Bis(acetophenone oxime) O,O′-methyl­ene ether

Zhang, Y.; Zang, H.-J.; Cheng, B.-W.; Song, J.

doi:10.1107/S160053680803897X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2452

doi:10.1107/S160053680803897X

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Bis(acetophenone oxime) O,O′-methylene ether

Yong Zhang,^a Hong-Jun Zang,^a ^* Bo-Wen Cheng ^a and Jun Song ^a

^aSchool of Materials and Chemical Engineering and Key Laboratory of Hollow Fiber Membrane Materials & Membrane Processes, Tianjin Polytechnic University, Tianjin 300160, People's Republic of China
^*Correspondence e-mail: chemhong@126.com

(Received 18 November 2008; accepted 20 November 2008; online 26 November 2008)

In the molecule of the title compound, C₁₇H₁₈N₂O₂, the dihedral angle between the aromatic rings is 74.26 (3)°. The oxime units are oriented at dihedral angles of 7.66 (3) and 33.06 (3)° with respect to the adjacent rings, and they have E configurations about the C=N bonds.

Related literature

For general background on oximes and their varied applications, see: Jones et al. (1961 ); Schrauzer & Kohnle (1964 ); Hashemi et al. (2006 ); Ghiasvand et al. (2004 , 2005 ); Kakanejadifard et al. (2007 ); Otsuka Pharmaceutical Co Ltd (1981 ); Chertanova et al. (1994 ).

Experimental

Crystal data

C₁₇H₁₈N₂O₂
M_r = 282.33
Monoclinic, P 2₁ /n
a = 9.875 (2) Å
b = 8.8409 (18) Å
c = 17.290 (4) Å
β = 101.13 (3)°
V = 1481.1 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 113 (2) K
0.14 × 0.04 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.988, T_max = 0.997
9665 measured reflections
2612 independent reflections
1724 reflections with I > 2σ(I)
R_int = 0.104

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.097
S = 0.96
2612 reflections
193 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680803897X/hk2580sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803897X/hk2580Isup2.hkl

checkCIF report

Comment top

Some oximes are widely used for various purposes in organic, inorganic, bioinorganic, pigment, analytical, dyes and medical chemistry (Jones et al., 1961; Schrauzer & Kohnle, 1964; Hashemi et al., 2006; Ghiasvand et al., 2004; Ghiasvand et al., 2005; Kakanejadifard et al., 2007). Methylene dioximes are important chemicals useful as metal capturers, and antiinflammatory and antibacterial agents (Otsuka Pharmaceutical Co Ltd, 1981). We report herein the synthesis and crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths and angles are within normal ranges. Rings A (C1-C6) and B (C12-C17) are, of course, planar, and they are oriented at a dihedral angle of 74.26 (3)°. The (C1-C7-N1-O1) and (C12/C10/N2/O2) moieties are oriented with respect to the adjacent rings at dihedral angles of 7.66 (3)° and 33.06 (3)°, respectively. The oxime moieties have E configurations [C1-C7-N1-O1 178.38 (12)° and C12-C10-N2-O2 179.02 (10)°; Chertanova et al., 1994].

Related literature top

For general background on oximes and their varied applications, see: Jones et al. (1961); Schrauzer & Kohnle (1964); Hashemi et al. (2006); Ghiasvand et al. (2004, 2005); Kakanejadifard et al. (2007); Otsuka Pharmaceutical Co Ltd (1981); Chertanova et al. (1994).

Experimental top

For the preparation of the title compound, the acetophenone oxime (0.5 mmol) was dissolved in dichloromethane (3.5 ml). [bmim]BF₄ (0.2269 g, 0.1 mmol) and sodium hydroxide (0.167 g) were added. The reaction mixture was stirred at room temperature for 30 min. The mixture was washed with water (10 ml) and extracted with CH₂Cl₂ (15 ml). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and evaporated to dryness in vacuo. The product was purified by chromatography on silica (200–300 mesh). Elution with a mixture of petroleum ether and ethyl acetate [1/20(v/v)] afforded the methylene dioxime. Crystals suitable for X-ray analysis were obtained by slow evaporation of a water solution.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Bis(acetophenone oxime) O,O'-methylene ether top

Crystal data top

C₁₇H₁₈N₂O₂	F(000) = 600
M_r = 282.33	D_x = 1.266 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2756 reflections
a = 9.875 (2) Å	θ = 2.4–27.5°
b = 8.8409 (18) Å	µ = 0.08 mm⁻¹
c = 17.290 (4) Å	T = 113 K
β = 101.13 (3)°	Prism, colorless
V = 1481.1 (6) Å³	0.14 × 0.04 × 0.04 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	2612 independent reflections
Radiation source: rotating anode	1724 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.105
ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −11→11
T_min = 0.988, T_max = 0.997	k = −9→10
9665 measured reflections	l = −20→16

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0345P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.001
2612 reflections	Δρ_max = 0.23 e Å⁻³
193 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (2)

Crystal data top

C₁₇H₁₈N₂O₂	V = 1481.1 (6) Å³
M_r = 282.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.875 (2) Å	µ = 0.08 mm⁻¹
b = 8.8409 (18) Å	T = 113 K
c = 17.290 (4) Å	0.14 × 0.04 × 0.04 mm
β = 101.13 (3)°

Data collection top

Rigaku Saturn diffractometer	2612 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1724 reflections with I > 2σ(I)
T_min = 0.988, T_max = 0.997	R_int = 0.105
9665 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 0.96	Δρ_max = 0.23 e Å⁻³
2612 reflections	Δρ_min = −0.19 e Å⁻³
193 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.36208 (10)	0.65077 (13)	0.02442 (6)	0.0284 (3)
O2	0.14145 (11)	0.61984 (13)	0.05282 (6)	0.0284 (4)
N1	0.39081 (13)	0.79925 (17)	0.05526 (7)	0.0270 (4)
N2	0.15155 (13)	0.46386 (16)	0.07470 (8)	0.0257 (4)
C1	0.55638 (16)	0.9740 (2)	0.11238 (8)	0.0247 (4)
C2	0.45724 (17)	1.0888 (2)	0.10304 (9)	0.0274 (5)
H2	0.3675	1.0676	0.0774	0.033*
C3	0.48996 (17)	1.2324 (2)	0.13110 (9)	0.0315 (5)
H3	0.4223	1.3070	0.1246	0.038*
C4	0.62333 (18)	1.2665 (2)	0.16904 (9)	0.0357 (5)
H4	0.6457	1.3636	0.1879	0.043*
C5	0.72255 (18)	1.1545 (2)	0.17853 (10)	0.0360 (5)
H5	0.8121	1.1765	0.2041	0.043*
C6	0.69013 (17)	1.0102 (2)	0.15045 (9)	0.0328 (5)
H6	0.7583	0.9362	0.1570	0.039*
C7	0.52021 (16)	0.8199 (2)	0.08160 (9)	0.0251 (4)
C8	0.62975 (17)	0.7028 (2)	0.08213 (10)	0.0362 (5)
H8A	0.5891	0.6128	0.0565	0.054*
H8B	0.6721	0.6797	0.1356	0.054*
H8C	0.6983	0.7408	0.0546	0.054*
C9	0.21947 (16)	0.6427 (2)	−0.00642 (9)	0.0283 (5)
H9A	0.2020	0.5603	−0.0441	0.034*
H9B	0.1899	0.7358	−0.0343	0.034*
C10	0.09103 (15)	0.4381 (2)	0.13271 (9)	0.0231 (4)
C11	0.02188 (17)	0.5564 (2)	0.17390 (10)	0.0329 (5)
H11A	0.0883	0.6006	0.2157	0.049*
H11B	−0.0509	0.5107	0.1954	0.049*
H11C	−0.0159	0.6337	0.1369	0.049*
C12	0.09387 (15)	0.2791 (2)	0.15882 (9)	0.0241 (4)
C13	0.09137 (16)	0.1598 (2)	0.10568 (9)	0.0278 (5)
H13	0.0876	0.1804	0.0526	0.033*
C14	0.09444 (16)	0.0116 (2)	0.13108 (10)	0.0324 (5)
H14	0.0931	−0.0670	0.0952	0.039*
C15	0.09958 (16)	−0.0200 (2)	0.20996 (10)	0.0327 (5)
H15	0.1010	−0.1199	0.2269	0.039*
C16	0.10255 (16)	0.0964 (2)	0.26369 (10)	0.0303 (5)
H16	0.1065	0.0751	0.3167	0.036*
C17	0.09954 (15)	0.2444 (2)	0.23818 (9)	0.0265 (5)
H17	0.1013	0.3224	0.2744	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0275 (7)	0.0271 (9)	0.0310 (7)	0.0022 (6)	0.0069 (5)	−0.0017 (5)
O2	0.0292 (7)	0.0262 (9)	0.0310 (7)	0.0010 (6)	0.0085 (5)	0.0017 (5)
N1	0.0287 (8)	0.0268 (10)	0.0262 (8)	0.0008 (7)	0.0071 (6)	0.0000 (6)
N2	0.0248 (8)	0.0211 (10)	0.0305 (8)	−0.0004 (7)	0.0031 (6)	0.0003 (7)
C1	0.0231 (9)	0.0314 (13)	0.0209 (9)	0.0014 (9)	0.0073 (7)	0.0047 (8)
C2	0.0244 (9)	0.0333 (13)	0.0246 (9)	−0.0004 (9)	0.0050 (7)	−0.0009 (8)
C3	0.0325 (10)	0.0335 (14)	0.0296 (10)	0.0025 (9)	0.0085 (8)	0.0005 (8)
C4	0.0412 (12)	0.0374 (14)	0.0286 (10)	−0.0098 (10)	0.0073 (8)	0.0012 (9)
C5	0.0265 (10)	0.0471 (16)	0.0328 (11)	−0.0084 (10)	0.0018 (8)	0.0047 (9)
C6	0.0252 (10)	0.0420 (15)	0.0317 (10)	0.0013 (9)	0.0070 (7)	0.0069 (9)
C7	0.0250 (9)	0.0308 (12)	0.0205 (9)	0.0053 (8)	0.0068 (7)	0.0052 (8)
C8	0.0293 (10)	0.0370 (14)	0.0416 (11)	0.0072 (9)	0.0051 (8)	0.0005 (9)
C9	0.0278 (10)	0.0332 (13)	0.0236 (10)	−0.0026 (8)	0.0044 (8)	0.0017 (8)
C10	0.0173 (9)	0.0276 (12)	0.0237 (9)	−0.0008 (8)	0.0024 (7)	−0.0040 (8)
C11	0.0334 (10)	0.0299 (13)	0.0369 (10)	0.0031 (9)	0.0100 (8)	−0.0027 (8)
C12	0.0167 (9)	0.0258 (12)	0.0294 (10)	−0.0002 (8)	0.0038 (7)	−0.0014 (8)
C13	0.0255 (10)	0.0300 (14)	0.0288 (10)	−0.0012 (9)	0.0075 (7)	−0.0028 (8)
C14	0.0301 (10)	0.0265 (13)	0.0411 (11)	0.0014 (9)	0.0082 (8)	−0.0058 (9)
C15	0.0252 (10)	0.0278 (13)	0.0440 (11)	0.0011 (9)	0.0037 (8)	0.0050 (9)
C16	0.0254 (10)	0.0332 (14)	0.0310 (10)	−0.0004 (9)	0.0023 (8)	0.0044 (9)
C17	0.0203 (9)	0.0278 (13)	0.0309 (10)	−0.0008 (8)	0.0041 (7)	−0.0059 (8)

Geometric parameters (Å, º) top

O1—C9	1.4081 (17)	C8—H8B	0.9600
O1—N1	1.4246 (17)	C8—H8C	0.9600
O2—C9	1.4100 (19)	C9—H9A	0.9700
O2—N2	1.4283 (17)	C9—H9B	0.9700
N1—C7	1.2842 (19)	C10—C12	1.476 (2)
N2—C10	1.283 (2)	C10—C11	1.502 (2)
C1—C6	1.394 (2)	C11—H11A	0.9600
C1—C2	1.397 (2)	C11—H11B	0.9600
C1—C7	1.481 (2)	C11—H11C	0.9600
C2—C3	1.375 (2)	C12—C13	1.396 (2)
C2—H2	0.9300	C12—C17	1.397 (2)
C3—C4	1.386 (2)	C13—C14	1.381 (2)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.380 (2)	C14—C15	1.383 (2)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.381 (2)	C15—C16	1.383 (2)
C5—H5	0.9300	C15—H15	0.9300
C6—H6	0.9300	C16—C17	1.379 (2)
C7—C8	1.496 (2)	C16—H16	0.9300
C8—H8A	0.9600	C17—H17	0.9300

C9—O1—N1	107.51 (12)	O1—C9—H9A	109.1
C9—O2—N2	108.10 (12)	O2—C9—H9A	109.1
C7—N1—O1	112.12 (13)	O1—C9—H9B	109.1
C10—N2—O2	111.03 (14)	O2—C9—H9B	109.1
C6—C1—C2	117.83 (17)	H9A—C9—H9B	107.9
C6—C1—C7	121.41 (15)	N2—C10—C12	115.07 (16)
C2—C1—C7	120.75 (14)	N2—C10—C11	124.78 (17)
C3—C2—C1	121.18 (15)	C12—C10—C11	120.15 (16)
C3—C2—H2	119.4	C10—C11—H11A	109.5
C1—C2—H2	119.4	C10—C11—H11B	109.5
C2—C3—C4	120.31 (17)	H11A—C11—H11B	109.5
C2—C3—H3	119.8	C10—C11—H11C	109.5
C4—C3—H3	119.8	H11A—C11—H11C	109.5
C5—C4—C3	119.23 (18)	H11B—C11—H11C	109.5
C5—C4—H4	120.4	C13—C12—C17	118.25 (17)
C3—C4—H4	120.4	C13—C12—C10	121.45 (16)
C4—C5—C6	120.65 (16)	C17—C12—C10	120.30 (15)
C4—C5—H5	119.7	C14—C13—C12	120.74 (16)
C6—C5—H5	119.7	C14—C13—H13	119.6
C5—C6—C1	120.80 (17)	C12—C13—H13	119.6
C5—C6—H6	119.6	C13—C14—C15	119.97 (17)
C1—C6—H6	119.6	C13—C14—H14	120.0
N1—C7—C1	114.38 (15)	C15—C14—H14	120.0
N1—C7—C8	124.93 (16)	C16—C15—C14	120.26 (18)
C1—C7—C8	120.69 (14)	C16—C15—H15	119.9
C7—C8—H8A	109.5	C14—C15—H15	119.9
C7—C8—H8B	109.5	C17—C16—C15	119.67 (17)
H8A—C8—H8B	109.5	C17—C16—H16	120.2
C7—C8—H8C	109.5	C15—C16—H16	120.2
H8A—C8—H8C	109.5	C16—C17—C12	121.11 (16)
H8B—C8—H8C	109.5	C16—C17—H17	119.4
O1—C9—O2	112.27 (12)	C12—C17—H17	119.4

C9—O1—N1—C7	−176.97 (13)	N1—O1—C9—O2	−79.77 (15)
C9—O2—N2—C10	175.14 (11)	N2—O2—C9—O1	−78.02 (14)
C6—C1—C2—C3	−0.6 (2)	O2—N2—C10—C12	179.02 (10)
C7—C1—C2—C3	−179.71 (15)	O2—N2—C10—C11	−1.56 (19)
C1—C2—C3—C4	0.4 (3)	N2—C10—C12—C13	−32.7 (2)
C2—C3—C4—C5	−0.2 (3)	C11—C10—C12—C13	147.83 (15)
C3—C4—C5—C6	0.2 (3)	N2—C10—C12—C17	147.12 (15)
C4—C5—C6—C1	−0.4 (3)	C11—C10—C12—C17	−32.3 (2)
C2—C1—C6—C5	0.6 (2)	C17—C12—C13—C14	0.0 (2)
C7—C1—C6—C5	179.70 (16)	C10—C12—C13—C14	179.83 (14)
O1—N1—C7—C1	178.38 (12)	C12—C13—C14—C15	0.2 (2)
O1—N1—C7—C8	−1.2 (2)	C13—C14—C15—C16	−0.4 (2)
C6—C1—C7—N1	173.26 (15)	C14—C15—C16—C17	0.4 (2)
C2—C1—C7—N1	−7.7 (2)	C15—C16—C17—C12	−0.2 (2)
C6—C1—C7—C8	−7.1 (2)	C13—C12—C17—C16	0.0 (2)
C2—C1—C7—C8	171.95 (15)	C10—C12—C17—C16	−179.87 (14)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₈N₂O₂
M_r	282.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	9.875 (2), 8.8409 (18), 17.290 (4)
β (°)	101.13 (3)
V (Å³)	1481.1 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.14 × 0.04 × 0.04

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.988, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	9665, 2612, 1724
R_int	0.105
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.097, 0.96
No. of reflections	2612
No. of parameters	193
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.19

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank Tianjin Natural Science Foundation (grant No. 07JCYBJC02200) for financial support.

References

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