3,3'-({4-[(4,5-Di-cyano-1H-imidazol-2-yl)diazen-yl]phen-yl}imino)-dipropionic acid.

The title compound, C17H15N7O4, is a push-pull non-linear optical chromophore containing a di-alkyl-amino donor group and the di-cyano-imidazolyl acceptor separated by a π-conjugated path. The benzene and imidazole rings are not coplanar, making a dihedral angle of 10.0 (2)°. In the crystal, mol-ecules are linked by an extended set of hydrogen bonds and several motifs are recognized. Pairs of mol-ecules are held together by hydrogen bonding between carb-oxy O-H donor groups and diazenyl N-atom acceptors, forming R 2 (2)(24) ring patterns across inversion centres. Four-mol-ecule R 4 (4)(28) ring motifs are formed, again across inversion centres, through hydrogen bonding involving carb-oxy O-H donor groups and diazenyl and imidazole N-atom acceptors. Four-mol-ecule R 4 (4)(42) patterns are formed among mol-ecules related by translation and involve carb-oxy O-H and imidazole N-H donor groups with carbonyl O-atom and imidazole N-atom acceptors.

Related literature

For a general survey of advanced materials based on heterocycles, see: Dalton (2002 ▶); Heeger (2010 ▶). For semiconductor, optoelectronic and piezoelectric materials containing heterocycles, see: Centore, Ricciotti et al. (2012 ▶); Centore, Concilio et al. (2012 ▶). For structural analysis of conjugation in heterocycle-based organic mol­ecules, see: Carella, Centore, Fort et al. (2004 ▶); Gainsford et al. (2008 ▶). For structural and theoretical analysis of conjugation in metallorganic compounds containing heterocycles, see: Takjoo et al. (2011 ▶); Takjoo & Centore (2013 ▶). For theoretical computations on π-conjugated compounds, see: Capobianco et al. (2012 ▶, 2013 ▶). For the synthesis of related heterocyclic compounds, see: Carella, Centore, Sirigu et al. (2004 ▶); Piccialli et al. (2013 ▶); Centore, Fusco, Capobianco et al. (2013 ▶). For the local packing modes of non-linear optical chromophores see: Thallapally et al. (2002 ▶); Centore & Piccialli (2012 ▶); Centore, Piccialli & Tuzi (2013 ▶). For hydrogen bonding in crystal structures, see: Allen et al. (1999 ▶); Steiner (2002 ▶); Centore, Jazbinsek et al. (2012 ▶); Centore, Fusco, Jazbinsek et al. (2013 ▶). For the synthesis of similar diazo-chromophores, see: Centore et al. (2007 ▶).

Experimental

Crystal data

C17H15N7O4

M = 381.36

Triclinic,

a = 6.895 (5) Å

b = 10.443 (3) Å

c = 13.373 (3) Å

α = 105.40 (2)°

β = 103.96 (4)°

γ = 104.84 (4)°

V = 846.5 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.26 × 0.13 × 0.07 mm

Data collection

Enraf–Nonius MACH3 diffractometer

4256 measured reflections

4082 independent reflections

1220 reflections with I > 2σ(I)

R int = 0.074

1 standard reflections every 120 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.075

wR(F 2) = 0.216

S = 0.91

4082 reflections

262 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.33 e Å−3

Data collection: MACH3/PC Software (Nonius, 1996 ▶); cell refinement: CELLFITW (Centore, 2004 ▶); data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011185/bx2439sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011185/bx2439Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813011185/bx2439Isup3.cml

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

C17H15N7O4	Z = 2
Mr = 381.36	F(000) = 396
Triclinic, P1	Dx = 1.496 Mg m−3
a = 6.895 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.443 (3) Å	Cell parameters from 25 reflections
c = 13.373 (3) Å	θ = 7.2–9.8°
α = 105.40 (2)°	µ = 0.11 mm−1
β = 103.96 (4)°	T = 293 K
γ = 104.84 (4)°	Plate, red
V = 846.5 (7) Å3	0.26 × 0.13 × 0.07 mm

Enraf–Nonius MACH3 diffractometer	Rint = 0.074
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 1.7°
Graphite monochromator	h = −9→8
Nonprofiled ω scans	k = −13→13
4256 measured reflections	l = 0→17
4082 independent reflections	1 standard reflections every 120 min
1220 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.216	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ2(Fo2) + (0.072P)2] where P = (Fo2 + 2Fc2)/3
4082 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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.Several crystal specimens were tested but their quality was, in general, rather poor, as witnessed by the relatively high fraction of low intensity reflections. The poorly diffracting nature of the crystals is the reason for the relatively high R factors.

	x	y	z	Uiso*/Ueq
O1	0.5087 (7)	0.2972 (5)	0.6271 (4)	0.0695 (14)
O2	0.7415 (7)	0.2144 (5)	0.5641 (3)	0.0546 (13)
H2	0.828 (10)	0.252 (7)	0.625 (5)	0.065*
O3	−0.6820 (6)	−0.1393 (4)	0.2211 (3)	0.0449 (11)
H3	−0.791 (9)	−0.207 (6)	0.168 (4)	0.054*
O4	−0.4973 (6)	−0.2424 (4)	0.1314 (3)	0.0579 (13)
N1	0.0479 (6)	0.1074 (4)	0.3096 (3)	0.0347 (11)
N2	0.1576 (6)	0.3969 (4)	0.0245 (3)	0.0330 (11)
N3	0.0616 (7)	0.3422 (4)	−0.0794 (4)	0.0351 (11)
N4	0.2872 (7)	0.5635 (5)	−0.0763 (4)	0.0321 (12)
H4	0.327 (8)	0.603 (6)	−0.010 (4)	0.039*
N5	0.0928 (6)	0.3985 (4)	−0.2380 (3)	0.0350 (11)
N6	0.2377 (9)	0.5392 (6)	−0.4342 (5)	0.0736 (18)
N7	0.5606 (7)	0.8734 (5)	−0.1101 (4)	0.0530 (15)
C1	0.5542 (10)	0.2307 (6)	0.5524 (5)	0.0443 (16)
C2	0.4013 (8)	0.1581 (6)	0.4388 (4)	0.0410 (15)
H2A	0.3851	0.0586	0.4165	0.049*
H2B	0.4604	0.1965	0.3898	0.049*
C3	0.1838 (8)	0.1715 (6)	0.4252 (4)	0.0390 (14)
H3A	0.1175	0.1254	0.4685	0.047*
H3B	0.1990	0.2707	0.4522	0.047*
C4	−0.5053 (8)	−0.1506 (6)	0.2034 (4)	0.0360 (14)
C5	−0.3145 (8)	−0.0271 (6)	0.2831 (4)	0.0443 (15)
H5A	−0.3144	−0.0190	0.3570	0.053*
H5B	−0.3294	0.0582	0.2714	0.053*
C6	−0.1030 (8)	−0.0340 (6)	0.2757 (4)	0.0379 (14)
H6A	−0.0501	−0.0828	0.3226	0.045*
H6B	−0.1197	−0.0867	0.2007	0.045*
C7	0.0604 (7)	0.1772 (6)	0.2383 (4)	0.0327 (13)
C8	−0.0607 (8)	0.1135 (5)	0.1257 (4)	0.0327 (13)
H8	−0.1607	0.0232	0.1005	0.039*
C9	−0.0354 (7)	0.1804 (5)	0.0534 (4)	0.0318 (13)
H9	−0.1138	0.1331	−0.0208	0.038*
C10	0.1061 (7)	0.3192 (5)	0.0874 (4)	0.0319 (13)
C11	0.2172 (8)	0.3865 (5)	0.2009 (4)	0.0354 (14)
H11	0.3079	0.4797	0.2262	0.042*
C12	0.1978 (8)	0.3213 (5)	0.2750 (4)	0.0350 (13)
H12	0.2732	0.3700	0.3494	0.042*
C13	0.1445 (7)	0.4320 (5)	−0.1300 (4)	0.0303 (13)
C14	0.3292 (8)	0.6199 (5)	−0.1517 (4)	0.0342 (14)
C15	0.2101 (8)	0.5140 (6)	−0.2531 (4)	0.0371 (14)
C16	0.4603 (8)	0.7600 (6)	−0.1284 (4)	0.0382 (14)
C17	0.2170 (9)	0.5250 (6)	−0.3564 (5)	0.0457 (16)

	U11	U22	U33	U12	U13	U23
O1	0.074 (3)	0.066 (3)	0.041 (3)	0.025 (3)	−0.002 (2)	−0.005 (2)
O2	0.041 (3)	0.058 (3)	0.042 (3)	0.008 (2)	−0.007 (2)	0.010 (2)
O3	0.031 (2)	0.048 (3)	0.039 (2)	−0.0005 (19)	0.0067 (19)	0.007 (2)
O4	0.051 (3)	0.051 (3)	0.040 (2)	0.001 (2)	0.010 (2)	−0.013 (2)
N1	0.031 (2)	0.030 (3)	0.029 (3)	−0.002 (2)	0.001 (2)	0.008 (2)
N2	0.030 (2)	0.030 (3)	0.030 (3)	0.005 (2)	0.007 (2)	0.005 (2)
N3	0.037 (3)	0.030 (3)	0.034 (3)	0.007 (2)	0.012 (2)	0.009 (2)
N4	0.029 (2)	0.025 (3)	0.030 (2)	0.001 (2)	0.006 (2)	0.003 (2)
N5	0.027 (2)	0.030 (3)	0.035 (3)	0.003 (2)	−0.001 (2)	0.010 (2)
N6	0.074 (4)	0.083 (5)	0.053 (4)	0.009 (3)	0.015 (3)	0.029 (3)
N7	0.044 (3)	0.040 (3)	0.067 (4)	0.005 (3)	0.020 (3)	0.015 (3)
C1	0.052 (4)	0.030 (4)	0.037 (4)	0.005 (3)	0.002 (3)	0.010 (3)
C2	0.041 (3)	0.040 (4)	0.033 (3)	0.007 (3)	0.003 (3)	0.012 (3)
C3	0.033 (3)	0.041 (4)	0.033 (3)	0.001 (3)	0.007 (3)	0.011 (3)
C4	0.034 (3)	0.038 (4)	0.031 (3)	0.004 (3)	0.007 (3)	0.015 (3)
C5	0.039 (3)	0.040 (4)	0.039 (3)	0.000 (3)	0.011 (3)	0.005 (3)
C6	0.034 (3)	0.035 (3)	0.034 (3)	0.002 (3)	0.005 (3)	0.010 (3)
C7	0.021 (3)	0.029 (3)	0.035 (3)	0.005 (2)	0.005 (2)	0.000 (3)
C8	0.027 (3)	0.026 (3)	0.036 (3)	0.002 (2)	0.006 (2)	0.007 (3)
C9	0.029 (3)	0.024 (3)	0.030 (3)	−0.002 (2)	0.002 (2)	0.007 (2)
C10	0.022 (3)	0.032 (3)	0.032 (3)	0.009 (2)	0.002 (2)	0.002 (3)
C11	0.033 (3)	0.025 (3)	0.040 (3)	0.002 (2)	0.012 (3)	0.006 (3)
C12	0.035 (3)	0.033 (3)	0.024 (3)	0.006 (3)	0.005 (2)	0.000 (2)
C13	0.024 (3)	0.033 (3)	0.028 (3)	0.008 (2)	0.006 (2)	0.006 (2)
C14	0.029 (3)	0.031 (3)	0.036 (3)	0.005 (3)	0.008 (2)	0.008 (3)
C15	0.028 (3)	0.042 (4)	0.031 (3)	0.007 (3)	0.003 (2)	0.008 (3)
C16	0.031 (3)	0.038 (4)	0.045 (4)	0.011 (3)	0.013 (3)	0.014 (3)
C17	0.040 (3)	0.049 (4)	0.037 (4)	0.004 (3)	0.006 (3)	0.014 (3)

O1—C1	1.213 (7)	C2—H2B	0.9700
O2—C1	1.323 (7)	C3—H3A	0.9700
O2—H2	0.80 (6)	C3—H3B	0.9700
O3—C4	1.324 (7)	C4—C5	1.502 (7)
O3—H3	0.88 (5)	C5—C6	1.504 (7)
O4—C4	1.187 (6)	C5—H5A	0.9700
N1—C7	1.350 (7)	C5—H5B	0.9700
N1—C6	1.449 (6)	C6—H6A	0.9700
N1—C3	1.465 (6)	C6—H6B	0.9700
N2—N3	1.278 (5)	C7—C8	1.408 (7)
N2—C10	1.361 (6)	C7—C12	1.434 (7)
N3—C13	1.384 (6)	C8—C9	1.353 (7)
N4—C13	1.346 (6)	C8—H8	0.9300
N4—C14	1.347 (7)	C9—C10	1.404 (7)
N4—H4	0.81 (5)	C9—H9	0.9300
N5—C13	1.325 (6)	C10—C11	1.408 (7)
N5—C15	1.363 (6)	C11—C12	1.356 (7)
N6—C17	1.127 (7)	C11—H11	0.9300
N7—C16	1.133 (6)	C12—H12	0.9300
C1—C2	1.483 (7)	C14—C15	1.392 (7)
C2—C3	1.514 (7)	C14—C16	1.415 (8)
C2—H2A	0.9700	C15—C17	1.427 (8)
C1—O2—H2	116 (5)	N1—C6—C5	110.1 (4)
C4—O3—H3	108 (4)	N1—C6—H6A	109.6
C7—N1—C6	121.5 (4)	C5—C6—H6A	109.6
C7—N1—C3	121.7 (4)	N1—C6—H6B	109.6
C6—N1—C3	116.7 (4)	C5—C6—H6B	109.6
N3—N2—C10	118.0 (4)	H6A—C6—H6B	108.2
N2—N3—C13	109.7 (4)	N1—C7—C8	122.1 (5)
C13—N4—C14	108.1 (4)	N1—C7—C12	120.9 (5)
C13—N4—H4	124 (4)	C8—C7—C12	117.0 (5)
C14—N4—H4	127 (4)	C9—C8—C7	121.7 (5)
C13—N5—C15	105.1 (4)	C9—C8—H8	119.1
O1—C1—O2	123.8 (6)	C7—C8—H8	119.1
O1—C1—C2	122.5 (6)	C8—C9—C10	121.7 (5)
O2—C1—C2	113.7 (6)	C8—C9—H9	119.1
C1—C2—C3	114.2 (5)	C10—C9—H9	119.1
C1—C2—H2A	108.7	N2—C10—C9	128.5 (5)
C3—C2—H2A	108.7	N2—C10—C11	114.8 (4)
C1—C2—H2B	108.7	C9—C10—C11	116.6 (5)
C3—C2—H2B	108.7	C12—C11—C10	122.9 (5)
H2A—C2—H2B	107.6	C12—C11—H11	118.6
N1—C3—C2	111.0 (4)	C10—C11—H11	118.6
N1—C3—H3A	109.4	C11—C12—C7	119.8 (5)
C2—C3—H3A	109.4	C11—C12—H12	120.1
N1—C3—H3B	109.4	C7—C12—H12	120.1
C2—C3—H3B	109.4	N5—C13—N4	111.6 (5)
H3A—C3—H3B	108.0	N5—C13—N3	123.9 (4)
O4—C4—O3	125.1 (5)	N4—C13—N3	124.5 (4)
O4—C4—C5	123.8 (5)	N4—C14—C15	105.3 (5)
O3—C4—C5	111.0 (5)	N4—C14—C16	125.5 (5)
C4—C5—C6	115.5 (5)	C15—C14—C16	129.1 (5)
C4—C5—H5A	108.4	N5—C15—C14	109.8 (5)
C6—C5—H5A	108.4	N5—C15—C17	125.8 (5)
C4—C5—H5B	108.4	C14—C15—C17	124.4 (5)
C6—C5—H5B	108.4	N7—C16—C14	178.1 (6)
H5A—C5—H5B	107.5	N6—C17—C15	175.0 (6)
C10—N2—N3—C13	−175.9 (4)	C9—C10—C11—C12	2.4 (8)
O1—C1—C2—C3	−1.3 (8)	C10—C11—C12—C7	0.5 (8)
O2—C1—C2—C3	177.9 (5)	N1—C7—C12—C11	176.1 (5)
C7—N1—C3—C2	−81.8 (6)	C8—C7—C12—C11	−4.6 (7)
C6—N1—C3—C2	99.1 (5)	C15—N5—C13—N4	0.6 (6)
C1—C2—C3—N1	175.3 (5)	C15—N5—C13—N3	−179.4 (5)
O4—C4—C5—C6	−7.2 (8)	C14—N4—C13—N5	0.9 (6)
O3—C4—C5—C6	175.8 (5)	C14—N4—C13—N3	−179.2 (5)
C7—N1—C6—C5	−85.4 (6)	N2—N3—C13—N5	172.9 (5)
C3—N1—C6—C5	93.7 (6)	N2—N3—C13—N4	−7.0 (7)
C4—C5—C6—N1	150.8 (5)	C13—N4—C14—C15	−2.0 (6)
C6—N1—C7—C8	−4.7 (8)	C13—N4—C14—C16	175.5 (5)
C3—N1—C7—C8	176.2 (5)	C13—N5—C15—C14	−1.8 (6)
C6—N1—C7—C12	174.7 (5)	C13—N5—C15—C17	176.3 (6)
C3—N1—C7—C12	−4.4 (7)	N4—C14—C15—N5	2.4 (6)
N1—C7—C8—C9	−174.8 (5)	C16—C14—C15—N5	−175.0 (5)
C12—C7—C8—C9	5.8 (8)	N4—C14—C15—C17	−175.8 (5)
C7—C8—C9—C10	−2.9 (8)	C16—C14—C15—C17	6.9 (10)
N3—N2—C10—C9	3.2 (8)	N4—C14—C16—N7	−92 (19)
N3—N2—C10—C11	−179.6 (5)	C15—C14—C16—N7	85 (19)
C8—C9—C10—N2	175.9 (5)	N5—C15—C17—N6	−143 (8)
C8—C9—C10—C11	−1.3 (7)	C14—C15—C17—N6	35 (9)
N2—C10—C11—C12	−175.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N5i	0.80 (6)	2.12 (6)	2.896 (6)	162 (6)
O3—H3···N3ii	0.88 (5)	1.89 (6)	2.750 (6)	165 (5)
N4—H4···O4iii	0.81 (5)	1.98 (5)	2.740 (6)	156 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N5i	0.80 (6)	2.12 (6)	2.896 (6)	162 (6)
O3—H3⋯N3ii	0.88 (5)	1.89 (6)	2.750 (6)	165 (5)
N4—H4⋯O4iii	0.81 (5)	1.98 (5)	2.740 (6)	156 (5)

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