4-Methyl-5-(4-nitro-benzyl-idene)-2-oxo-2,5-di-hydro-1H-pyrrole-3-carbo-nitrile.

Mol-ecules of the potential non-linear optical title compound, C13H9N3O3, form dimeric stacks of mol-ecules along the a axis cross-linked around inversion centers by N-H⋯O hydrogen bonds and weak (phen-yl)C-H⋯O inter-molecular inter-actions, forming a 'collaboration' of R 2 (2)(8) and R 2 (2)(16) ring motifs. The mol-ecules are then further linked by weak C-H⋯O and C-H⋯N inter-actions into sheets parallel to (121).

Related literature

For hydrogen-bonding motifs, see: Bernstein et al. (1995 ▶). For chemical synthesis literature, see: Shrestha-Dawadi & Lugtenburg (2007 ▶). For background literature, see: Bert et al. (2006 ▶); Colin et al. (2002 ▶); Hasan et al. (2012 ▶); Stephen et al. (2011 ▶); Tarek et al. (2013 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C13H9N3O3

M = 255.23

Monoclinic,

a = 3.7456 (2) Å

b = 14.9193 (9) Å

c = 21.6077 (17) Å

β = 92.273 (7)°

V = 1206.52 (14) Å3

Z = 4

Cu Kα radiation

μ = 0.86 mm−1

T = 120 K

0.44 × 0.05 × 0.03 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.633, T max = 1.000

7096 measured reflections

2283 independent reflections

1941 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.139

S = 1.05

2283 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.25 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813017066/jj2169sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813017066/jj2169Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813017066/jj2169Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H9N3O3	Z = 4
Mr = 255.23	F(000) = 528
Monoclinic, P21/c	Dx = 1.405 Mg m−3
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54184 Å
a = 3.7456 (2) Å	µ = 0.86 mm−1
b = 14.9193 (9) Å	T = 120 K
c = 21.6077 (17) Å	Needle, yellow
β = 92.273 (7)°	0.44 × 0.05 × 0.03 mm
V = 1206.52 (14) Å3

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2283 independent reflections
Radiation source: fine-focus sealed tube	1941 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 10.6501 pixels mm-1	θmax = 70.0°, θmin = 3.6°
ω scans	h = −4→4
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −17→18
Tmin = 0.633, Tmax = 1.000	l = −26→18
7096 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0824P)2 + 0.3085P] where P = (Fo2 + 2Fc2)/3
2283 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. (MNa)+ m/z 278.0540; C13H9N3O3 requires (MNa)+ m/z 278.0542). 1H NMR (500 MHz, d6-DMSO) 2.46 (s, 3H, CH3), 6.84 (s, 1H, CH), 7.88 (d, 2H, J = 4.9 Hz, ArH), 8.25 (d, 2H, J = 4.9 Hz, ArH), 10.91 (s, 1H, NH). 13C NMR (75 MHz, d6 –DMSO) 12.3, 105.9, 112.7, 113.4, 123.9, 130.9, 138.2, 139.9, 146.7, 161.7, 166.9.

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.

	x	y	z	Uiso*/Ueq
O1	0.8538 (3)	0.44087 (8)	0.56486 (6)	0.0277 (3)
O2	0.9729 (4)	0.64031 (9)	0.18759 (7)	0.0452 (4)
O3	1.1572 (4)	0.52825 (10)	0.13455 (7)	0.0453 (4)
N1	0.7576 (4)	0.40243 (9)	0.46186 (7)	0.0243 (3)
H1	0.8491	0.4502	0.4446	0.029*
N2	0.3889 (4)	0.24706 (12)	0.63898 (9)	0.0403 (4)
N3	1.0168 (4)	0.55927 (10)	0.17993 (8)	0.0323 (4)
C1	0.7387 (4)	0.39026 (11)	0.52376 (8)	0.0236 (4)
C2	0.5581 (4)	0.30283 (11)	0.53143 (9)	0.0253 (4)
C3	0.4940 (4)	0.26523 (11)	0.47533 (8)	0.0252 (4)
C4	0.6126 (4)	0.32905 (11)	0.42854 (8)	0.0246 (4)
C5	0.4693 (5)	0.27012 (11)	0.59072 (9)	0.0283 (4)
C6	0.3332 (5)	0.17567 (11)	0.46080 (9)	0.0296 (4)
H6A	0.1407	0.1825	0.4291	0.044*
H6B	0.2362	0.1501	0.4984	0.044*
H6C	0.5171	0.1356	0.4454	0.044*
C7	0.5892 (4)	0.31806 (11)	0.36711 (8)	0.0264 (4)
H7	0.4945	0.2624	0.3527	0.032*
C8	0.6925 (4)	0.38178 (11)	0.31925 (8)	0.0256 (4)
C9	0.6636 (4)	0.47494 (11)	0.32720 (9)	0.0268 (4)
H9	0.5724	0.4981	0.3644	0.032*
C10	0.7663 (5)	0.53323 (11)	0.28161 (9)	0.0283 (4)
H10	0.7463	0.5962	0.2869	0.034*
C11	0.8990 (4)	0.49794 (12)	0.22809 (8)	0.0276 (4)
C12	0.9235 (5)	0.40627 (12)	0.21750 (9)	0.0287 (4)
H12	1.0116	0.3838	0.1799	0.034*
C13	0.8157 (5)	0.34892 (12)	0.26339 (8)	0.0285 (4)
H13	0.8255	0.2860	0.2569	0.034*

	U11	U22	U33	U12	U13	U23
O1	0.0363 (6)	0.0202 (6)	0.0267 (7)	−0.0029 (5)	0.0031 (5)	−0.0007 (5)
O2	0.0724 (10)	0.0219 (7)	0.0415 (9)	−0.0063 (6)	0.0049 (7)	0.0049 (6)
O3	0.0579 (9)	0.0402 (8)	0.0392 (9)	0.0065 (7)	0.0202 (7)	0.0088 (7)
N1	0.0314 (7)	0.0158 (7)	0.0258 (8)	−0.0023 (5)	0.0032 (6)	0.0007 (6)
N2	0.0449 (9)	0.0378 (9)	0.0387 (11)	−0.0049 (7)	0.0067 (8)	0.0095 (8)
N3	0.0379 (8)	0.0273 (8)	0.0315 (9)	−0.0017 (6)	0.0015 (7)	0.0049 (7)
C1	0.0264 (7)	0.0178 (8)	0.0268 (9)	0.0020 (6)	0.0036 (6)	0.0007 (7)
C2	0.0278 (8)	0.0184 (8)	0.0300 (10)	0.0014 (6)	0.0054 (7)	0.0025 (7)
C3	0.0268 (8)	0.0179 (8)	0.0313 (10)	0.0005 (6)	0.0048 (7)	0.0010 (7)
C4	0.0283 (8)	0.0168 (8)	0.0289 (9)	0.0012 (6)	0.0045 (7)	0.0001 (7)
C5	0.0311 (8)	0.0196 (8)	0.0342 (11)	−0.0010 (6)	0.0023 (7)	0.0024 (7)
C6	0.0348 (8)	0.0188 (8)	0.0356 (10)	−0.0040 (7)	0.0060 (7)	−0.0009 (7)
C7	0.0296 (8)	0.0179 (8)	0.0320 (10)	−0.0005 (6)	0.0041 (7)	−0.0014 (7)
C8	0.0256 (7)	0.0230 (8)	0.0280 (10)	−0.0008 (6)	0.0003 (7)	−0.0004 (7)
C9	0.0285 (8)	0.0231 (9)	0.0290 (10)	0.0015 (6)	0.0038 (7)	−0.0033 (7)
C10	0.0332 (8)	0.0197 (8)	0.0318 (10)	0.0006 (7)	0.0000 (7)	−0.0001 (7)
C11	0.0289 (8)	0.0253 (9)	0.0285 (10)	−0.0012 (7)	0.0014 (7)	0.0035 (8)
C12	0.0336 (8)	0.0256 (9)	0.0272 (10)	0.0031 (7)	0.0043 (7)	−0.0007 (7)
C13	0.0365 (9)	0.0206 (8)	0.0287 (10)	0.0018 (7)	0.0027 (7)	−0.0019 (7)

O1—C1	1.231 (2)	C6—H6B	0.9800
O2—N3	1.232 (2)	C6—H6C	0.9800
O3—N3	1.222 (2)	C7—C8	1.468 (2)
N1—C1	1.354 (2)	C7—H7	0.9500
N1—C4	1.407 (2)	C8—C13	1.398 (2)
N1—H1	0.8800	C8—C9	1.405 (2)
N2—C5	1.149 (3)	C9—C10	1.380 (2)
N3—C11	1.467 (2)	C9—H9	0.9500
C1—C2	1.482 (2)	C10—C11	1.381 (3)
C2—C3	1.349 (3)	C10—H10	0.9500
C2—C5	1.423 (3)	C11—C12	1.390 (2)
C3—C4	1.470 (2)	C12—C13	1.382 (3)
C3—C6	1.494 (2)	C12—H12	0.9500
C4—C7	1.337 (3)	C13—H13	0.9500
C6—H6A	0.9800
C1—N1—C4	111.50 (14)	H6A—C6—H6C	109.5
C1—N1—H1	124.3	H6B—C6—H6C	109.5
C4—N1—H1	124.3	C4—C7—C8	127.68 (16)
O3—N3—O2	122.93 (16)	C4—C7—H7	116.2
O3—N3—C11	118.96 (15)	C8—C7—H7	116.2
O2—N3—C11	118.11 (16)	C13—C8—C9	118.82 (16)
O1—C1—N1	126.85 (15)	C13—C8—C7	119.10 (15)
O1—C1—C2	127.44 (16)	C9—C8—C7	122.06 (16)
N1—C1—C2	105.70 (15)	C10—C9—C8	120.73 (16)
C3—C2—C5	128.83 (16)	C10—C9—H9	119.6
C3—C2—C1	109.36 (15)	C8—C9—H9	119.6
C5—C2—C1	121.80 (16)	C9—C10—C11	118.51 (16)
C2—C3—C4	107.50 (15)	C9—C10—H10	120.7
C2—C3—C6	128.09 (16)	C11—C10—H10	120.7
C4—C3—C6	124.41 (16)	C10—C11—C12	122.76 (16)
C7—C4—N1	127.73 (15)	C10—C11—N3	118.99 (16)
C7—C4—C3	126.41 (16)	C12—C11—N3	118.24 (16)
N1—C4—C3	105.85 (15)	C13—C12—C11	117.89 (16)
N2—C5—C2	176.98 (19)	C13—C12—H12	121.1
C3—C6—H6A	109.5	C11—C12—H12	121.1
C3—C6—H6B	109.5	C12—C13—C8	121.21 (16)
H6A—C6—H6B	109.5	C12—C13—H13	119.4
C3—C6—H6C	109.5	C8—C13—H13	119.4
C4—N1—C1—O1	177.31 (15)	C3—C4—C7—C8	177.49 (16)
C4—N1—C1—C2	−1.53 (17)	C4—C7—C8—C13	148.90 (18)
O1—C1—C2—C3	−175.91 (16)	C4—C7—C8—C9	−32.6 (3)
N1—C1—C2—C3	2.92 (18)	C13—C8—C9—C10	−2.2 (3)
O1—C1—C2—C5	5.4 (3)	C7—C8—C9—C10	179.34 (16)
N1—C1—C2—C5	−175.75 (15)	C8—C9—C10—C11	−0.2 (3)
C5—C2—C3—C4	175.48 (16)	C9—C10—C11—C12	1.9 (3)
C1—C2—C3—C4	−3.06 (18)	C9—C10—C11—N3	−178.58 (16)
C5—C2—C3—C6	−4.5 (3)	O3—N3—C11—C10	174.92 (17)
C1—C2—C3—C6	176.91 (15)	O2—N3—C11—C10	−4.3 (3)
C1—N1—C4—C7	−179.52 (16)	O3—N3—C11—C12	−5.6 (3)
C1—N1—C4—C3	−0.25 (18)	O2—N3—C11—C12	175.26 (17)
C2—C3—C4—C7	−178.61 (16)	C10—C11—C12—C13	−1.2 (3)
C6—C3—C4—C7	1.4 (3)	N3—C11—C12—C13	179.27 (16)
C2—C3—C4—N1	2.11 (18)	C11—C12—C13—C8	−1.3 (3)
C6—C3—C4—N1	−177.87 (15)	C9—C8—C13—C12	2.9 (3)
N1—C4—C7—C8	−3.4 (3)	C7—C8—C13—C12	−178.56 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.88	1.98	2.8256 (18)	159
C9—H9···O1ii	0.95	2.43	3.336 (2)	159
C12—H12···N2iii	0.95	2.59	3.374 (3)	141
C13—H13···O2iv	0.95	2.58	3.372 (2)	141

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.88	1.98	2.8256 (18)	159
C9—H9⋯O1ii	0.95	2.43	3.336 (2)	159
C12—H12⋯N2iii	0.95	2.59	3.374 (3)	141
C13—H13⋯O2iv	0.95	2.58	3.372 (2)	141

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