1-Methyl-1-phenyl-3-[1-hydroxy­imino-2-(succinimido)­ethyl]­cyclo­butane

In the title compound, C₁₇H₂₀N₂O₃, the cyclo­butane ring is puckered, with a dihedral angle of 19.11 (15)°. The 1-phenyl and 3-[1-hydroxy­imino-2-(succinimido)­ethyl] groups are in cis positions. The mol­ecules are linked by O-H...O and C-H...[pi](benzene) interactions, forming a two-dimensional network.

S1. Comment

3-Substituted cyclobutane carboxylic acid derivatives exhibit antiinflammatory and antidepressant activities (Dehmlow & Schmidt, 1990), and also liquid crystal properties (Coghi et al., 1976). Oximes show geometric isomerism, due to the double bond between the N and C atoms (Mixich & Thiele, 1979; Migrdichian, 1957). Because of the significant differences in the physical, chemical and biological properties of the geometric isomers, determination of the configuration of these isomers is important (Mathison et al., 1989). Oximes and oxime ethers also have a broad pharmacological activity spectrum, encompassing antifungal, antibacterial, antidepressant and insecticidal activities, as well as activity as a nerve-gas antidote, depending on the pharmacophoric group of the molecule (Polak, 1982; Balsamo et al., 1990; Holan et al., 1984; Forman, 1964). The oxime (C═N—OH) group possesses stronger hydrogen-bonding capabilities than alcohols, phenols and carboxylic acids (Marsman et al., 1999). Hydrogen bonding plays a key role in molecular recognition in chemical engineering (Bertolasi et al., 1982; Gilli et al., 1983; Hökelek et al., 2001). As part of our ongoing study of the relationship between the molecular and crystal structures of cyclobutane and oxime derivatives, a crystal structure determination of the title compound, (I), has been undertaken and the results are presented here. \sch

Previously, we have reported the closely related compound 2-[2-hydroxyimino-2-(3-methyl-3-phenylcyclobutyl)ethyl]isoindole-1,3-dione, (II) (Özdemir et al., 2004). The main aim of the present investigation is to study the types of differences which are present in the structure of (I) compared with (II), and to determine the strength of the hydrogen-bonding capabilities of the oxime group.

Fig. 1 shows the molecular structure and conformation of (I), with the atomic numbering scheme. The structure of (I) can be described as being built from planar fragments, viz. a cyclobutane ring (C1—C4), an oxime group (C10/N1/O1), a succinimide ring (O2/O3/N2/C5/C6/C7/C8), a phenyl ring (C12—C17), and a four-atom bridge (C3/C10/C9/N2) linking the cyclobutane and succinimide rings. The maximum deviation of the succinimide ring from planarity is 0.0413 (13) Å for atom C6. The C3—C10—C9—N2 torsion angle is 8.5 (2)°, corresponding to a (+)-synperiplanar configuration, and the plane of the four-atom bridge is almost perpendicular to the succinimide ring (Table 1). The plane of these four atoms makes a dihedral angle of 76.19 (8)° with the mean plane of the cyclobutane ring.

Although close to planar, the cyclobutane ring is more puckered than in (II). The C4/C1/C2 plane forms a dihedral angle of 19.26 (17)° with the C2/C3/C4 plane [11.55 (3)° in (II); Özdemir et al., 2004]. The mean plane of the cyclobutane ring forms a dihedral angle of 81.62 (6)° with the plane of the succinimide ring. The oxime moiety has an E configuration, with a C3—C10—N1—O1 torsion angle of 175.95 (14)°, which corresponds to a (+)-antiperiplanar configuration. In this configuration, atom O1 acts as hydrogen-bond donor to atom O2 of the succimido group at (1 − x, 1/2 + y, 1/2 − z). The O···O distance is 2.7594 (16) Å, which is a little shorter than that in (II) [2.814 (3) Å]. In (I), the plane of the oxime moiety is twisted by 74.95 (13)° out of the mean plane of the cyclobutane ring, and it is almost coplanar with the four-atom bridge, with a dihedral angle of 3.2 (2)°. The bond lengths and angles of the oxime moiety in (I) are close to those in (II).

There are two weak intramolecular C—H···N interactions in (I) (Fig. 1). Each of these interactions forms a five-membered ring. As a point of difference from (II), two intermolecular C—H···π(phenyl) interactions are also observed (Fig. 2 and Table 2). The centroid (Cg3) of the C12—C17 ring acts as a single acceptor for both these C—H···π interactions. A two-dimensional network is formed by these O—H···O and C—H···π(phenyl) interactions. There are no intermolecular π–π interactions in the crystal of (I).

S2. Experimental

A mixture of 1-phenyl-1-methyl-3-(2-succinimido-1-oxoethyl)cyclobutane (2.853 g, 0.01 mol), synthesized according to the literature method of Ahmedzade et al. (2003), hydroxylamine hydrochloride (0.695 g, 0.01 mol) and pyridine (5 ml) in ethanol (100 ml) was refluxed for 3 h. The solvent was removed by distillation, and the resulting solid was filtered off, washed with cold water, dried and recrystallized from ethanol to obtain the title compound (yield 2.8 g, 85%; m.p. 426 K). Elemental analysis calculated for C₁₇H₂₀N₂O₃: C 67.98, H 6.71, N 9.33%; found: C 68.02, H 6.84, N 9.45%. IR spectroscopy (KBr pellet, ν, cm⁻¹): 1620 (C═N), 3253 (–OH oxime). ¹H NMR (CDCl₃, δ, p.p.m.): 7.10–7.30 (m, 5H, aromatics), 4.4 (s, 2H, CH₂ cyclobutane), 3.5 (quint, 1H, J = 8.9 Hz, CH cyclobutane), 1.74–2.75 (m, 8H, CH₂ cyclobutane plus succinimide), 1.49 (s, 3H, CH₃).

S3. Refinement

The oxime H atom was located from a difference density map and the other H atoms were positioned geometrically. All H atoms were treated using a riding model, with an O—H distance of 0.82 Å and C—H distances of 0.93–0.98 Å, and with U_iso(H) = 1.2U_eq (1.5U_eq for methyl) of the parent atom. The maximum difference density (0.73 e Å⁻³) is located 0.70 Å from atom C3, and the minimum difference density (−0.74 e Å⁻³) is 0.59 Å from atom C11.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate the C—H···N interactions.
	Fig. 2. A projection of the crystal structure of (I) along the b axis. Dashed lines show the O—H···O and C—H···π interactions.

1-Methyl-1-phenyl-3-[1-hydroxyimino-2-(succinimido)ethyl]cyclobutane

Crystal data

C17H20N2O3	F(000) = 640
Mr = 300.35	Dx = 1.281 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12629 reflections
a = 8.8356 (7) Å	θ = 1.3–26.1°
b = 5.7520 (5) Å	µ = 0.09 mm^−1
c = 30.803 (2) Å	T = 250 K
β = 95.821 (6)°	Prism, colourless
V = 1557.4 (2) Å^3	0.63 × 0.53 × 0.35 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer	2179 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.062
Plane graphite monochromator	θmax = 25.0°, θmin = 2.3°
Detector resolution: 6.67 pixels mm^-1	h = −10→10
w scans	k = −6→6
11598 measured reflections	l = −34→36
2694 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + (0.112P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2694 reflections	Δρmax = 0.73 e Å^−3
200 parameters	Δρmin = −0.74 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.027 (6)

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
O1	0.57548 (13)	1.1129 (2)	0.23301 (5)	0.0624 (4)
H1	0.6667	1.1301	0.2402	0.094*
O2	0.11958 (13)	0.6729 (2)	0.24004 (5)	0.0624 (4)
O3	0.09359 (17)	1.2749 (3)	0.14455 (5)	0.0717 (4)
N1	0.55473 (14)	0.9532 (3)	0.19850 (5)	0.0489 (4)
N2	0.13975 (13)	0.9843 (2)	0.19487 (4)	0.0385 (3)
C1	0.47200 (17)	0.6567 (3)	0.08929 (5)	0.0390 (4)
C2	0.48672 (18)	0.5782 (3)	0.13774 (6)	0.0434 (4)
H2A	0.4502	0.4215	0.1419	0.052*
H2B	0.5879	0.5992	0.1526	0.052*
C3	0.37278 (16)	0.7693 (3)	0.14827 (5)	0.0418 (4)
H3	0.2701	0.7055	0.1487	0.050*
C4	0.39321 (19)	0.8815 (3)	0.10328 (6)	0.0473 (4)
H4A	0.2979	0.9151	0.0859	0.057*
H4B	0.4592	1.0167	0.1052	0.057*
C5	0.06559 (16)	0.7988 (3)	0.21082 (6)	0.0422 (4)
C6	−0.08827 (17)	0.7771 (3)	0.18585 (6)	0.0481 (4)
H6A	−0.1675	0.7790	0.2055	0.058*
H6B	−0.0960	0.6339	0.1692	0.058*
C7	−0.10169 (19)	0.9863 (3)	0.15585 (6)	0.0511 (5)
H7A	−0.1241	0.9382	0.1257	0.061*
H7B	−0.1817	1.0896	0.1634	0.061*
C8	0.05026 (18)	1.1044 (3)	0.16255 (6)	0.0449 (4)
C9	0.29534 (16)	1.0509 (3)	0.20969 (6)	0.0420 (4)
H9A	0.3137	1.0219	0.2408	0.050*
H9B	0.3069	1.2165	0.2051	0.050*
C10	0.41363 (16)	0.9229 (3)	0.18684 (5)	0.0386 (4)
C11	0.3634 (2)	0.5056 (3)	0.05978 (7)	0.0538 (5)
H11A	0.2699	0.4864	0.0727	0.081*
H11B	0.4089	0.3561	0.0562	0.081*
H11C	0.3431	0.5790	0.0318	0.081*
C12	0.62057 (17)	0.6868 (3)	0.06964 (5)	0.0388 (4)
C13	0.6486 (2)	0.8772 (3)	0.04414 (6)	0.0498 (4)
H13	0.5745	0.9915	0.0389	0.060*
C14	0.7856 (2)	0.8995 (4)	0.02626 (7)	0.0645 (6)
H14	0.8022	1.0276	0.0089	0.077*
C15	0.8970 (2)	0.7336 (4)	0.03394 (7)	0.0679 (6)
H15	0.9893	0.7502	0.0222	0.081*
C16	0.8716 (2)	0.5443 (4)	0.05893 (7)	0.0617 (5)
H16	0.9466	0.4313	0.0641	0.074*
C17	0.7339 (2)	0.5200 (3)	0.07668 (6)	0.0488 (4)
H17	0.7175	0.3899	0.0935	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0343 (6)	0.0811 (9)	0.0709 (9)	−0.0085 (6)	0.0010 (6)	−0.0336 (7)
O2	0.0361 (6)	0.0784 (9)	0.0716 (9)	0.0017 (6)	0.0009 (6)	0.0308 (7)
O3	0.0647 (9)	0.0677 (9)	0.0820 (11)	−0.0027 (7)	0.0041 (7)	0.0286 (8)
N1	0.0312 (7)	0.0637 (9)	0.0522 (9)	−0.0050 (6)	0.0061 (6)	−0.0148 (7)
N2	0.0264 (6)	0.0478 (7)	0.0414 (8)	0.0027 (5)	0.0049 (5)	0.0001 (5)
C1	0.0387 (8)	0.0389 (7)	0.0396 (9)	0.0022 (6)	0.0050 (6)	−0.0034 (6)
C2	0.0463 (9)	0.0412 (8)	0.0439 (10)	0.0024 (6)	0.0105 (7)	0.0009 (6)
C3	0.0323 (7)	0.0489 (9)	0.0449 (9)	−0.0029 (6)	0.0077 (6)	−0.0080 (7)
C4	0.0493 (9)	0.0475 (9)	0.0448 (10)	0.0122 (7)	0.0024 (7)	−0.0031 (7)
C5	0.0291 (7)	0.0506 (9)	0.0477 (10)	0.0038 (6)	0.0070 (6)	0.0056 (7)
C6	0.0293 (7)	0.0545 (9)	0.0599 (11)	0.0001 (6)	0.0019 (7)	0.0007 (8)
C7	0.0353 (8)	0.0673 (11)	0.0492 (11)	0.0072 (7)	−0.0026 (7)	0.0031 (8)
C8	0.0405 (8)	0.0498 (9)	0.0447 (10)	0.0056 (7)	0.0062 (7)	0.0028 (7)
C9	0.0286 (8)	0.0493 (8)	0.0485 (10)	−0.0021 (6)	0.0054 (6)	−0.0089 (7)
C10	0.0291 (7)	0.0469 (8)	0.0408 (9)	−0.0031 (6)	0.0075 (6)	−0.0023 (6)
C11	0.0483 (10)	0.0572 (10)	0.0554 (12)	−0.0046 (8)	0.0037 (8)	−0.0111 (8)
C12	0.0417 (8)	0.0403 (8)	0.0345 (8)	−0.0013 (6)	0.0041 (6)	−0.0039 (6)
C13	0.0588 (10)	0.0470 (9)	0.0438 (10)	0.0004 (7)	0.0065 (7)	0.0031 (7)
C14	0.0750 (13)	0.0653 (12)	0.0562 (13)	−0.0174 (10)	0.0206 (10)	0.0047 (9)
C15	0.0510 (11)	0.0889 (15)	0.0677 (14)	−0.0137 (10)	0.0249 (9)	−0.0107 (11)
C16	0.0476 (10)	0.0747 (12)	0.0646 (13)	0.0091 (9)	0.0145 (9)	−0.0064 (10)
C17	0.0472 (9)	0.0503 (9)	0.0503 (11)	0.0064 (7)	0.0121 (7)	0.0020 (7)

Geometric parameters (Å, º)

O1—N1	1.4030 (18)	C6—H6A	0.9700
O1—H1	0.8200	C6—H6B	0.9700
O2—C5	1.214 (2)	C7—C8	1.500 (2)
O3—C8	1.208 (2)	C7—H7A	0.9700
N1—C10	1.274 (2)	C7—H7B	0.9700
N2—C5	1.369 (2)	C9—C10	1.510 (2)
N2—C8	1.391 (2)	C9—H9A	0.9700
N2—C9	1.4552 (18)	C9—H9B	0.9700
C1—C12	1.510 (2)	C11—H11A	0.9600
C1—C11	1.525 (2)	C11—H11B	0.9600
C1—C4	1.550 (2)	C11—H11C	0.9600
C1—C2	1.552 (2)	C12—C13	1.385 (2)
C2—C3	1.547 (2)	C12—C17	1.388 (2)
C2—H2A	0.9700	C13—C14	1.386 (3)
C2—H2B	0.9700	C13—H13	0.9300
C3—C10	1.495 (2)	C14—C15	1.375 (3)
C3—C4	1.556 (2)	C14—H14	0.9300
C3—H3	0.9800	C15—C16	1.365 (3)
C4—H4A	0.9700	C15—H15	0.9300
C4—H4B	0.9700	C16—C17	1.391 (3)
C5—C6	1.498 (2)	C16—H16	0.9300
C6—C7	1.514 (3)	C17—H17	0.9300
N1—O1—H1	109.5	C6—C7—H7A	110.7
C10—N1—O1	110.61 (13)	C8—C7—H7B	110.7
C5—N2—C8	112.71 (13)	C6—C7—H7B	110.7
C5—N2—C9	124.33 (13)	H7A—C7—H7B	108.8
C8—N2—C9	122.96 (13)	O3—C8—N2	123.25 (15)
C12—C1—C11	110.26 (14)	O3—C8—C7	128.73 (16)
C12—C1—C4	116.66 (13)	N2—C8—C7	108.02 (14)
C11—C1—C4	111.60 (13)	N2—C9—C10	113.71 (12)
C12—C1—C2	115.30 (12)	N2—C9—H9A	108.8
C11—C1—C2	113.17 (14)	C10—C9—H9A	108.8
C4—C1—C2	88.39 (12)	N2—C9—H9B	108.8
C3—C2—C1	90.11 (12)	C10—C9—H9B	108.8
C3—C2—H2A	113.6	H9A—C9—H9B	107.7
C1—C2—H2A	113.6	N1—C10—C3	117.08 (13)
C3—C2—H2B	113.6	N1—C10—C9	120.40 (14)
C1—C2—H2B	113.6	C3—C10—C9	122.40 (12)
H2A—C2—H2B	110.9	C1—C11—H11A	109.5
C10—C3—C2	118.48 (13)	C1—C11—H11B	109.5
C10—C3—C4	114.97 (13)	H11A—C11—H11B	109.5
C2—C3—C4	88.35 (12)	C1—C11—H11C	109.5
C10—C3—H3	111.1	H11A—C11—H11C	109.5
C2—C3—H3	111.1	H11B—C11—H11C	109.5
C4—C3—H3	111.1	C13—C12—C17	117.90 (15)
C1—C4—C3	89.85 (12)	C13—C12—C1	122.05 (14)
C1—C4—H4A	113.7	C17—C12—C1	120.05 (14)
C3—C4—H4A	113.7	C12—C13—C14	120.82 (17)
C1—C4—H4B	113.7	C12—C13—H13	119.6
C3—C4—H4B	113.7	C14—C13—H13	119.6
H4A—C4—H4B	110.9	C15—C14—C13	120.44 (18)
O2—C5—N2	124.36 (14)	C15—C14—H14	119.8
O2—C5—C6	126.78 (14)	C13—C14—H14	119.8
N2—C5—C6	108.85 (13)	C16—C15—C14	119.69 (17)
C5—C6—C7	104.96 (13)	C16—C15—H15	120.2
C5—C6—H6A	110.8	C14—C15—H15	120.2
C7—C6—H6A	110.8	C15—C16—C17	120.15 (19)
C5—C6—H6B	110.8	C15—C16—H16	119.9
C7—C6—H6B	110.8	C17—C16—H16	119.9
H6A—C6—H6B	108.8	C12—C17—C16	121.00 (17)
C8—C7—C6	105.20 (13)	C12—C17—H17	119.5
C8—C7—H7A	110.7	C16—C17—H17	119.5
C12—C1—C2—C3	132.62 (13)	C8—N2—C9—C10	−94.48 (18)
C11—C1—C2—C3	−99.14 (14)	O1—N1—C10—C3	175.95 (14)
C4—C1—C2—C3	13.72 (12)	O1—N1—C10—C9	−0.2 (2)
C1—C2—C3—C10	−131.38 (14)	C2—C3—C10—N1	26.6 (2)
C1—C2—C3—C4	−13.67 (12)	C4—C3—C10—N1	−75.92 (19)
C12—C1—C4—C3	−131.31 (13)	C2—C3—C10—C9	−157.32 (15)
C11—C1—C4—C3	100.70 (15)	C4—C3—C10—C9	100.17 (17)
C2—C1—C4—C3	−13.65 (12)	N2—C9—C10—N1	−175.52 (15)
C10—C3—C4—C1	134.54 (13)	N2—C9—C10—C3	8.5 (2)
C2—C3—C4—C1	13.69 (12)	C11—C1—C12—C13	94.81 (18)
C8—N2—C5—O2	−177.81 (16)	C4—C1—C12—C13	−33.8 (2)
C9—N2—C5—O2	2.3 (3)	C2—C1—C12—C13	−135.52 (16)
C8—N2—C5—C6	3.31 (19)	C11—C1—C12—C17	−84.77 (18)
C9—N2—C5—C6	−176.61 (14)	C4—C1—C12—C17	146.60 (15)
O2—C5—C6—C7	176.13 (17)	C2—C1—C12—C17	44.9 (2)
N2—C5—C6—C7	−5.03 (19)	C17—C12—C13—C14	0.0 (3)
C5—C6—C7—C8	4.77 (19)	C1—C12—C13—C14	−179.53 (17)
C5—N2—C8—O3	179.18 (17)	C12—C13—C14—C15	−0.7 (3)
C9—N2—C8—O3	−0.9 (3)	C13—C14—C15—C16	0.8 (3)
C5—N2—C8—C7	−0.10 (19)	C14—C15—C16—C17	−0.3 (3)
C9—N2—C8—C7	179.83 (14)	C13—C12—C17—C16	0.5 (3)
C6—C7—C8—O3	177.71 (19)	C1—C12—C17—C16	−179.95 (17)
C6—C7—C8—N2	−3.06 (19)	C15—C16—C17—C12	−0.4 (3)
C5—N2—C9—C10	85.44 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N2	0.98	2.50	2.9030 (19)	104
C2—H2B···N1	0.97	2.51	2.879 (2)	102
O1—H1···O2^i	0.82	1.94	2.7594 (16)	177
C7—H7A···Cg3^ii	0.97	2.74	3.68	163
C11—H11C···Cg3^iii	0.96	3.12	3.71	121

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