2-[(E)-(2-Morpholinoeth-yl)iminiometh-yl]-4-nitro-1-oxocyclo-hexa-dienide.

The mol-ecule of the title compound, C(13)H(17)N(3)O(4), exists as a zwitterion, with the H atom of the phenol group being transferred to the imine N atom. The C=O, C(Ar)-C(Ar) and C-N bond lengths are in agreement with the oxocyclo-hexa-dienide-iminium zwitterionic form. A strong intra-molecular N(+)-H⋯O hydrogen bond generates an S(6) ring motif. The morpholine ring adopts a chair conformation. In the crystal, mol-ecules are linked into centrosymmetric dimers by inter-molecular N-H⋯O hydrogen bonds. In addition, C-H⋯O hydrogen bonds and very weak C-H⋯π inter-actions are observed.

Related literature

For general background, photochromic and thermochromic characteristics of Schiff base compounds, see: Calligaris et al. (1972 ▶); Cohen et al. (1964 ▶); Hadjoudis et al. (1987 ▶); Karabıyık et al. (2008 ▶). For related structures, see: Butt et al. (1987 ▶); Petek et al. (2006 ▶); Krygowski & Stepien (2005 ▶); Santos-Contreras et al. (2009 ▶). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C13H17N3O4

M = 279.30

Triclinic,

a = 5.3520 (4) Å

b = 10.8972 (9) Å

c = 12.4537 (9) Å

α = 102.329 (7)°

β = 97.143 (6)°

γ = 104.173 (9)°

V = 675.91 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.75 × 0.70 × 0.40 mm

Data collection

Stoe IPDSII diffractometer

Absorption correction: none

11340 measured reflections

3094 independent reflections

2664 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.110

S = 1.06

3094 reflections

186 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.17 e Å−3

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, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026191/ci2842sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026191/ci2842Isup2.hkl

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

C13H17N3O4	Z = 2
Mr = 279.30	F(000) = 296
Triclinic, P1	Dx = 1.372 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3520 (4) Å	Cell parameters from 23053 reflections
b = 10.8972 (9) Å	θ = 1.7–28.0°
c = 12.4537 (9) Å	µ = 0.10 mm−1
α = 102.329 (7)°	T = 296 K
β = 97.143 (6)°	Prism, orange
γ = 104.173 (9)°	0.75 × 0.70 × 0.40 mm
V = 675.91 (10) Å3

Stoe IPDSII diffractometer	2664 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
graphite	θmax = 27.6°, θmin = 1.7°
Detector resolution: 6.67 pixels mm-1	h = −6→6
ω scans	k = −14→14
11340 measured reflections	l = −16→16
3094 independent reflections

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.0512P)2 + 0.1309P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
3094 reflections	Δρmax = 0.26 e Å−3
186 parameters	Δρmin = −0.17 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: 0.077 (7)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.4611 (2)	0.77887 (11)	0.53094 (9)	0.0335 (2)
C2	0.6439 (2)	0.90243 (11)	0.56526 (9)	0.0341 (2)
H2	0.7896	0.9204	0.5315	0.041*
C3	0.6067 (2)	0.99713 (10)	0.64924 (9)	0.0348 (3)
C4	0.3899 (3)	0.97257 (12)	0.70256 (10)	0.0396 (3)
H4	0.3692	1.0377	0.7597	0.048*
C5	0.2112 (3)	0.85348 (12)	0.67033 (11)	0.0426 (3)
H5	0.0698	0.8382	0.7069	0.051*
C6	0.2318 (2)	0.74989 (11)	0.58183 (10)	0.0363 (3)
C7	0.5074 (2)	0.68324 (11)	0.44412 (9)	0.0358 (3)
H7	0.6566	0.7074	0.4138	0.043*
C8	0.4146 (3)	0.46932 (12)	0.31724 (10)	0.0430 (3)
H8A	0.3937	0.3878	0.3393	0.052*
H8B	0.5956	0.5004	0.3093	0.052*
C9	0.2370 (3)	0.44450 (12)	0.20590 (10)	0.0437 (3)
H9A	0.0572	0.4050	0.2113	0.052*
H9B	0.2453	0.5268	0.1865	0.052*
C10	0.2038 (3)	0.36092 (15)	0.00679 (11)	0.0513 (3)
H10A	0.2527	0.4500	−0.0009	0.062*
H10B	0.0140	0.3307	−0.0047	0.062*
C11	0.3025 (3)	0.27445 (17)	−0.07913 (12)	0.0640 (4)
H11A	0.2304	0.2783	−0.1534	0.077*
H11B	0.4920	0.3062	−0.0681	0.077*
C12	0.3364 (4)	0.13651 (16)	0.03730 (15)	0.0665 (5)
H12A	0.5264	0.1645	0.0487	0.080*
H12B	0.2834	0.0467	0.0429	0.080*
C13	0.2450 (3)	0.22200 (13)	0.12725 (12)	0.0504 (3)
H13A	0.0561	0.1904	0.1194	0.060*
H13B	0.3244	0.2177	0.2002	0.060*
N1	0.7884 (2)	1.12600 (10)	0.68031 (9)	0.0410 (3)
N2	0.3567 (2)	0.56554 (9)	0.40467 (8)	0.0378 (2)
N3	0.3171 (2)	0.35764 (10)	0.11888 (8)	0.0422 (3)
O1	0.06162 (19)	0.64042 (9)	0.55030 (9)	0.0513 (3)
O2	0.7384 (2)	1.21314 (9)	0.74731 (9)	0.0600 (3)
O3	0.9854 (2)	1.14568 (9)	0.63771 (9)	0.0549 (3)
O4	0.2302 (3)	0.14272 (12)	−0.07115 (9)	0.0727 (4)
H1	0.214 (4)	0.5433 (18)	0.4335 (15)	0.065 (5)*

	U11	U22	U33	U12	U13	U23
C1	0.0382 (6)	0.0302 (5)	0.0305 (5)	0.0089 (4)	0.0086 (4)	0.0041 (4)
C2	0.0370 (6)	0.0324 (5)	0.0316 (5)	0.0083 (4)	0.0096 (4)	0.0055 (4)
C3	0.0410 (6)	0.0286 (5)	0.0310 (5)	0.0073 (4)	0.0048 (4)	0.0035 (4)
C4	0.0493 (7)	0.0363 (6)	0.0335 (6)	0.0162 (5)	0.0120 (5)	0.0020 (4)
C5	0.0450 (7)	0.0419 (6)	0.0422 (6)	0.0125 (5)	0.0198 (5)	0.0065 (5)
C6	0.0388 (6)	0.0319 (5)	0.0372 (6)	0.0085 (4)	0.0102 (5)	0.0063 (4)
C7	0.0398 (6)	0.0336 (5)	0.0323 (5)	0.0088 (5)	0.0098 (4)	0.0049 (4)
C8	0.0508 (7)	0.0361 (6)	0.0374 (6)	0.0151 (5)	0.0086 (5)	−0.0038 (5)
C9	0.0545 (7)	0.0391 (6)	0.0375 (6)	0.0195 (5)	0.0105 (5)	0.0008 (5)
C10	0.0532 (8)	0.0582 (8)	0.0358 (7)	0.0119 (6)	0.0063 (6)	0.0030 (6)
C11	0.0646 (10)	0.0736 (10)	0.0367 (7)	0.0046 (8)	0.0132 (6)	−0.0071 (7)
C12	0.0776 (11)	0.0501 (8)	0.0648 (10)	0.0231 (8)	0.0203 (8)	−0.0105 (7)
C13	0.0625 (9)	0.0409 (7)	0.0457 (7)	0.0180 (6)	0.0147 (6)	−0.0003 (5)
N1	0.0491 (6)	0.0311 (5)	0.0371 (5)	0.0070 (4)	0.0045 (4)	0.0030 (4)
N2	0.0443 (6)	0.0317 (5)	0.0331 (5)	0.0083 (4)	0.0105 (4)	−0.0002 (4)
N3	0.0497 (6)	0.0406 (5)	0.0324 (5)	0.0146 (5)	0.0088 (4)	−0.0020 (4)
O1	0.0483 (5)	0.0358 (5)	0.0617 (6)	−0.0002 (4)	0.0219 (4)	0.0025 (4)
O2	0.0719 (7)	0.0337 (5)	0.0622 (6)	0.0106 (4)	0.0133 (5)	−0.0092 (4)
O3	0.0556 (6)	0.0417 (5)	0.0564 (6)	−0.0031 (4)	0.0169 (5)	0.0047 (4)
O4	0.0816 (8)	0.0612 (7)	0.0526 (6)	0.0055 (6)	0.0197 (6)	−0.0207 (5)

C1—C2	1.3994 (16)	C9—H9A	0.97
C1—C7	1.4241 (15)	C9—H9B	0.97
C1—C6	1.4478 (16)	C10—N3	1.4625 (17)
C2—C3	1.3748 (15)	C10—C11	1.505 (2)
C2—H2	0.93	C10—H10A	0.97
C3—C4	1.4051 (17)	C10—H10B	0.97
C3—N1	1.4398 (15)	C11—O4	1.421 (2)
C4—C5	1.3543 (18)	C11—H11A	0.97
C4—H4	0.93	C11—H11B	0.97
C5—C6	1.4357 (16)	C12—O4	1.421 (2)
C5—H5	0.93	C12—C13	1.5086 (19)
C6—O1	1.2594 (14)	C12—H12A	0.97
C7—N2	1.2894 (15)	C12—H12B	0.97
C7—H7	0.93	C13—N3	1.4632 (18)
C8—N2	1.4615 (14)	C13—H13A	0.97
C8—C9	1.5117 (18)	C13—H13B	0.97
C8—H8A	0.97	N1—O2	1.2293 (14)
C8—H8B	0.97	N1—O3	1.2315 (14)
C9—N3	1.4596 (15)	N2—H1	0.887 (19)
C2—C1—C7	117.84 (10)	N3—C10—H10A	109.8
C2—C1—C6	120.88 (10)	C11—C10—H10A	109.8
C7—C1—C6	121.27 (10)	N3—C10—H10B	109.8
C3—C2—C1	119.54 (10)	C11—C10—H10B	109.8
C3—C2—H2	120.2	H10A—C10—H10B	108.2
C1—C2—H2	120.2	O4—C11—C10	111.17 (13)
C2—C3—C4	121.54 (10)	O4—C11—H11A	109.4
C2—C3—N1	119.24 (10)	C10—C11—H11A	109.4
C4—C3—N1	119.18 (10)	O4—C11—H11B	109.4
C5—C4—C3	119.65 (11)	C10—C11—H11B	109.4
C5—C4—H4	120.2	H11A—C11—H11B	108.0
C3—C4—H4	120.2	O4—C12—C13	111.48 (14)
C4—C5—C6	122.50 (11)	O4—C12—H12A	109.3
C4—C5—H5	118.8	C13—C12—H12A	109.3
C6—C5—H5	118.8	O4—C12—H12B	109.3
O1—C6—C5	122.23 (11)	C13—C12—H12B	109.3
O1—C6—C1	121.91 (10)	H12A—C12—H12B	108.0
C5—C6—C1	115.86 (10)	N3—C13—C12	110.35 (13)
N2—C7—C1	124.56 (11)	N3—C13—H13A	109.6
N2—C7—H7	117.7	C12—C13—H13A	109.6
C1—C7—H7	117.7	N3—C13—H13B	109.6
N2—C8—C9	111.99 (10)	C12—C13—H13B	109.6
N2—C8—H8A	109.2	H13A—C13—H13B	108.1
C9—C8—H8A	109.2	O2—N1—O3	122.35 (11)
N2—C8—H8B	109.2	O2—N1—C3	118.53 (11)
C9—C8—H8B	109.2	O3—N1—C3	119.11 (10)
H8A—C8—H8B	107.9	C7—N2—C8	122.84 (11)
N3—C9—C8	110.22 (10)	C7—N2—H1	117.3 (12)
N3—C9—H9A	109.6	C8—N2—H1	119.8 (12)
C8—C9—H9A	109.6	C9—N3—C10	111.82 (10)
N3—C9—H9B	109.6	C9—N3—C13	112.22 (10)
C8—C9—H9B	109.6	C10—N3—C13	108.56 (11)
H9A—C9—H9B	108.1	C12—O4—C11	109.63 (11)
N3—C10—C11	109.46 (13)
C7—C1—C2—C3	−179.68 (10)	N3—C10—C11—O4	60.36 (17)
C6—C1—C2—C3	0.69 (17)	O4—C12—C13—N3	−57.64 (18)
C1—C2—C3—C4	0.62 (18)	C2—C3—N1—O2	172.71 (11)
C1—C2—C3—N1	−176.92 (10)	C4—C3—N1—O2	−4.89 (17)
C2—C3—C4—C5	−0.61 (18)	C2—C3—N1—O3	−6.09 (17)
N1—C3—C4—C5	176.93 (11)	C4—C3—N1—O3	176.31 (11)
C3—C4—C5—C6	−0.7 (2)	C1—C7—N2—C8	−178.52 (11)
C4—C5—C6—O1	−178.16 (12)	C9—C8—N2—C7	−106.90 (14)
C4—C5—C6—C1	1.93 (19)	C8—C9—N3—C10	−163.51 (11)
C2—C1—C6—O1	178.21 (11)	C8—C9—N3—C13	74.22 (14)
C7—C1—C6—O1	−1.41 (18)	C11—C10—N3—C9	177.47 (12)
C2—C1—C6—C5	−1.89 (17)	C11—C10—N3—C13	−58.19 (15)
C7—C1—C6—C5	178.49 (11)	C12—C13—N3—C9	−178.84 (12)
C2—C1—C7—N2	179.62 (11)	C12—C13—N3—C10	57.05 (16)
C6—C1—C7—N2	−0.75 (18)	C13—C12—O4—C11	57.82 (18)
N2—C8—C9—N3	174.64 (11)	C10—C11—O4—C12	−59.34 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1	0.89 (2)	1.99 (2)	2.6760 (14)	133 (2)
N2—H1···O1i	0.89 (2)	2.24 (2)	2.9587 (14)	138 (2)
C4—H4···O4ii	0.93	2.47	3.3547 (16)	160
C7—H7···O3iii	0.93	2.43	3.3020 (15)	157
C13—H13B···Cg2iv	0.97	2.99	3.9254	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O1	0.89 (2)	1.99 (2)	2.6760 (14)	133 (2)
N2—H1⋯O1i	0.89 (2)	2.24 (2)	2.9587 (14)	138 (2)
C4—H4⋯O4ii	0.93	2.47	3.3547 (16)	160
C7—H7⋯O3iii	0.93	2.43	3.3020 (15)	157
C13—H13B⋯Cg2iv	0.97	2.99	3.9254	162

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the C1–C6 ring.