(E)-2-Methyl-4-[(4-nitro­phen­yl)diazen­yl]phenol dimethyl­formamide solvate

Koşar, B.; Albayrak, Ç.; Gümrükçüoglu, \\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\?I.; Büyükgüngör, O.

doi:10.1107/S1600536807059454

(E)-2-Methyl-4-[(4-nitrophenyl)diazenyl]phenol dimethylformamide solvate

B. Koşar, Ç. Albayrak, I. Gümrükçüoglu and O. Büyükgüngör

The title compound, C₁₃H₁₁N₃O₃·C₃H₇NO, displays an intermolecular O—H

O hydrogen bond between the hydroxyl group and the carbonyl O atom of the solvent molecule. The configuration of the N=N double bond is trans and the dihedral angle between the two aromatic rings is 24.85 (6)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059454/bt2612sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059454/bt2612Isup2.hkl Contains datablock I

CCDC reference: 672988

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.052
wR factor = 0.142
Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.134
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.13
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         40 Perc.
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3     -   C11     ..       5.39 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C8     -   C13     ..       6.69 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N4
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Azo compounds are used as dyes in textile, printing, paper manufacturing, pharmaceutial and food industries. All of them contain at least one azo group, which links two sp²-hybridized C atoms. In our ongoing work, these C atoms are part of aromatic systems.

Related literature top

For the related compounds 4-[(4-methylphenyl)diazenyl]-6- methoxy-2-{[tris(hydroxymethyl)-methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one and 4-[(3-chlorophenyl)diazenyl]-6-methoxy-2-{[tris(hydroxymethyl)-methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one, see: Koşar et al. (2004a,b).

Experimental top

A mixture of 4-nitroaniline (4.47 g, 32.4 mmol), water (50 ml) and concentrated hydrochloric acid (8.14 ml, 97.2 mmol) was stirred until a clear solution was obtained. This solution was cooled to 273–278 K and a solution of sodium nitrite (3,13 g, 45.36 mmol) in water was added dropwise while the temperature was maintained below 278 K. The resulting mixture was stirred for 30 min in an ice bath. An o-Cresol (3.5 g, 32.4 mmol) solution (pH 9) was gradually added to a cooled solution of 4-nitrobenzenediazonium chloride, prepared as described above, and the resulting mixture was stirred at 273–278 K for 60 min in ice bath. The product was recrystallized from ethyl alcohol to obtain solid (E)-2-methyl-4-[(4-nitrophenyl)diazenyl]phenol. Crystals were obtained by slow evaporation from DMF (yield %75, m.p. 480–482 K).

Computing details top

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

Figures top

Fig. 1. A view of the molecule, with atom labels and 30% probability displacement ellipsoids for non-H atoms.

(E)-2-Methyl-4-[(4-nitrophenyl)diazenyl]phenol dimethylformamide solvate top

Crystal data top

C₁₃H₁₁N₃O₃·C₃H₇NO	D_x = 1.323 Mg m⁻³
M_r = 330.34	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1369 reflections
a = 7.1951 (6) Å	θ = 1.8–24.9°
b = 11.4501 (7) Å	µ = 0.10 mm⁻¹
c = 40.252 (2) Å	T = 293 K
V = 3316.1 (4) Å³	Plate, red
Z = 8	0.50 × 0.40 × 0.09 mm
F(000) = 1392

Data collection top

STOE IPDS 2 diffractometer	2925 independent reflections
Radiation source: fine-focus sealed tube	1177 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.134
Detector resolution: 6.67 pixels mm^-1	θ_max = 25.1°, θ_min = 3.0°
ω scan	h = −8→8
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
T_min = 0.473, T_max = 0.877	l = −45→47
28423 measured reflections

Refinement top

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)] = 0.052	H-atom parameters constrained
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.0656P)²] where P = (F_o² + 2F_c²)/3
S = 0.84	(Δ/σ)_max < 0.001
2925 reflections	Δρ_max = 0.17 e Å⁻³
221 parameters	Δρ_min = −0.15 e Å⁻³
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0035 (5)

Crystal data top

C₁₃H₁₁N₃O₃·C₃H₇NO	V = 3316.1 (4) Å³
M_r = 330.34	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.1951 (6) Å	µ = 0.10 mm⁻¹
b = 11.4501 (7) Å	T = 293 K
c = 40.252 (2) Å	0.50 × 0.40 × 0.09 mm

Data collection top

STOE IPDS 2 diffractometer	2925 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	1177 reflections with I > 2σ(I)
T_min = 0.473, T_max = 0.877	R_int = 0.134
28423 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	2 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 0.84	Δρ_max = 0.17 e Å⁻³
2925 reflections	Δρ_min = −0.15 e Å⁻³
221 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	0.5794 (4)	0.5894 (3)	0.35445 (8)	0.0724 (9)
C2	0.5428 (4)	0.7036 (2)	0.36521 (8)	0.0720 (8)
C3	0.5668 (4)	0.7278 (3)	0.39844 (8)	0.0739 (9)
H3	0.5447	0.8031	0.4061	0.089*
C4	0.6239 (4)	0.6415 (3)	0.42095 (8)	0.0724 (8)
C5	0.6587 (4)	0.5303 (3)	0.40948 (8)	0.0795 (9)
H5	0.6969	0.4726	0.4242	0.095*
C6	0.6374 (5)	0.5044 (3)	0.37665 (8)	0.0794 (9)
H6	0.6619	0.4292	0.3691	0.095*
C7	0.4750 (5)	0.7943 (2)	0.34091 (8)	0.0906 (11)
H7A	0.3609	0.7683	0.3310	0.136*
H7B	0.5668	0.8057	0.3239	0.136*
H7C	0.4540	0.8666	0.3524	0.136*
C8	0.6317 (4)	0.7776 (3)	0.49993 (8)	0.0721 (8)
C9	0.6518 (5)	0.8906 (3)	0.51015 (8)	0.0849 (10)
H9	0.6685	0.9491	0.4944	0.102*
C10	0.6479 (5)	0.9190 (3)	0.54313 (8)	0.0800 (9)
H10	0.6615	0.9963	0.5498	0.096*
C11	0.6239 (4)	0.8322 (3)	0.56618 (7)	0.0700 (8)
C12	0.6051 (4)	0.7175 (3)	0.55705 (9)	0.0807 (9)
H12	0.5899	0.6594	0.5730	0.097*
C13	0.6093 (4)	0.6899 (3)	0.52346 (9)	0.0798 (9)
H13	0.5972	0.6126	0.5167	0.096*
C14	0.5340 (6)	0.2559 (4)	0.30409 (9)	0.0985 (11)
H14	0.6045	0.2312	0.3221	0.118*
C15	0.3192 (7)	0.2085 (5)	0.26042 (11)	0.1502 (18)
H15A	0.3223	0.2916	0.2573	0.225*
H15B	0.1943	0.1843	0.2652	0.225*
H15C	0.3615	0.1705	0.2405	0.225*
C16	0.4454 (7)	0.0558 (3)	0.29793 (13)	0.1434 (17)
H16A	0.5206	0.0489	0.3175	0.215*
H16B	0.4983	0.0095	0.2804	0.215*
H16C	0.3219	0.0287	0.3026	0.215*
N1	0.6423 (4)	0.6580 (2)	0.45645 (6)	0.0793 (7)
N2	0.6258 (4)	0.7616 (2)	0.46413 (6)	0.0795 (8)
N3	0.6146 (4)	0.8638 (3)	0.60128 (8)	0.0869 (8)
N4	0.4384 (4)	0.1770 (2)	0.28767 (7)	0.0891 (8)
O1	0.5537 (3)	0.56890 (17)	0.32164 (5)	0.0928 (7)
H1	0.5784	0.5005	0.3175	0.139*
O2	0.6458 (4)	0.9649 (2)	0.60921 (6)	0.1128 (9)
O3	0.5750 (4)	0.7869 (2)	0.62114 (6)	0.1149 (9)
O4	0.5362 (5)	0.3596 (2)	0.29714 (7)	0.1331 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.074 (2)	0.080 (2)	0.063 (2)	−0.0053 (16)	0.0035 (16)	−0.0091 (16)
C2	0.075 (2)	0.0710 (18)	0.070 (2)	−0.0002 (15)	0.0017 (17)	−0.0048 (16)
C3	0.067 (2)	0.0716 (18)	0.083 (3)	−0.0058 (16)	0.0047 (17)	−0.0120 (17)
C4	0.061 (2)	0.0793 (19)	0.0768 (15)	−0.0057 (16)	0.0004 (17)	0.0016 (17)
C5	0.084 (2)	0.076 (2)	0.079 (3)	0.0004 (16)	0.0020 (19)	0.0042 (17)
C6	0.090 (2)	0.0761 (19)	0.072 (2)	−0.0020 (18)	0.0029 (19)	−0.0085 (18)
C7	0.115 (3)	0.0817 (19)	0.076 (2)	0.0060 (19)	−0.007 (2)	0.0028 (17)
C8	0.064 (2)	0.080 (2)	0.0721 (14)	0.0041 (16)	−0.0040 (17)	0.0034 (17)
C9	0.097 (3)	0.082 (2)	0.076 (3)	0.0024 (19)	−0.0035 (19)	0.0017 (17)
C10	0.094 (3)	0.0737 (19)	0.072 (2)	−0.0006 (17)	0.000 (2)	−0.0055 (17)
C11	0.069 (2)	0.082 (2)	0.059 (2)	0.0024 (16)	0.0004 (16)	−0.0065 (17)
C12	0.082 (3)	0.084 (2)	0.077 (3)	0.0038 (18)	−0.0007 (18)	0.0031 (17)
C13	0.079 (3)	0.0688 (19)	0.092 (3)	0.0039 (16)	−0.0053 (19)	−0.0145 (19)
C14	0.114 (3)	0.109 (3)	0.072 (3)	0.002 (3)	0.007 (2)	−0.004 (2)
C15	0.142 (4)	0.208 (5)	0.101 (4)	0.022 (4)	−0.030 (3)	−0.013 (3)
C16	0.164 (5)	0.088 (3)	0.178 (5)	−0.016 (3)	0.020 (4)	0.008 (3)
N1	0.0747 (18)	0.0811 (17)	0.0820 (15)	−0.0049 (14)	−0.0012 (15)	−0.0062 (14)
N2	0.089 (2)	0.0741 (16)	0.0752 (14)	0.0021 (14)	0.0016 (15)	−0.0015 (13)
N3	0.074 (2)	0.111 (2)	0.076 (2)	0.0067 (17)	0.0012 (16)	−0.0116 (19)
N4	0.095 (2)	0.0920 (19)	0.080 (2)	0.0020 (17)	−0.0018 (17)	−0.0043 (16)
O1	0.125 (2)	0.0827 (13)	0.0706 (16)	0.0053 (13)	−0.0023 (13)	−0.0112 (11)
O2	0.140 (2)	0.1082 (18)	0.0901 (19)	0.0084 (16)	−0.0070 (16)	−0.0325 (14)
O3	0.135 (2)	0.140 (2)	0.0699 (17)	−0.0055 (18)	0.0115 (15)	0.0098 (15)
O4	0.201 (3)	0.0948 (17)	0.104 (2)	−0.0107 (18)	0.011 (2)	−0.0246 (15)

Geometric parameters (Å, º) top

C1—O1	1.354 (3)	C10—H10	0.9300
C1—C6	1.386 (4)	C11—C12	1.370 (4)
C1—C2	1.402 (4)	C11—N3	1.460 (4)
C2—C3	1.377 (4)	C12—C13	1.389 (4)
C2—C7	1.508 (4)	C12—H12	0.9300
C3—C4	1.402 (4)	C13—H13	0.9300
C3—H3	0.9300	C14—O4	1.219 (4)
C4—C5	1.377 (4)	C14—N4	1.314 (4)
C4—N1	1.447 (4)	C14—H14	0.9300
C5—C6	1.363 (4)	C15—N4	1.438 (5)
C5—H5	0.9300	C15—H15A	0.9600
C6—H6	0.9300	C15—H15B	0.9600
C7—H7A	0.9600	C15—H15C	0.9600
C7—H7B	0.9600	C16—N4	1.449 (4)
C7—H7C	0.9600	C16—H16A	0.9600
C8—C9	1.365 (4)	C16—H16B	0.9600
C8—C13	1.390 (4)	C16—H16C	0.9600
C8—N2	1.453 (4)	N1—N2	1.231 (3)
C9—C10	1.367 (4)	N3—O2	1.222 (3)
C9—H9	0.9300	N3—O3	1.222 (3)
C10—C11	1.371 (4)	O1—H1	0.8200

O1—C1—C6	123.2 (3)	C12—C11—C10	121.8 (3)
O1—C1—C2	116.0 (3)	C12—C11—N3	119.5 (3)
C6—C1—C2	120.8 (3)	C10—C11—N3	118.7 (3)
C3—C2—C1	117.6 (3)	C11—C12—C13	118.5 (3)
C3—C2—C7	122.2 (3)	C11—C12—H12	120.8
C1—C2—C7	120.2 (3)	C13—C12—H12	120.8
C2—C3—C4	121.6 (3)	C12—C13—C8	120.1 (3)
C2—C3—H3	119.2	C12—C13—H13	119.9
C4—C3—H3	119.2	C8—C13—H13	119.9
C5—C4—C3	119.2 (3)	O4—C14—N4	124.1 (4)
C5—C4—N1	115.8 (3)	O4—C14—H14	117.9
C3—C4—N1	125.0 (3)	N4—C14—H14	117.9
C6—C5—C4	120.4 (3)	N4—C15—H15A	109.5
C6—C5—H5	119.8	N4—C15—H15B	109.5
C4—C5—H5	119.8	H15A—C15—H15B	109.5
C5—C6—C1	120.4 (3)	N4—C15—H15C	109.5
C5—C6—H6	119.8	H15A—C15—H15C	109.5
C1—C6—H6	119.8	H15B—C15—H15C	109.5
C2—C7—H7A	109.5	N4—C16—H16A	109.5
C2—C7—H7B	109.5	N4—C16—H16B	109.5
H7A—C7—H7B	109.5	H16A—C16—H16B	109.5
C2—C7—H7C	109.5	N4—C16—H16C	109.5
H7A—C7—H7C	109.5	H16A—C16—H16C	109.5
H7B—C7—H7C	109.5	H16B—C16—H16C	109.5
C9—C8—C13	119.4 (3)	N2—N1—C4	111.4 (3)
C9—C8—N2	114.9 (3)	N1—N2—C8	111.6 (2)
C13—C8—N2	125.5 (3)	O2—N3—O3	123.7 (3)
C8—C9—C10	121.1 (3)	O2—N3—C11	118.6 (3)
C8—C9—H9	119.5	O3—N3—C11	117.7 (3)
C10—C9—H9	119.5	C14—N4—C15	121.6 (3)
C9—C10—C11	119.1 (3)	C14—N4—C16	119.8 (4)
C9—C10—H10	120.4	C15—N4—C16	118.6 (4)
C11—C10—H10	120.4	C1—O1—H1	109.5

O1—C1—C2—C3	179.8 (3)	C9—C10—C11—N3	−178.3 (3)
C6—C1—C2—C3	0.1 (5)	C10—C11—C12—C13	−0.6 (5)
O1—C1—C2—C7	1.3 (4)	N3—C11—C12—C13	178.3 (3)
C6—C1—C2—C7	−178.4 (3)	C11—C12—C13—C8	−0.1 (5)
C1—C2—C3—C4	−0.7 (4)	C9—C8—C13—C12	0.9 (5)
C7—C2—C3—C4	177.8 (3)	N2—C8—C13—C12	−175.6 (3)
C2—C3—C4—C5	0.7 (4)	C5—C4—N1—N2	173.7 (3)
C2—C3—C4—N1	−176.3 (3)	C3—C4—N1—N2	−9.1 (4)
C3—C4—C5—C6	−0.2 (5)	C4—N1—N2—C8	176.1 (2)
N1—C4—C5—C6	177.2 (3)	C9—C8—N2—N1	167.4 (3)
C4—C5—C6—C1	−0.4 (5)	C13—C8—N2—N1	−16.0 (4)
O1—C1—C6—C5	−179.3 (3)	C12—C11—N3—O2	174.4 (3)
C2—C1—C6—C5	0.4 (5)	C10—C11—N3—O2	−6.7 (4)
C13—C8—C9—C10	−0.9 (5)	C12—C11—N3—O3	−5.9 (4)
N2—C8—C9—C10	175.9 (3)	C10—C11—N3—O3	173.0 (3)
C8—C9—C10—C11	0.2 (5)	O4—C14—N4—C15	−2.9 (6)
C9—C10—C11—C12	0.5 (5)	O4—C14—N4—C16	179.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.82	1.84	2.595 (3)	153

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁N₃O₃·C₃H₇NO
M_r	330.34
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	7.1951 (6), 11.4501 (7), 40.252 (2)
V (Å³)	3316.1 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.40 × 0.09

Data collection
Diffractometer	STOE IPDS 2 diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.473, 0.877
No. of measured, independent and observed [I > 2σ(I)] reflections	28423, 2925, 1177
R_int	0.134
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.143, 0.84
No. of reflections	2925
No. of parameters	221
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).