Crystal structure of (E)-furan-2-carbaldehyde O-benzoyloxime

Hijji, Y.M.; Rajan, R.; Mansour, S.; Ben Yahia, H.

doi:10.1107/S2056989017011562

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 73| Part 9| September 2017| Pages 1326-1328

https://doi.org/10.1107/S2056989017011562

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Crystal structure of (E)-furan-2-carbaldehyde O-benzoyloxime

Yousef M. Hijji,^a ^* Rajeesha Rajan,^a Said Mansour ^b and Hamdi Ben Yahia ^b ^*

^aDepartment of Chemistry and Earth Sciences, Qatar University, PO Box 2713, Doha, Qatar, and ^bQatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, PO Box 34110, Doha, Qatar
^*Correspondence e-mail: yousef.hijji@qu.edu.qa, hyahia@qf.org.qa

Edited by T. N. Guru Row, Indian Institute of Science, India (Received 14 July 2017; accepted 4 August 2017; online 8 August 2017)

In the title compound, C₁₂H₉NO₃, the benzoate and furan rings are almost coplanar, making a dihedral angle of 11.68 (9)°. The twist angle between the –COO group and the benzene ring is only 2.79 (16)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming chains along [100]. The molecules stack in a herringbone fashion and inversion-related chains are linked by offset π–π interactions [intercentroid distance = 3.931 (1) Å], forming ribbons propagating along the a-axis direction.

Keywords: crystal structure; oxime; 2-furanaldoxime; benzoyloxime ester; hydrogen bonding.

CCDC reference: 1549733

1. Chemical context

Oxime esters have shown potencies for inhibiting lipoprotein-associated phospholipase A2 (Lp-PLA2) activity. Their derivatives are used for the prevention and treatment of cardiovascular disease (Jeong et al., 2013 , 2006 ). These compounds are good antioxidants and are used in pharmaceutical compositions for their anti-microbial activity (Liu et al., 2008 ; Harini et al., 2012 ; Ahluwalia et al., 2017 ). In view of this interest, we have synthesized the title oxime ester derivative and report herein on its crystal structure.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. An intramolecular short contact (C8—H8⋯O2) is present (Table 1), which may prevent the –COO group from tilting, since the twist angle between the –C6/O2/O3 unit and the benzene ring (C7–C12) is only 2.79 (16)°. This also might be the reason why the molecule is almost planar. The dihedral angle between the furan (O1/C1–C4) ring and the benzene ring is 11.68 (9)°. The C6—O2 and C6=O3 distances of 1.352 (2) and 1.195 (2) Å, respectively, are typical values for single and double C-O bonds. This overall geometry is very similar to that observed for E-benzaldehyde O-benzoyloxime (Altinbas et al., 2004 ). Within the five-membered furan ring, the interatomic O1—C1 and O1—C4 distances of 1.369 (2) and 1.367 (2) Å, respectively, are typical values for O—Csp² bonds. The short C4—C3 and C1—C2 bond lengths of 1.324 (4) and 1.347 (3) Å, respectively, and the stretched C2—C3 bond distance of 1.408 (2) Å are typical values observed for double C=C and single C—C bonds, respectively. The –C5/N1/O2 group is twisted by 4.40 (13) ° with respect to the furan ring. The N1—O2 distance of 1.444 (1) Å is only slightly longer than reported in other oxime compounds (Wetherington & Moncrief, 1973 ), whereas the C=N—O angle of 106.73 (11)° is slightly smaller.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2	0.93 (2)	2.384 (13)	2.724 (2)	102 (1)
C5—H5⋯O3ⁱ	0.97 (2)	2.312 (16)	3.159 (2)	145 (1)
Symmetry code: (i) x-1, y, z.

Figure 1
View of the molecular structure of the title compound, with the atom labelling and 50% probability displacement ellipsoids.

3. Supramolecular features

In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming chains along the a-axis direction (Table 1 and Fig. 2). The molecules stack in a herringbone fashion and inversion-related chains are linked by offset π–π interactions [Cg1⋯Cg1ⁱ = 3.931 (1) Å, interplanar distance = 3.574 (1) Å, slippage = 1.64 Å, α = 0.03 (7)°, Cg1 is the centroid of the benzene ring (C7–C12); symmetry code: (i) −x + 1, −y + 2, −z], forming ribbons propagating along the a-axis direction (Fig. 3).

Figure 2
A view along the b axis of the crystal packing of the title compound. The C—H⋯O hydrogen bonds, linking molecules to form chains along [100], are shown as dashed lines [see Table 1

; only H atom H5 (grey ball) has been included].

Figure 3
A view along the a axis of the crystal packing of the title compound. The offset π–π interactions are shown as blue double arrows, and only H atom H5 (grey ball) has been included.

4. Database survey

A search of the Cambridge Structural Database (Version 5.38, update May 2017; Groom et al., 2016 ) for the substructure furan-2-carbaldehyde oxime gave 20 hits, while for substructure formaldehyde O-benzoyloxime there were 24 hits. The O—N distances vary from ca 1.38 to 1.45 Å, while the N=C distances vary from ca 1.25 to 1.32 Å. In the title compound, these distances are N1—O2 = 1.444 (1) Å and N1=C5 is 1.270 (2) Å, within the limits observed. In the majority of the formaldehyde O-benzoyloxime structures, the dihedral angle between the plane of the –COO group and the benzene ring is <10 °. In the title compound, this dihedral angle is 2.79 (16)°.

5. Synthesis and crystallization

Synthesis of 2-furanaldoxime: A mixture of 5.0 g of furfuraldehyde (without further purification), 1.5 equiv. of NH₂OH·HCl and 1 mmol of pyridine was stirred for 3 h at rt until the NH₂OH·HCl was completely solubilized. The reaction mixture was then quenched in water and the furanaldoxime precipitated out. This solid was filtered and recrystallized from diethyl ether to give colourless needle-like crystals (yield 4.268 g, 74%; m.p. 349–351 K). FT–IR spectrum showed two peaks at 3166 and 1634 cm⁻¹. Elemental analysis: analysis calculated for C₅H₅NO₂ (111.10 g mol⁻¹): C, 54.05; H, 4.54; N, 12.61; O, 28.80%. Found: C, 53.13; H, 4.45; N, 12.99; O, 29.43%. ¹H NMR (DMSO-d₆): δ (ppm): 6.64 (dd, J = 3.42Hz, 0.49 Hz, 1H), 7.20 (d, J = 3.42Hz, 1H), 7.52 (s, 1H), 7.76 (s, 1H), 11.80 (s, 1H). ¹³C NMR (DMSO-d₆): δ (ppm) = 145.85, 143.80, 135.92, 116.89, 112.67.

Preparation of the O-benzoyl ester of furanaldoxime: Benzoyl chloride (5.01 mmol) was added dropwise under stirring to 4.55 mmol of furanaldoxime. Since the reaction was vigorous and exothermic the mixture was placed in an ice bath for 30 min. The reaction mixture was then quenched in ice–water, and then extracted with EtOAc. The organic layer was separated and washed with 1M NaOH solution to remove the benzoic acid and HCl that had formed as by products. The EtOAc layer was passed through anhydrous Na₂SO₄ and dried in vacuo to give the title compound as a light-brown solid (0.9806 g). Recrystallization of the title compound from ethanol–EtOAc gave colourless needle-like crystals (yield 50%, m.p. 410–412 K). Elemental analysis: analysis calculated for C₁₂H₉NO₃ (215.20 g mol⁻¹): C, 66.97; H, 4.22; N, 6.51; O, 22.30%. Found: C, 67.00; H, 4.19; N, 6.40; O, 22.41%. ¹H NMR (DMSO-d₆): δ (ppm): 6.74–6.75 (dd, J = 3.67Hz,1.96Hz, 1H), 7.18 (d, J = 3.42Hz, 1H), 7.60 (t, J = 8.04 Hz, 2H), 7.73 (t, J = 7.58Hz, 1H), 8.01 (s, 1H), 8.07 (dd, J = 8.56 Hz,1.22 Hz 2H), 8.82 (s, 1H). ¹³C NMR (DMSO-d₆): δ ppm: 163.55, 148.05, 147.65, 145.28, 134.35, 129.77, 129.48, 128.52, 119.14, 113.07.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms were located from difference-Fourier maps and freely refined.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₉NO₃
M_r	215.2
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.3414 (3), 9.1268 (5), 18.1423 (9)
β (°)	95.634 (2)
V (Å³)	1044.94 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.1
Crystal size (mm)	0.19 × 0.06 × 0.04

Data collection
Diffractometer	D8 venture
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.87, 0.89
No. of measured, independent and observed [I > 3σ(I)] reflections	19019, 2480, 1245
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F > 3σ(F)], wR(F), S	0.037, 0.101, 1.05
No. of reflections	2480
No. of parameters	182
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.19
Computer programs: APEX3 and SAINT (Bruker, 2015), SIR2002 (Burla et al. 2003 ), JANA2006 (Petricek et al., 2014 ), DIAMOND (Brandenburg & Berndt, 1999 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1549733

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017011562/gw2156sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017011562/gw2156Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017011562/gw2156Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SIR2002 (Burla et al. 2003); program(s) used to refine structure: JANA2006 (Petricek et al., 2014); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999) and Mercury (Macrae et al., 2008); software used to prepare material for publication: JANA2006 (Petricek et al., 2014).

(E)-(Furan-2-ylmethylidene)amino benzoate top

Crystal data top

C₁₂H₉NO₃	F(000) = 448
M_r = 215.2	D_x = 1.368 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 19019 reflections
a = 6.3414 (3) Å	θ = 2.3–27.9°
b = 9.1268 (5) Å	µ = 0.1 mm⁻¹
c = 18.1423 (9) Å	T = 293 K
β = 95.634 (2)°	Needle, colourless
V = 1044.94 (9) Å³	0.19 × 0.06 × 0.04 mm
Z = 4

Data collection top

D8 venture diffractometer	1245 reflections with I > 3σ(I)
Radiation source: X-ray tube	R_int = 0.061
ω and π scans	θ_max = 27.9°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −7→8
T_min = 0.87, T_max = 0.89	k = −12→12
19019 measured reflections	l = −23→23
2480 independent reflections

Refinement top

Refinement on F²	All H-atom parameters refined
R[F > 3σ(F)] = 0.037	Weighting scheme based on measured s.u.'s w = 1/(σ²(I) + 0.001936I²)
wR(F) = 0.101	(Δ/σ)_max = 0.002
S = 1.05	Δρ_max = 0.24 e Å⁻³
2480 reflections	Δρ_min = −0.19 e Å⁻³
182 parameters	Extinction correction: B–C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 8600 (1100)
0 constraints

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

	x	y	z	U_iso*/U_eq
O1	0.30081 (17)	0.35070 (10)	0.20660 (6)	0.0583 (4)
O2	0.40886 (16)	0.65844 (10)	0.04205 (5)	0.0509 (4)
O3	0.76174 (18)	0.66965 (13)	0.06946 (6)	0.0708 (5)
N1	0.4062 (2)	0.55510 (12)	0.10223 (6)	0.0514 (5)
C1	0.1492 (3)	0.42685 (14)	0.16340 (8)	0.0476 (5)
C2	−0.0453 (3)	0.39050 (16)	0.18114 (10)	0.0599 (7)
H2	−0.177 (3)	0.4294 (17)	0.1589 (9)	0.071 (5)*
C3	−0.0152 (4)	0.28632 (18)	0.23844 (10)	0.0695 (8)
H3	−0.120 (3)	0.2372 (18)	0.2617 (9)	0.076 (5)*
C4	0.1916 (4)	0.26537 (18)	0.25172 (10)	0.0682 (8)
H4	0.279 (3)	0.2027 (17)	0.2837 (9)	0.074 (5)*
C5	0.2128 (3)	0.52772 (15)	0.10928 (8)	0.0468 (5)
H5	0.099 (3)	0.5716 (15)	0.0768 (8)	0.060 (4)*
C6	0.6056 (2)	0.70645 (15)	0.03182 (8)	0.0448 (5)
C7	0.6002 (2)	0.81086 (13)	−0.03072 (7)	0.0402 (5)
C8	0.4156 (3)	0.84781 (16)	−0.07375 (8)	0.0505 (6)
H8	0.290 (2)	0.8040 (15)	−0.0630 (7)	0.058 (4)*
C9	0.4214 (3)	0.94724 (17)	−0.13070 (10)	0.0600 (7)
H9	0.295 (3)	0.9700 (17)	−0.1605 (9)	0.073 (5)*
C10	0.6096 (3)	1.01023 (18)	−0.14491 (9)	0.0596 (7)
H10	0.617 (3)	1.0760 (16)	−0.1852 (9)	0.069 (5)*
C11	0.7926 (3)	0.97388 (18)	−0.10261 (9)	0.0619 (7)
H11	0.922 (3)	1.0175 (17)	−0.1118 (9)	0.072 (5)*
C12	0.7884 (3)	0.87486 (17)	−0.04569 (9)	0.0521 (6)
H12	0.917 (3)	0.8530 (15)	−0.0176 (9)	0.067 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0656 (9)	0.0566 (6)	0.0511 (6)	−0.0020 (5)	−0.0023 (5)	0.0048 (5)
O2	0.0418 (7)	0.0557 (6)	0.0551 (6)	0.0011 (5)	0.0037 (5)	0.0127 (5)
O3	0.0408 (8)	0.0946 (8)	0.0751 (8)	0.0062 (6)	−0.0033 (6)	0.0227 (6)
N1	0.0521 (10)	0.0499 (7)	0.0518 (8)	0.0018 (6)	0.0026 (6)	0.0090 (6)
C1	0.0539 (11)	0.0431 (7)	0.0458 (9)	0.0023 (7)	0.0056 (7)	−0.0043 (6)
C2	0.0589 (13)	0.0498 (9)	0.0740 (11)	0.0015 (8)	0.0217 (10)	0.0002 (8)
C3	0.0903 (18)	0.0522 (9)	0.0718 (12)	−0.0055 (10)	0.0368 (12)	−0.0006 (9)
C4	0.1016 (19)	0.0539 (10)	0.0491 (11)	−0.0050 (11)	0.0081 (10)	0.0044 (8)
C5	0.0443 (11)	0.0464 (8)	0.0498 (9)	0.0024 (7)	0.0052 (7)	−0.0011 (7)
C6	0.0350 (10)	0.0488 (7)	0.0506 (9)	0.0034 (6)	0.0043 (7)	−0.0060 (7)
C7	0.0347 (9)	0.0416 (7)	0.0447 (8)	0.0012 (6)	0.0061 (6)	−0.0067 (6)
C8	0.0385 (11)	0.0556 (8)	0.0577 (10)	−0.0016 (7)	0.0067 (8)	0.0046 (8)
C9	0.0482 (13)	0.0682 (10)	0.0627 (11)	0.0040 (8)	0.0019 (9)	0.0134 (8)
C10	0.0586 (13)	0.0624 (10)	0.0592 (11)	−0.0018 (9)	0.0134 (9)	0.0103 (8)
C11	0.0516 (13)	0.0694 (10)	0.0668 (11)	−0.0138 (9)	0.0171 (9)	0.0000 (9)
C12	0.0373 (11)	0.0643 (9)	0.0544 (10)	−0.0023 (8)	0.0032 (8)	−0.0035 (8)

Geometric parameters (Å, º) top

O1—C1	1.3688 (17)	C5—H5	0.970 (15)
O1—C4	1.367 (2)	C6—C7	1.4795 (19)
O2—N1	1.4441 (14)	C7—C8	1.383 (2)
O2—C6	1.3523 (19)	C7—C12	1.379 (2)
O3—C6	1.1945 (18)	C8—H8	0.927 (16)
N1—C5	1.270 (2)	C8—C9	1.378 (2)
C1—C2	1.347 (3)	C9—H9	0.944 (17)
C1—C5	1.433 (2)	C9—C10	1.372 (3)
C2—H2	0.957 (17)	C10—H10	0.950 (16)
C2—C3	1.408 (2)	C10—C11	1.368 (2)
C3—H3	0.936 (18)	C11—H11	0.943 (17)
C3—C4	1.324 (4)	C11—C12	1.374 (2)
C4—H4	0.952 (16)	C12—H12	0.941 (16)

C1—O1—C4	105.29 (14)	O3—C6—C7	125.11 (14)
N1—O2—C6	113.27 (10)	C6—C7—C8	122.99 (13)
O2—N1—C5	106.73 (11)	C6—C7—C12	117.92 (13)
O1—C1—C2	110.27 (13)	C8—C7—C12	119.09 (13)
O1—C1—C5	119.30 (14)	C7—C8—H8	118.1 (8)
C2—C1—C5	130.42 (15)	C7—C8—C9	120.00 (15)
C1—C2—H2	126.0 (10)	H8—C8—C9	121.9 (9)
C1—C2—C3	106.37 (18)	C8—C9—H9	119.4 (10)
H2—C2—C3	127.6 (10)	C8—C9—C10	120.31 (16)
C2—C3—H3	127.2 (10)	H9—C9—C10	120.2 (10)
C2—C3—C4	107.0 (2)	C9—C10—H10	121.1 (10)
H3—C3—C4	125.7 (10)	C9—C10—C11	119.92 (16)
O1—C4—C3	111.09 (16)	H10—C10—C11	118.9 (10)
O1—C4—H4	114.1 (11)	C10—C11—H11	120.3 (9)
C3—C4—H4	134.8 (11)	C10—C11—C12	120.21 (17)
N1—C5—C1	122.35 (14)	H11—C11—C12	119.5 (10)
N1—C5—H5	121.6 (9)	C7—C12—C11	120.48 (15)
C1—C5—H5	116.0 (9)	C7—C12—H12	121.7 (10)
O2—C6—O3	123.68 (13)	C11—C12—H12	117.8 (10)
O2—C6—C7	111.21 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2	0.93 (2)	2.384 (13)	2.724 (2)	102 (1)
C5—H5···O3ⁱ	0.97 (2)	2.312 (16)	3.159 (2)	145 (1)

Symmetry code: (i) x−1, y, z.

Acknowledgements

We are grateful to Mr Ahmed Abdelsalam Ali Easa of the Central Laboratory Unit, Qatar University, for the elemental analysis, and to Mr Ziad Sarah from the American University of Sharjah for measuring the NMR data.

Funding information

Funding for this research was provided by: Qatar National Research Fund (award No. NPRP-7-495-1-094).

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