Crystal structure of 3-(4-chloro-phen-oxy)-4-(2-nitro-phen-yl)azetidin-2-one with an unknown solvate.

In the title compound, C15H11ClN2O4, the central β-lactam ring is approximately planar [maximum deviation = 0.044 (2) Å for the N atom from the mean plane] and subtends dihedral angles of 61.17 (11) and 40.21 (12) °, respectively, with the nitro and chloro-benzene rings. Both substituents lie to the same side of the β-lactam core. In the crystal, N-H⋯O hydrogen bonds link the mol-ecules into C(4) chains propagating in [010]. The chains are cross-linked by C-H⋯O and weak C-H⋯π inter-actions, generating a three-dimensional network. The solvent mol-ecules were found to be highly disordered and their contribution to the scattering was removed with the SQUEEZE procedure in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155], which indicated a solvent cavity of volume 318 Å(3) containing approximately 114 electrons. These solvent mol-ecules are not considered in the given chemical formula and other crystal data.

Related literature

For the application of N-unsubstituted 2-azetidinones in the synthesis of β-lactam anti­biotics, see: Cossio et al. (1987 ▸); Jarrahpour & Zarei (2007 ▸, 2008 ▸). For a related structure with a β-lactam ring, see: Butcher et al. (2011 ▸).

Experimental

Crystal data

C15H11ClN2O4

M = 318.71

Monoclinic,

a = 16.9505 (4) Å

b = 4.6517 (1) Å

c = 21.7167 (6) Å

β = 99.757 (1)°

V = 1687.56 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 296 K

0.30 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

16293 measured reflections

4358 independent reflections

3158 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.135

S = 1.04

4358 reflections

199 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014025845/hb7322sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025845/hb7322Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014025845/hb7322Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989014025845/hb7322fig1.tif

View of the title compound with displacement ellipsoids for non-H atoms drawn at the 30% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989014025845/hb7322fig2.tif

View of the hydrogen bonding of the title compound along b axis. Only H atoms involved in H bonding are shown.

CCDC reference: 1036035

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H11ClN2O4	F(000) = 656
Mr = 318.71	Dx = 1.254 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6230 reflections
a = 16.9505 (4) Å	θ = 2.4–28.7°
b = 4.6517 (1) Å	µ = 0.24 mm−1
c = 21.7167 (6) Å	T = 296 K
β = 99.757 (1)°	Prism, colourless
V = 1687.56 (7) Å3	0.30 × 0.20 × 0.15 mm
Z = 4

Bruker APEXII CCD diffractometer	3158 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.022
Graphite monochromator	θmax = 28.8°, θmin = 1.7°
φ and ω scans	h = −21→22
16293 measured reflections	k = −6→6
4358 independent reflections	l = −28→29

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049	H-atom parameters constrained
wR(F2) = 0.135	w = 1/[σ2(Fo2) + (0.0607P)2 + 0.3362P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
4358 reflections	Δρmax = 0.35 e Å−3
199 parameters	Δρmin = −0.23 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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.

	x	y	z	Uiso*/Ueq
Cl1	0.77735 (3)	0.02466 (16)	0.86934 (3)	0.0896 (2)
O1	0.34325 (8)	0.4694 (3)	0.80529 (6)	0.0684 (5)
O2	0.49880 (7)	0.6846 (3)	0.60857 (6)	0.0615 (5)
O3	0.53550 (8)	0.3225 (3)	0.55969 (6)	0.0686 (5)
O4	0.46717 (6)	0.2832 (2)	0.71337 (5)	0.0437 (3)
N1	0.30955 (8)	0.6612 (4)	0.70465 (6)	0.0523 (5)
N2	0.48444 (8)	0.4599 (3)	0.58069 (6)	0.0440 (4)
C1	0.35588 (9)	0.5438 (4)	0.75408 (7)	0.0462 (5)
C2	0.42874 (8)	0.5444 (3)	0.72098 (7)	0.0374 (4)
C3	0.36874 (9)	0.6469 (4)	0.66256 (7)	0.0399 (5)
C4	0.34857 (9)	0.4352 (3)	0.60981 (7)	0.0377 (4)
C5	0.27331 (10)	0.3099 (4)	0.59775 (8)	0.0503 (5)
C6	0.25251 (11)	0.1159 (5)	0.54958 (9)	0.0632 (7)
C7	0.30631 (13)	0.0396 (4)	0.51201 (9)	0.0625 (7)
C8	0.38224 (11)	0.1547 (4)	0.52289 (7)	0.0509 (6)
C9	0.40248 (9)	0.3484 (3)	0.57097 (7)	0.0387 (5)
C10	0.54003 (8)	0.2358 (3)	0.75211 (7)	0.0387 (4)
C11	0.55796 (12)	0.3387 (5)	0.81220 (8)	0.0661 (7)
C12	0.63188 (13)	0.2760 (6)	0.84797 (8)	0.0733 (8)
C13	0.68458 (10)	0.1055 (5)	0.82418 (8)	0.0559 (6)
C14	0.66690 (10)	0.0022 (4)	0.76469 (9)	0.0555 (6)
C15	0.59401 (9)	0.0697 (4)	0.72819 (8)	0.0470 (5)
H1	0.26120	0.72420	0.69920	0.0630*
H2	0.46700	0.69550	0.73710	0.0450*
H3	0.38230	0.83720	0.64800	0.0480*
H5	0.23580	0.35770	0.62280	0.0600*
H6	0.20140	0.03640	0.54260	0.0760*
H7	0.29160	−0.08920	0.47930	0.0750*
H8	0.41950	0.10220	0.49800	0.0610*
H11	0.52090	0.44930	0.82870	0.0790*
H12	0.64530	0.35050	0.88810	0.0880*
H14	0.70350	−0.11280	0.74870	0.0670*
H15	0.58190	0.00190	0.68740	0.0560*

	U11	U22	U33	U12	U13	U23
Cl1	0.0624 (3)	0.1234 (6)	0.0723 (3)	0.0190 (3)	−0.0193 (3)	0.0066 (3)
O1	0.0550 (7)	0.1050 (12)	0.0494 (7)	−0.0149 (7)	0.0209 (6)	0.0013 (7)
O2	0.0577 (7)	0.0584 (9)	0.0733 (8)	−0.0162 (6)	0.0251 (6)	−0.0204 (7)
O3	0.0539 (7)	0.0755 (10)	0.0824 (9)	0.0055 (7)	0.0291 (7)	−0.0164 (8)
O4	0.0356 (5)	0.0379 (7)	0.0547 (6)	0.0017 (5)	−0.0002 (4)	−0.0061 (5)
N1	0.0371 (7)	0.0678 (11)	0.0547 (8)	0.0115 (7)	0.0153 (6)	−0.0048 (7)
N2	0.0467 (7)	0.0474 (9)	0.0407 (6)	−0.0008 (6)	0.0152 (5)	0.0008 (6)
C1	0.0378 (8)	0.0556 (11)	0.0471 (8)	−0.0065 (7)	0.0130 (6)	−0.0086 (8)
C2	0.0338 (7)	0.0349 (9)	0.0448 (7)	−0.0034 (6)	0.0107 (6)	−0.0054 (6)
C3	0.0388 (7)	0.0364 (9)	0.0468 (8)	0.0046 (6)	0.0139 (6)	0.0006 (7)
C4	0.0385 (7)	0.0336 (8)	0.0408 (7)	0.0029 (6)	0.0058 (6)	0.0060 (6)
C5	0.0383 (8)	0.0536 (11)	0.0582 (9)	0.0017 (7)	0.0057 (7)	0.0038 (8)
C6	0.0496 (10)	0.0607 (13)	0.0722 (12)	−0.0118 (9)	−0.0102 (9)	0.0016 (10)
C7	0.0732 (13)	0.0551 (12)	0.0522 (9)	−0.0058 (10)	−0.0093 (9)	−0.0082 (9)
C8	0.0623 (10)	0.0483 (11)	0.0408 (8)	0.0036 (9)	0.0051 (7)	−0.0030 (7)
C9	0.0431 (8)	0.0354 (9)	0.0375 (7)	0.0016 (7)	0.0065 (6)	0.0032 (6)
C10	0.0348 (7)	0.0390 (9)	0.0424 (7)	−0.0039 (6)	0.0069 (6)	0.0008 (6)
C11	0.0613 (11)	0.0918 (17)	0.0446 (9)	0.0206 (11)	0.0075 (8)	−0.0113 (10)
C12	0.0692 (12)	0.1051 (19)	0.0405 (9)	0.0120 (12)	−0.0056 (8)	−0.0085 (10)
C13	0.0451 (9)	0.0680 (13)	0.0511 (9)	0.0025 (9)	−0.0021 (7)	0.0074 (9)
C14	0.0402 (8)	0.0628 (13)	0.0621 (10)	0.0075 (8)	0.0050 (7)	−0.0067 (9)
C15	0.0396 (8)	0.0516 (11)	0.0481 (8)	−0.0014 (7)	0.0030 (6)	−0.0101 (8)

Cl1—C13	1.7474 (18)	C8—C9	1.378 (2)
O1—C1	1.218 (2)	C10—C15	1.366 (2)
O2—N2	1.2118 (19)	C10—C11	1.375 (2)
O3—N2	1.2245 (19)	C11—C12	1.389 (3)
O4—C2	1.4016 (17)	C12—C13	1.360 (3)
O4—C10	1.3891 (18)	C13—C14	1.363 (3)
N1—C1	1.335 (2)	C14—C15	1.386 (2)
N1—C3	1.469 (2)	C2—H2	0.9800
N2—C9	1.464 (2)	C3—H3	0.9800
C1—C2	1.531 (2)	C5—H5	0.9300
N1—H1	0.8600	C6—H6	0.9300
C2—C3	1.560 (2)	C7—H7	0.9300
C3—C4	1.505 (2)	C8—H8	0.9300
C4—C5	1.387 (2)	C11—H11	0.9300
C4—C9	1.404 (2)	C12—H12	0.9300
C5—C6	1.381 (3)	C14—H14	0.9300
C6—C7	1.370 (3)	C15—H15	0.9300
C7—C8	1.377 (3)
C2—O4—C10	116.71 (11)	C10—C11—C12	119.42 (18)
C1—N1—C3	96.38 (13)	C11—C12—C13	119.89 (18)
O2—N2—O3	122.79 (14)	Cl1—C13—C14	119.24 (15)
O2—N2—C9	118.87 (13)	Cl1—C13—C12	119.92 (14)
O3—N2—C9	118.34 (13)	C12—C13—C14	120.82 (17)
O1—C1—N1	132.86 (15)	C13—C14—C15	119.57 (17)
O1—C1—C2	135.24 (15)	C10—C15—C14	120.02 (16)
N1—C1—C2	91.90 (12)	O4—C2—H2	112.00
C1—N1—H1	132.00	C1—C2—H2	112.00
C3—N1—H1	132.00	C3—C2—H2	112.00
O4—C2—C1	118.81 (12)	N1—C3—H3	112.00
O4—C2—C3	114.90 (12)	C2—C3—H3	112.00
C1—C2—C3	85.17 (11)	C4—C3—H3	112.00
N1—C3—C2	85.85 (11)	C4—C5—H5	119.00
C2—C3—C4	116.85 (14)	C6—C5—H5	119.00
N1—C3—C4	114.34 (14)	C5—C6—H6	120.00
C3—C4—C9	123.94 (14)	C7—C6—H6	120.00
C3—C4—C5	120.12 (14)	C6—C7—H7	120.00
C5—C4—C9	115.94 (14)	C8—C7—H7	120.00
C4—C5—C6	121.75 (16)	C7—C8—H8	120.00
C5—C6—C7	120.68 (18)	C9—C8—H8	120.00
C6—C7—C8	119.63 (18)	C10—C11—H11	120.00
C7—C8—C9	119.33 (16)	C12—C11—H11	120.00
N2—C9—C8	116.69 (14)	C11—C12—H12	120.00
C4—C9—C8	122.66 (15)	C13—C12—H12	120.00
N2—C9—C4	120.65 (13)	C13—C14—H14	120.00
C11—C10—C15	120.23 (15)	C15—C14—H14	120.00
O4—C10—C11	123.40 (14)	C10—C15—H15	120.00
O4—C10—C15	116.34 (13)	C14—C15—H15	120.00
C10—O4—C2—C3	156.31 (12)	C2—C3—C4—C9	−70.06 (19)
C2—O4—C10—C11	32.5 (2)	C3—C4—C9—N2	1.0 (2)
C2—O4—C10—C15	−149.62 (14)	C3—C4—C9—C8	−179.81 (15)
C10—O4—C2—C1	−105.11 (15)	C3—C4—C5—C6	179.68 (17)
C3—N1—C1—C2	6.71 (14)	C9—C4—C5—C6	−1.2 (2)
C3—N1—C1—O1	−173.8 (2)	C5—C4—C9—N2	−178.08 (14)
C1—N1—C3—C2	−6.60 (14)	C5—C4—C9—C8	1.1 (2)
C1—N1—C3—C4	111.06 (16)	C4—C5—C6—C7	0.3 (3)
O3—N2—C9—C4	158.62 (14)	C5—C6—C7—C8	0.8 (3)
O2—N2—C9—C8	158.71 (15)	C6—C7—C8—C9	−0.9 (3)
O3—N2—C9—C8	−20.7 (2)	C7—C8—C9—C4	−0.1 (2)
O2—N2—C9—C4	−22.0 (2)	C7—C8—C9—N2	179.17 (15)
N1—C1—C2—C3	−6.30 (14)	O4—C10—C11—C12	178.78 (18)
N1—C1—C2—O4	−122.13 (15)	C15—C10—C11—C12	1.0 (3)
O1—C1—C2—O4	58.4 (3)	O4—C10—C15—C14	−177.37 (15)
O1—C1—C2—C3	174.2 (2)	C11—C10—C15—C14	0.6 (3)
O4—C2—C3—N1	125.34 (13)	C10—C11—C12—C13	−2.4 (3)
C1—C2—C3—N1	5.73 (12)	C11—C12—C13—Cl1	−179.60 (18)
C1—C2—C3—C4	−109.51 (14)	C11—C12—C13—C14	2.2 (4)
O4—C2—C3—C4	10.09 (19)	Cl1—C13—C14—C15	−178.84 (15)
N1—C3—C4—C9	−168.11 (14)	C12—C13—C14—C15	−0.6 (3)
C2—C3—C4—C5	108.95 (17)	C13—C14—C15—C10	−0.8 (3)
N1—C3—C4—C5	10.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86	2.09	2.936 (2)	166
C8—H8···O3ii	0.93	2.53	3.307 (2)	142
C15—H15···O2iii	0.93	2.51	3.338 (2)	149
C3—H3···Cg2iv	0.98	2.70	3.5118 (19)	141

Table 1

Hydrogen-bond geometry (, )

Cg2 is the centroid of the nitrobenzene ring (C4C9).

DHA	DH	HA	D A	DHA
N1H1O1i	0.86	2.09	2.936(2)	166
C8H8O3ii	0.93	2.53	3.307(2)	142
C15H15O2iii	0.93	2.51	3.338(2)	149
C3H3Cg2iv	0.98	2.70	3.5118(19)	141

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .