Ethyl 4-[3-(1H-imidazol-1-yl)propyl-amino]-3-nitro-benzoate.

In the title compound, C(15)H(18)N(4)O(4), the 1H-imidazole ring forms a dihedral angle of 67.12 (8)° with the benzene ring. An S(6) ring motif is formed via an intra-molecular N-H⋯O hydrogen bond. In the crystal, neighbouring mol-ecules are linked by a pair of inter-molecular N-H⋯N hydrogen bonds, forming an inversion dimer. The dimers are further linked by a pair of C-H⋯O hydrogen bonds, leading to the formation of chain along [021]. A C-H⋯π inter-action involving the centroid of the benzene ring is also observed between the chains.

Related literature

For applications of phenyl­enediamines, see: Sabelle (2006 ▶); Glebowska et al. (2009 ▶); Remusat et al. (2004 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C15H18N4O4

M = 318.33

Triclinic,

a = 8.4860 (4) Å

b = 8.6175 (4) Å

c = 11.7507 (6) Å

α = 77.489 (1)°

β = 81.732 (1)°

γ = 67.977 (1)°

V = 775.83 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 297 K

0.43 × 0.37 × 0.23 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.958, T max = 0.978

15358 measured reflections

4470 independent reflections

3627 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.173

S = 1.05

4470 reflections

213 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036300/is2771sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036300/is2771Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811036300/is2771Isup3.cml

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

C15H18N4O4	Z = 2
Mr = 318.33	F(000) = 336
Triclinic, P1	Dx = 1.363 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4860 (4) Å	Cell parameters from 6626 reflections
b = 8.6175 (4) Å	θ = 2.6–32.5°
c = 11.7507 (6) Å	µ = 0.10 mm−1
α = 77.489 (1)°	T = 297 K
β = 81.732 (1)°	Block, yellow
γ = 67.977 (1)°	0.43 × 0.37 × 0.23 mm
V = 775.83 (7) Å3

Bruker SMART APEXII DUO CCD area-detector diffractometer	4470 independent reflections
Radiation source: fine-focus sealed tube	3627 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 30.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.958, Tmax = 0.978	k = −11→12
15358 measured reflections	l = −16→16

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.1056P)2 + 0.1039P] where P = (Fo2 + 2Fc2)/3
4470 reflections	(Δ/σ)max = 0.001
213 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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
O1	0.70039 (15)	1.08819 (19)	0.76638 (14)	0.0819 (4)
O2	0.66111 (13)	0.92725 (15)	0.66648 (11)	0.0630 (3)
O3	0.28465 (12)	1.36380 (12)	1.04716 (9)	0.0495 (2)
O4	0.04276 (15)	1.30975 (15)	1.09224 (9)	0.0602 (3)
N1	0.39536 (14)	0.82823 (14)	0.71627 (10)	0.0439 (3)
N2	0.16593 (13)	0.56169 (13)	0.55424 (9)	0.0411 (2)
N3	0.32584 (19)	0.38579 (17)	0.43667 (11)	0.0598 (3)
N4	0.61326 (13)	1.01531 (14)	0.74276 (10)	0.0457 (3)
C1	0.1987 (2)	0.4015 (2)	0.61436 (12)	0.0579 (4)
H1A	0.1613	0.3702	0.6912	0.069*
C2	0.2965 (2)	0.29595 (19)	0.54111 (13)	0.0586 (4)
H2A	0.3376	0.1779	0.5601	0.070*
C3	0.2444 (2)	0.5452 (2)	0.44782 (13)	0.0605 (4)
H3A	0.2415	0.6368	0.3883	0.073*
C4	0.06090 (17)	0.72024 (18)	0.59566 (13)	0.0511 (3)
H4A	0.0024	0.6934	0.6702	0.061*
H4B	−0.0249	0.7878	0.5406	0.061*
C5	0.16440 (18)	0.82458 (16)	0.60979 (12)	0.0487 (3)
H5A	0.0879	0.9313	0.6318	0.058*
H5B	0.2240	0.8505	0.5355	0.058*
C6	0.29333 (16)	0.73156 (15)	0.70181 (11)	0.0423 (3)
H6A	0.2332	0.7064	0.7760	0.051*
H6B	0.3686	0.6242	0.6801	0.051*
C7	0.34741 (14)	0.94586 (14)	0.78555 (10)	0.0364 (2)
C8	0.18281 (16)	0.98950 (16)	0.84576 (11)	0.0432 (3)
H8A	0.1076	0.9408	0.8327	0.052*
C9	0.13241 (16)	1.10113 (16)	0.92231 (11)	0.0435 (3)
H9A	0.0238	1.1261	0.9598	0.052*
C10	0.23935 (15)	1.17874 (14)	0.94578 (10)	0.0383 (2)
C11	0.39749 (15)	1.14588 (14)	0.88549 (10)	0.0379 (2)
H11A	0.4695	1.1985	0.8982	0.045*
C12	0.44984 (14)	1.03452 (14)	0.80583 (10)	0.0361 (2)
C13	0.17697 (17)	1.28977 (15)	1.03544 (10)	0.0417 (3)
C14	0.22780 (19)	1.47706 (18)	1.13211 (12)	0.0512 (3)
H14A	0.2402	1.4115	1.2107	0.061*
H14B	0.1087	1.5475	1.1245	0.061*
C15	0.3332 (3)	1.5847 (2)	1.10987 (17)	0.0705 (5)
H15A	0.2972	1.6612	1.1648	0.106*
H15B	0.3203	1.6488	1.0319	0.106*
H15C	0.4506	1.5140	1.1185	0.106*
H1N1	0.495 (2)	0.808 (2)	0.6809 (15)	0.058 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0597 (7)	0.1035 (10)	0.1167 (11)	−0.0523 (7)	0.0326 (7)	−0.0724 (9)
O2	0.0512 (5)	0.0719 (7)	0.0792 (7)	−0.0281 (5)	0.0258 (5)	−0.0497 (6)
O3	0.0513 (5)	0.0525 (5)	0.0546 (5)	−0.0209 (4)	0.0062 (4)	−0.0319 (4)
O4	0.0660 (6)	0.0713 (7)	0.0563 (6)	−0.0357 (5)	0.0245 (5)	−0.0365 (5)
N1	0.0431 (5)	0.0441 (5)	0.0525 (6)	−0.0187 (4)	0.0085 (4)	−0.0272 (4)
N2	0.0406 (5)	0.0477 (5)	0.0404 (5)	−0.0169 (4)	0.0025 (4)	−0.0202 (4)
N3	0.0698 (8)	0.0594 (7)	0.0533 (7)	−0.0226 (6)	0.0142 (6)	−0.0296 (6)
N4	0.0406 (5)	0.0446 (5)	0.0577 (6)	−0.0183 (4)	0.0090 (4)	−0.0235 (5)
C1	0.0748 (9)	0.0574 (8)	0.0400 (6)	−0.0233 (7)	0.0052 (6)	−0.0120 (6)
C2	0.0720 (9)	0.0480 (7)	0.0528 (8)	−0.0128 (6)	−0.0063 (7)	−0.0170 (6)
C3	0.0832 (10)	0.0545 (8)	0.0434 (7)	−0.0261 (7)	0.0163 (7)	−0.0186 (6)
C4	0.0396 (6)	0.0556 (7)	0.0600 (8)	−0.0093 (5)	−0.0002 (5)	−0.0302 (6)
C5	0.0544 (7)	0.0413 (6)	0.0514 (7)	−0.0126 (5)	−0.0025 (5)	−0.0194 (5)
C6	0.0470 (6)	0.0380 (5)	0.0482 (6)	−0.0172 (5)	0.0019 (5)	−0.0203 (5)
C7	0.0416 (5)	0.0336 (5)	0.0368 (5)	−0.0146 (4)	0.0032 (4)	−0.0133 (4)
C8	0.0458 (6)	0.0454 (6)	0.0478 (6)	−0.0245 (5)	0.0110 (5)	−0.0215 (5)
C9	0.0470 (6)	0.0436 (6)	0.0454 (6)	−0.0221 (5)	0.0132 (5)	−0.0193 (5)
C10	0.0463 (6)	0.0359 (5)	0.0357 (5)	−0.0165 (4)	0.0053 (4)	−0.0144 (4)
C11	0.0416 (5)	0.0356 (5)	0.0407 (5)	−0.0157 (4)	0.0012 (4)	−0.0143 (4)
C12	0.0373 (5)	0.0344 (5)	0.0386 (5)	−0.0136 (4)	0.0043 (4)	−0.0136 (4)
C13	0.0500 (6)	0.0406 (6)	0.0379 (5)	−0.0179 (5)	0.0047 (4)	−0.0159 (4)
C14	0.0616 (8)	0.0506 (7)	0.0481 (7)	−0.0195 (6)	0.0019 (6)	−0.0275 (5)
C15	0.0860 (12)	0.0714 (10)	0.0742 (10)	−0.0428 (9)	0.0087 (9)	−0.0364 (8)

O1—N4	1.2251 (15)	C5—C6	1.5217 (19)
O2—N4	1.2261 (14)	C5—H5A	0.9700
O3—C13	1.3313 (15)	C5—H5B	0.9700
O3—C14	1.4533 (14)	C6—H6A	0.9700
O4—C13	1.2067 (16)	C6—H6B	0.9700
N1—C7	1.3449 (13)	C7—C8	1.4249 (16)
N1—C6	1.4551 (15)	C7—C12	1.4257 (15)
N1—H1N1	0.856 (19)	C8—C9	1.3686 (15)
N2—C3	1.3395 (16)	C8—H8A	0.9300
N2—C1	1.3518 (19)	C9—C10	1.3978 (17)
N2—C4	1.4657 (15)	C9—H9A	0.9300
N3—C3	1.3120 (19)	C10—C11	1.3826 (16)
N3—C2	1.346 (2)	C10—C13	1.4840 (15)
N4—C12	1.4440 (15)	C11—C12	1.3944 (14)
C1—C2	1.351 (2)	C11—H11A	0.9300
C1—H1A	0.9300	C14—C15	1.476 (2)
C2—H2A	0.9300	C14—H14A	0.9700
C3—H3A	0.9300	C14—H14B	0.9700
C4—C5	1.5186 (19)	C15—H15A	0.9600
C4—H4A	0.9700	C15—H15B	0.9600
C4—H4B	0.9700	C15—H15C	0.9600
C13—O3—C14	115.30 (10)	C5—C6—H6B	108.9
C7—N1—C6	124.49 (10)	H6A—C6—H6B	107.8
C7—N1—H1N1	116.5 (12)	N1—C7—C8	119.86 (10)
C6—N1—H1N1	119.0 (12)	N1—C7—C12	125.14 (10)
C3—N2—C1	105.75 (12)	C8—C7—C12	115.00 (9)
C3—N2—C4	127.17 (12)	C9—C8—C7	121.81 (11)
C1—N2—C4	127.05 (11)	C9—C8—H8A	119.1
C3—N3—C2	104.48 (12)	C7—C8—H8A	119.1
O1—N4—O2	121.58 (11)	C8—C9—C10	121.93 (11)
O1—N4—C12	119.17 (10)	C8—C9—H9A	119.0
O2—N4—C12	119.25 (10)	C10—C9—H9A	119.0
C2—C1—N2	106.62 (13)	C11—C10—C9	118.24 (10)
C2—C1—H1A	126.7	C11—C10—C13	123.90 (11)
N2—C1—H1A	126.7	C9—C10—C13	117.86 (10)
N3—C2—C1	110.43 (13)	C10—C11—C12	120.55 (11)
N3—C2—H2A	124.8	C10—C11—H11A	119.7
C1—C2—H2A	124.8	C12—C11—H11A	119.7
N3—C3—N2	112.72 (13)	C11—C12—C7	122.29 (10)
N3—C3—H3A	123.6	C11—C12—N4	116.41 (10)
N2—C3—H3A	123.6	C7—C12—N4	121.29 (9)
N2—C4—C5	112.73 (10)	O4—C13—O3	123.64 (11)
N2—C4—H4A	109.0	O4—C13—C10	123.26 (11)
C5—C4—H4A	109.0	O3—C13—C10	113.10 (10)
N2—C4—H4B	109.0	O3—C14—C15	108.04 (12)
C5—C4—H4B	109.0	O3—C14—H14A	110.1
H4A—C4—H4B	107.8	C15—C14—H14A	110.1
C4—C5—C6	112.09 (11)	O3—C14—H14B	110.1
C4—C5—H5A	109.2	C15—C14—H14B	110.1
C6—C5—H5A	109.2	H14A—C14—H14B	108.4
C4—C5—H5B	109.2	C14—C15—H15A	109.5
C6—C5—H5B	109.2	C14—C15—H15B	109.5
H5A—C5—H5B	107.9	H15A—C15—H15B	109.5
N1—C6—C5	113.19 (11)	C14—C15—H15C	109.5
N1—C6—H6A	108.9	H15A—C15—H15C	109.5
C5—C6—H6A	108.9	H15B—C15—H15C	109.5
N1—C6—H6B	108.9
C3—N2—C1—C2	0.29 (18)	C9—C10—C11—C12	−1.70 (18)
C4—N2—C1—C2	178.23 (13)	C13—C10—C11—C12	177.37 (10)
C3—N3—C2—C1	−0.4 (2)	C10—C11—C12—C7	−2.12 (18)
N2—C1—C2—N3	0.0 (2)	C10—C11—C12—N4	176.86 (11)
C2—N3—C3—N2	0.6 (2)	N1—C7—C12—C11	−175.11 (11)
C1—N2—C3—N3	−0.5 (2)	C8—C7—C12—C11	4.66 (17)
C4—N2—C3—N3	−178.48 (13)	N1—C7—C12—N4	5.96 (19)
C3—N2—C4—C5	−70.00 (19)	C8—C7—C12—N4	−174.27 (11)
C1—N2—C4—C5	112.49 (16)	O1—N4—C12—C11	4.07 (19)
N2—C4—C5—C6	−62.97 (15)	O2—N4—C12—C11	−175.55 (12)
C7—N1—C6—C5	85.02 (15)	O1—N4—C12—C7	−176.93 (13)
C4—C5—C6—N1	179.45 (10)	O2—N4—C12—C7	3.44 (19)
C6—N1—C7—C8	−3.56 (19)	C14—O3—C13—O4	−1.8 (2)
C6—N1—C7—C12	176.19 (11)	C14—O3—C13—C10	178.66 (10)
N1—C7—C8—C9	176.17 (12)	C11—C10—C13—O4	−175.61 (13)
C12—C7—C8—C9	−3.61 (18)	C9—C10—C13—O4	3.5 (2)
C7—C8—C9—C10	0.0 (2)	C11—C10—C13—O3	3.97 (18)
C8—C9—C10—C11	2.76 (19)	C9—C10—C13—O3	−176.96 (11)
C8—C9—C10—C13	−176.37 (12)	C13—O3—C14—C15	−163.51 (13)

Cg1 is the centroid of the C7–C12 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.859 (18)	2.004 (18)	2.6464 (18)	130.9 (15)
N1—H1N1···N3i	0.859 (18)	2.345 (17)	3.0281 (18)	136.7 (15)
C15—H15A···O1ii	0.96	2.47	3.346 (2)	151
C1—H1A···Cg1iii	0.93	2.90	3.5962 (16)	132

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C12 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.859 (18)	2.004 (18)	2.6464 (18)	130.9 (15)
N1—H1N1⋯N3i	0.859 (18)	2.345 (17)	3.0281 (18)	136.7 (15)
C15—H15A⋯O1ii	0.96	2.47	3.346 (2)	151
C1—H1A⋯Cg1iii	0.93	2.90	3.5962 (16)	132

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