1.371 (2)	N2—C2	1.344 (3)
O3—C16	1.380 (2)	N2—C1	1.346 (3)
C12—C10	1.391 (3)	N2—C11	1.477 (3)
C12—C13	1.396 (2)	C3—C2	1.357 (4)
C12—C15	1.458 (3)	C3—C4	1.377 (3)
C15—N1	1.296 (2)	C20—C19	1.382 (3)
N1—C17	1.395 (3)	C20—C21	1.390 (3)
C7—C6	1.325 (3)	C17—C18	1.398 (3)
C7—C8	1.459 (3)	C18—C19	1.377 (4)
C8—C14	1.393 (3)	O2—C23	1.222 (3)
C8—C9	1.402 (3)	C23—O1	1.215 (3)
C5—C1	1.374 (3)	C23—C22	1.525 (4)
C5—C4	1.390 (3)	C22—F1'	1.184 (6)
C5—C6	1.461 (3)	C22—F3	1.203 (7)
C10—C9	1.375 (3)	C22—F2	1.348 (6)
C14—C13	1.376 (3)	C22—F3'	1.365 (8)
C16—C21	1.376 (3)	C22—F2'	1.456 (6)
C16—C17	1.380 (3)	C22—F1	1.467 (7)

C15—O3—C16	104.12 (13)	N2—C1—C5	121.8 (2)
C10—C12—C13	118.74 (17)	C2—C3—C4	120.1 (2)
C10—C12—C15	121.51 (16)	N2—C2—C3	119.6 (2)
C13—C12—C15	119.74 (16)	C19—C20—C21	121.2 (2)
N1—C15—O3	114.91 (16)	C16—C17—C18	119.3 (2)
N1—C15—C12	128.15 (16)	C16—C17—N1	109.01 (16)
O3—C15—C12	116.93 (14)	C18—C17—N1	131.69 (19)
C15—N1—C17	104.48 (15)	C16—C21—C20	115.8 (2)
C6—C7—C8	126.23 (18)	C3—C4—C5	120.6 (2)
C14—C8—C9	117.73 (17)	C19—C18—C17	117.3 (2)
C14—C8—C7	119.54 (17)	C20—C19—C18	122.2 (2)
C9—C8—C7	122.72 (17)	O1—C23—O2	128.7 (3)
C1—C5—C4	116.73 (19)	O1—C23—C22	115.8 (3)
C1—C5—C6	118.07 (17)	O2—C23—C22	115.3 (2)
C4—C5—C6	125.20 (19)	F3—C22—F2	113.1 (6)
C9—C10—C12	120.73 (17)	F1'—C22—F3'	109.1 (7)
C13—C14—C8	121.50 (17)	F1'—C22—F2'	110.1 (6)
C14—C13—C12	120.30 (17)	F3'—C22—F2'	98.1 (5)
C7—C6—C5	125.69 (18)	F3—C22—F1	102.3 (6)
C21—C16—C17	124.16 (19)	F2—C22—F1	98.7 (5)
C21—C16—O3	128.35 (17)	F1'—C22—C23	122.4 (4)
C17—C16—O3	107.47 (16)	F3—C22—C23	124.4 (6)
C10—C9—C8	120.99 (17)	F2—C22—C23	110.9 (3)
C2—N2—C1	121.1 (2)	F3'—C22—C23	108.9 (4)
C2—N2—C11	120.2 (2)	F2'—C22—C23	105.5 (4)
C1—N2—C11	118.7 (2)	F1—C22—C23	102.9 (4)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C5/N2 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.93	2.49	3.375 (3)	158
C3—H3···O2ⁱⁱ	0.93	2.40	3.213 (3)	146
C11—H11A···O1ⁱ	0.96	2.34	3.245 (5)	157
C22—F2···Cg2ⁱⁱⁱ	1.35 (1)	3.24 (1)	4.072 (4)	120 (1)

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

Funding information

This work was supported by the Graduate Students Innovative Program of Anhui University (J18515024, J18515019, 201310357155).

References

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