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

Zhang, L.; Qu, Z.-R.

doi:10.1107/S1600536808032819

organic compounds

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Volume 64| Part 11| November 2008| Page o2202

doi:10.1107/S1600536808032819

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

Li Zhang ^a and Zhi-Rong Qu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: quzr@seu.edu.cn

(Received 15 September 2008; accepted 10 October 2008; online 25 October 2008)

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 [2 $[\overline{1}]$ 0].

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.052
wR(F²) = 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

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) x, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) x, y, z-1.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808032819/rz2248sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032819/rz2248Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures top

	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.

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

Crystal data top

C₁₆H₁₀N₂O₈·2C₃H₇NO	Z = 1
M_r = 504.45	F(000) = 264
Triclinic, P1	D_x = 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 top

Rigaku SCXmini diffractometer	2363 independent reflections
Radiation source: fine-focus sealed tube	1607 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 2.9°
ω scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.971, T_max = 0.979	l = −16→16
5593 measured reflections

Refinement top

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(F_o²) + (0.0869P)² + 0.0094P] where P = (F_o² + 2F_c²)/3
2363 reflections	(Δ/σ)_max < 0.001
167 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₆H₁₀N₂O₈·2C₃H₇NO	γ = 81.72 (3)°
M_r = 504.45	V = 604.3 (3) Å³
Triclinic, P1	Z = 1
a = 6.2926 (13) Å	Mo Kα radiation
b = 7.2114 (13) Å	µ = 0.11 mm⁻¹
c = 13.653 (4) Å	T = 293 K
α = 80.94 (4)°	0.20 × 0.20 × 0.20 mm
β = 85.30 (4)°

Data collection top

Rigaku SCXmini diffractometer	2363 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1607 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.979	R_int = 0.029
5593 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
2363 reflections	Δρ_min = −0.19 e Å⁻³
167 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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 code: (i) −x+3, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

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···O2^iv	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.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₀N₂O₈·2C₃H₇NO
M_r	504.45
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.2926 (13), 7.2114 (13), 13.653 (4)
α, β, γ (°)	80.94 (4), 85.30 (4), 81.72 (3)
V (Å³)	604.3 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.971, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5593, 2363, 1607
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.154, 1.04
No. of reflections	2363
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O3	0.93	2.38	2.704 (3)	100.3
C9—H9A···O5	0.96	2.37	2.763 (3)	103.8
O1—H1···O5ⁱ	0.82	1.72	2.541 (2)	174.0
O3—H3···O2ⁱⁱ	0.82	1.94	2.697 (2)	154.0
C4—H4···O3ⁱⁱ	0.93	2.42	3.305 (2)	158.8
C11—H11···O2ⁱⁱⁱ	0.93	2.58	3.240 (3)	128.4

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

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to Dr Z.-R. Qu.

References

Carliell, C. M., Barclay, S. J., Naidoo, N., Buckley, C. A., Mulholland, D. A. & Senior, E. (1995). Water SA, 21, 61–69. CAS Google Scholar
Chung, K.-T. & Stevens, S. E. Jr (1993). Environ. Toxicol. Chem. 2, 2121–2132. CrossRef Web of Science Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 64| Part 11| November 2008| Page o2202

doi:10.1107/S1600536808032819

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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