(E)-5,5′-(Diazene-1,2-di­yl)diisophthalic acid N,N-dimethyl­formamide disolvate

Abstract

The title compound, C₁₆H₁₀N₂O₈·2C₃H₇NO, was synthesized by the reductive condensation reaction of 5-nitro­isophthalic acid in the presence of NaOH. The tetra-acid mol­ecule, which has a crystallographically imposed centre of symmetry, adopts an E configuration with respect to the azo group. In the crystal packing, mol­ecules are linked through inter­molecular O—H⋯O and C—H⋯O hydrogen-bonding inter­actions, forming chains propagating in [20].

Related literature

For general background information on the applications of azo compounds, see: Chung & Stevens (1993 ▶); Carliell et al. (1995 ▶).

Experimental

Crystal data

• C₁₆H₁₀N₂O₈·2C₃H₇NO

• M _r = 504.45

• Triclinic,

• a = 6.2926 (13) Å

• b = 7.2114 (13) Å

• c = 13.653 (4) Å

• α = 80.94 (4)°

• β = 85.30 (4)°

• γ = 81.72 (3)°

• V = 604.3 (3) ų

• Z = 1

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 293 (2) K

• 0.20 × 0.20 × 0.20 mm

Data collection

• Rigaku SCXmini diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.971, T _max = 0.979

• 5593 measured reflections

• 2363 independent reflections

• 1607 reflections with I > 2σ(I)

• R _int = 0.029

Refinement

• R[F ² > 2σ(F ²)] = 0.052

• wR(F ²) = 0.154

• S = 1.04

• 2363 reflections

• 167 parameters

• H-atom parameters constrained

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O5i	0.82	1.72	2.541 (2)	174
O3—H3⋯O2ii	0.82	1.94	2.697 (2)	154
C4—H4⋯O3ii	0.93	2.42	3.305 (2)	159
C11—H11⋯O2iii	0.93	2.58	3.240 (3)	128

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

supplementary crystallographic information

Comment

Azo compounds are used as dyes in textile, paper manufacturing, pharmaceutial and food industries (Chung & Stevens, 1993; Carliell et al., 1995). Herein, we report the crystal structure of the title compound, which was obtained by reductive condensation reaction of 5-nitroisophthalic acid in the presence of NaOH.

The acid molecule of the title compound (Fig. 1) has a crystallographically imposed centre of symmetry and adopts an E-configuration with respect to the azo group. The molecular conformation is stabilized by intramolecular C—H···O hydrogen bonds (Table 1). In the crystal packing (Fig. 2), molecules are linked into layers parallel to the (210) plane by intermolecular O—H···O and C—H···O hydrogen bonds (Table 1).

Experimental

A solution of sodium hydroxide (35.9 g, 0.9 mol) in H₂O (125 ml) was added dropwise to a suspension of 5-nitroisophthalic acid (10 g, 50.3 mmol) in H₂O (125 ml). The mixture was heated at 50°C for 18 h. After filtration, the yellow solid obtained was dissolved in H₂O and acidified with HCl. Crystals suitable for X-ray analysis were obtained after 10 days by slow evaporation of a DMF solution.

Refinement

All H atoms were positioned geometrically and were allowed to ride on their parent atoms, with C—H = 0.93-0.96 Å, O—H = 0.82 Å, and with U_iso(H) = 1.5U_eq(C, O) or 1.2U_eq(C) for aromatic and aldehyde H atoms.

Figures

Fig. 1.

The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. [Symmetry code: (A) -x+3, -y, -z+1].

Fig. 2.

Packing diagram of the title compound, showing the structure along the c axis. Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C16H10N2O8·2C3H7NO	Z = 1
Mr = 504.45	F(000) = 264
Triclinic, P1	Dx = 1.386 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2926 (13) Å	Cell parameters from 1381 reflections
b = 7.2114 (13) Å	θ = 2.9–27.4°
c = 13.653 (4) Å	µ = 0.11 mm−1
α = 80.94 (4)°	T = 293 K
β = 85.30 (4)°	Cuboid, colourless
γ = 81.72 (3)°	0.20 × 0.20 × 0.20 mm
V = 604.3 (3) Å3

Data collection

Rigaku SCXmini diffractometer	2363 independent reflections
Radiation source: fine-focus sealed tube	1607 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0°, θmin = 2.9°
ω scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
Tmin = 0.971, Tmax = 0.979	l = −16→16
5593 measured reflections

Refinement

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0869P)2 + 0.0094P] where P = (Fo2 + 2Fc2)/3
2363 reflections	(Δ/σ)max < 0.001
167 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	1.2504 (3)	0.1247 (3)	0.53879 (14)	0.0368 (5)
C2	1.1485 (3)	0.1486 (3)	0.63147 (14)	0.0388 (5)
H2	1.2213	0.1037	0.6889	0.047*
C3	0.9387 (3)	0.2393 (3)	0.63829 (14)	0.0362 (4)
C4	0.8321 (3)	0.3072 (3)	0.55177 (14)	0.0361 (5)
H4	0.6909	0.3664	0.5558	0.043*
C5	0.9357 (3)	0.2870 (2)	0.45901 (13)	0.0340 (4)
C6	1.1450 (3)	0.1962 (2)	0.45217 (14)	0.0360 (4)
H6	1.2144	0.1830	0.3903	0.043*
C7	0.8248 (3)	0.3644 (3)	0.36581 (14)	0.0393 (5)
C8	0.8253 (3)	0.2634 (3)	0.73691 (14)	0.0429 (5)
C9	0.5021 (5)	0.1873 (5)	0.1616 (2)	0.0951 (10)
H9A	0.6554	0.1852	0.1536	0.143*
H9B	0.4689	0.0633	0.1894	0.143*
H9C	0.4427	0.2763	0.2052	0.143*
C10	0.1791 (4)	0.2888 (5)	0.0659 (2)	0.0897 (10)
H10A	0.1367	0.3194	−0.0013	0.135*
H10B	0.1337	0.3953	0.1003	0.135*
H10C	0.1133	0.1817	0.0988	0.135*
C11	0.5328 (4)	0.2465 (4)	−0.01670 (17)	0.0583 (6)
H11	0.4662	0.2823	−0.0764	0.070*
N1	1.4637 (2)	0.0230 (2)	0.54104 (12)	0.0396 (4)
N2	0.4107 (3)	0.2433 (3)	0.06578 (13)	0.0560 (5)
O1	0.9368 (2)	0.1852 (3)	0.81263 (10)	0.0609 (5)
H1	0.8628	0.1957	0.8643	0.091*
O2	0.6425 (2)	0.3456 (2)	0.74637 (11)	0.0587 (5)
O3	0.6225 (2)	0.4372 (2)	0.38429 (11)	0.0559 (5)
H3	0.5702	0.4880	0.3321	0.084*
O4	0.9084 (2)	0.3631 (3)	0.28388 (11)	0.0658 (5)
O5	0.7304 (3)	0.2054 (3)	−0.02061 (11)	0.0725 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0248 (10)	0.0368 (10)	0.0480 (12)	−0.0002 (7)	0.0004 (8)	−0.0085 (9)
C2	0.0308 (10)	0.0441 (11)	0.0393 (10)	0.0020 (8)	−0.0022 (8)	−0.0062 (9)
C3	0.0287 (10)	0.0376 (10)	0.0404 (11)	0.0008 (7)	0.0016 (8)	−0.0067 (8)
C4	0.0256 (10)	0.0376 (10)	0.0428 (11)	0.0035 (7)	0.0003 (8)	−0.0074 (8)
C5	0.0280 (10)	0.0340 (9)	0.0390 (10)	0.0004 (7)	0.0000 (7)	−0.0077 (8)
C6	0.0313 (10)	0.0375 (10)	0.0383 (10)	−0.0012 (8)	0.0023 (8)	−0.0083 (8)
C7	0.0334 (11)	0.0427 (11)	0.0401 (11)	0.0018 (8)	0.0006 (8)	−0.0084 (8)
C8	0.0368 (11)	0.0525 (12)	0.0356 (11)	0.0035 (9)	−0.0004 (8)	−0.0042 (9)
C9	0.097 (2)	0.142 (3)	0.0424 (15)	−0.011 (2)	−0.0023 (14)	−0.0094 (17)
C10	0.0544 (18)	0.110 (2)	0.093 (2)	0.0092 (15)	0.0136 (15)	−0.0082 (19)
C11	0.0547 (15)	0.0755 (16)	0.0417 (12)	0.0016 (12)	−0.0043 (10)	−0.0081 (11)
N1	0.0257 (9)	0.0437 (9)	0.0473 (9)	0.0046 (7)	0.0009 (7)	−0.0097 (8)
N2	0.0496 (12)	0.0716 (13)	0.0446 (10)	−0.0024 (9)	0.0042 (8)	−0.0110 (9)
O1	0.0468 (9)	0.0897 (12)	0.0349 (8)	0.0200 (8)	−0.0010 (7)	−0.0018 (8)
O2	0.0395 (9)	0.0859 (11)	0.0401 (8)	0.0211 (8)	0.0030 (6)	−0.0069 (8)
O3	0.0372 (9)	0.0786 (11)	0.0427 (8)	0.0188 (7)	−0.0053 (6)	−0.0032 (8)
O4	0.0494 (10)	0.1019 (13)	0.0383 (9)	0.0144 (8)	0.0017 (7)	−0.0113 (9)
O5	0.0458 (10)	0.1218 (16)	0.0445 (10)	0.0002 (9)	0.0043 (7)	−0.0103 (10)

Geometric parameters (Å, °)

C1—C6	1.394 (3)	C8—O1	1.304 (2)
C1—C2	1.395 (3)	C9—N2	1.447 (3)
C1—N1	1.434 (2)	C9—H9A	0.9600
C2—C3	1.389 (2)	C9—H9B	0.9600
C2—H2	0.9300	C9—H9C	0.9600
C3—C4	1.392 (3)	C10—N2	1.447 (3)
C3—C8	1.494 (3)	C10—H10A	0.9600
C4—C5	1.395 (3)	C10—H10B	0.9600
C4—H4	0.9300	C10—H10C	0.9600
C5—C6	1.387 (2)	C11—O5	1.235 (3)
C5—C7	1.492 (3)	C11—N2	1.309 (3)
C6—H6	0.9300	C11—H11	0.9300
C7—O4	1.197 (2)	N1—N1i	1.251 (3)
C7—O3	1.325 (2)	O1—H1	0.8200
C8—O2	1.222 (2)	O3—H3	0.8200
C6—C1—C2	120.34 (17)	O1—C8—C3	114.04 (17)
C6—C1—N1	124.35 (17)	N2—C9—H9A	109.5
C2—C1—N1	115.31 (17)	N2—C9—H9B	109.5
C3—C2—C1	120.22 (18)	H9A—C9—H9B	109.5
C3—C2—H2	119.9	N2—C9—H9C	109.5
C1—C2—H2	119.9	H9A—C9—H9C	109.5
C2—C3—C4	119.34 (17)	H9B—C9—H9C	109.5
C2—C3—C8	121.08 (18)	N2—C10—H10A	109.5
C4—C3—C8	119.57 (17)	N2—C10—H10B	109.5
C3—C4—C5	120.42 (17)	H10A—C10—H10B	109.5
C3—C4—H4	119.8	N2—C10—H10C	109.5
C5—C4—H4	119.8	H10A—C10—H10C	109.5
C6—C5—C4	120.25 (17)	H10B—C10—H10C	109.5
C6—C5—C7	118.99 (17)	O5—C11—N2	124.4 (2)
C4—C5—C7	120.75 (16)	O5—C11—H11	117.8
C5—C6—C1	119.40 (18)	N2—C11—H11	117.8
C5—C6—H6	120.3	N1i—N1—C1	113.5 (2)
C1—C6—H6	120.3	C11—N2—C10	122.1 (2)
O4—C7—O3	123.70 (19)	C11—N2—C9	121.0 (2)
O4—C7—C5	124.31 (18)	C10—N2—C9	116.8 (2)
O3—C7—C5	111.99 (17)	C8—O1—H1	109.5
O2—C8—O1	122.62 (18)	C7—O3—H3	109.5
O2—C8—C3	123.32 (18)

Symmetry codes: (i) −x+3, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3	0.93	2.38	2.704 (3)	100
C9—H9A···O5	0.96	2.37	2.763 (3)	104
O1—H1···O5ii	0.82	1.72	2.541 (2)	174
O3—H3···O2iii	0.82	1.94	2.697 (2)	154
C4—H4···O3iii	0.93	2.42	3.305 (2)	159
C11—H11···O2iv	0.93	2.58	3.240 (3)	128

Symmetry codes: (ii) x, y, z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y, z−1.