3-Methyl-4-nitro­phenol–4-dimethyl­amino­pyridine (1/1)

Muralidharan, S.; Nagapandiselvi, P.; Srinivasan, T.; Gopalakrishnan, R.; Velmurugan, D.

doi:10.1107/S1600536812041670

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3106

doi:10.1107/S1600536812041670

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3-Methyl-4-nitrophenol–4-dimethylaminopyridine (1/1)

Srinivasan Muralidharan,^a Perumal Nagapandiselvi,^a Thothadri Srinivasan,^b Rengasamy Gopalakrishnan ^a and Devadasan Velmurugan ^b ^*

^aDepartment of Physics, Anna University, Chennai 600 025, India, and ^bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 20 September 2012; accepted 5 October 2012; online 13 October 2012)

In the title adduct, C₇H₇NO₃^.C₇H₁₀N₂, the dihedral angle betwen the benzene ring and pyridine rings is 9.60 (8)° while the nitro group attached to the benzene ring makes a dihedral angle of 21.76 (13)°. The hydroxyl O atom deviates by 0.0247 (15) Å from the plane of the benzene ring. The crystal packing features O—H⋯N hydrogen bonds.

Related literature

For a related structure, see: Dong & Cheng (2012 ).

Experimental

Crystal data

C₇H₇NO₃·C₇H₁₀N₂
M_r = 275.31
Monoclinic, P 2₁ /c
a = 11.4923 (9) Å
b = 9.8362 (8) Å
c = 12.7781 (10) Å
β = 103.870 (5)°
V = 1402.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.30 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.968, T_max = 0.973
13307 measured reflections
3498 independent reflections
2469 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.185
S = 1.03
3498 reflections
184 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N3ⁱ	0.82	1.79	2.594 (2)	168
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812041670/pv2590sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041670/pv2590Isup2.hkl

checkCIF report

Comment top

In the molecule (fig.1),the pyridine ring (N3/C10/C11/C12/C13/C14) makes a dihedral angle of 9.60 (8)° with the phenyl ring (C1/C2/C3/C4/C5/C6) system. The oxygen atom O3 deviates by -0.0247 (15)Å from the plane of the phenyl ring. The carbon atom C7 deviates by deviates by 0.0677 (21)Å from the plane of the phenyl ring.

The nitrogen atom N1 deviates by -0.0285 (18)Å from the plane of the phenyl ring. The nitrogen atom N2 devaites by -0.0292 (18)Å from the plane of the pyridine ring. The crystal packing is stabilized by intermolecular O—H···N hydrogen bonds

Related literature top

For a related structure, see: Dong & Cheng (2012).

Experimental top

4-Dimethylaminopyridine and 3-methyl-4-nitrophenol were taken in equimolar (1:1) ratio using acetone as solvent. The solution was filtered in a clean beaker and optimally closed. The prepared solution was kept at room temperature for two days after which crystals suitable for X-ray diffraction were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. The crystal packing of the title compound viewed down c axis. H-atoms not involved in H-bonds have been excluded for clarity.

3-Methyl-4-nitrophenol–4-dimethylaminopyridine (1/1) top

Crystal data top

C₇H₇NO₃·C₇H₁₀N₂	F(000) = 584
M_r = 275.31	D_x = 1.304 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3498 reflections
a = 11.4923 (9) Å	θ = 1.8–28.4°
b = 9.8362 (8) Å	µ = 0.09 mm⁻¹
c = 12.7781 (10) Å	T = 293 K
β = 103.870 (5)°	Block, colourless
V = 1402.3 (2) Å³	0.35 × 0.30 × 0.30 mm
Z = 4

Data collection top

Bruker SMART APEXII area-detector diffractometer	3498 independent reflections
Radiation source: fine-focus sealed tube	2469 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and ϕ scans	θ_max = 28.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→12
T_min = 0.968, T_max = 0.973	k = −12→13
13307 measured reflections	l = −16→17

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0939P)² + 0.361P] where P = (F_o² + 2F_c²)/3
3498 reflections	(Δ/σ)_max = 0.001
184 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₇H₇NO₃·C₇H₁₀N₂	V = 1402.3 (2) Å³
M_r = 275.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.4923 (9) Å	µ = 0.09 mm⁻¹
b = 9.8362 (8) Å	T = 293 K
c = 12.7781 (10) Å	0.35 × 0.30 × 0.30 mm
β = 103.870 (5)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	3498 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2469 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.973	R_int = 0.028
13307 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.185	H-atom parameters constrained
S = 1.03	Δρ_max = 0.35 e Å⁻³
3498 reflections	Δρ_min = −0.27 e Å⁻³
184 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O3	0.15952 (12)	−0.10464 (16)	0.99019 (11)	0.0722 (4)
H3	0.1231	−0.0878	0.9281	0.108*
N3	−0.03318 (13)	0.41197 (16)	0.70694 (12)	0.0580 (4)
N1	0.55651 (14)	0.22673 (19)	1.12638 (14)	0.0661 (4)
O1	0.63106 (15)	0.1883 (2)	1.20437 (15)	0.0964 (6)
N2	0.17044 (15)	0.41211 (18)	1.02568 (13)	0.0637 (4)
C14	0.10524 (14)	0.41079 (16)	0.92229 (13)	0.0474 (4)
C6	0.38178 (14)	0.15782 (17)	0.97841 (13)	0.0475 (4)
C1	0.45173 (14)	0.14230 (17)	1.08398 (13)	0.0498 (4)
C13	0.13746 (15)	0.48787 (18)	0.84064 (15)	0.0524 (4)
H13	0.2061	0.5415	0.8567	0.063*
C3	0.32858 (16)	−0.0365 (2)	1.12182 (14)	0.0568 (4)
H3A	0.3113	−0.1011	1.1691	0.068*
C10	0.00038 (16)	0.33308 (18)	0.88898 (16)	0.0569 (4)
H10	−0.0253	0.2778	0.9381	0.068*
C5	0.28341 (14)	0.07288 (18)	0.94833 (13)	0.0499 (4)
H5	0.2347	0.0806	0.8791	0.060*
C4	0.25448 (14)	−0.02386 (17)	1.01789 (13)	0.0507 (4)
C11	−0.06391 (16)	0.33887 (19)	0.78414 (17)	0.0615 (5)
H11	−0.1342	0.2882	0.7652	0.074*
C2	0.42568 (15)	0.0457 (2)	1.15360 (13)	0.0558 (4)
H2	0.4749	0.0369	1.2226	0.067*
O2	0.56459 (19)	0.3367 (2)	1.08688 (19)	0.1206 (8)
C12	0.06747 (16)	0.48361 (18)	0.73744 (15)	0.0560 (4)
H12	0.0920	0.5343	0.6852	0.067*
C7	0.40796 (19)	0.2548 (2)	0.89618 (16)	0.0650 (5)
H7A	0.3587	0.2327	0.8264	0.098*
H7B	0.4909	0.2478	0.8948	0.098*
H7C	0.3910	0.3460	0.9148	0.098*
C9	0.1410 (3)	0.3213 (3)	1.10553 (18)	0.0842 (7)
H9A	0.0657	0.3478	1.1194	0.126*
H9B	0.2026	0.3264	1.1711	0.126*
H9C	0.1353	0.2297	1.0787	0.126*
C8	0.26892 (19)	0.5044 (3)	1.06203 (19)	0.0842 (7)
H8A	0.3380	0.4714	1.0400	0.126*
H8B	0.2870	0.5109	1.1392	0.126*
H8C	0.2475	0.5926	1.0311	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0643 (8)	0.0827 (10)	0.0624 (8)	−0.0234 (7)	0.0014 (6)	0.0170 (7)
N3	0.0535 (8)	0.0548 (8)	0.0598 (9)	0.0094 (7)	0.0020 (6)	−0.0021 (7)
N1	0.0526 (9)	0.0713 (11)	0.0682 (10)	−0.0036 (8)	0.0023 (7)	−0.0149 (8)
O1	0.0690 (10)	0.1098 (13)	0.0881 (11)	−0.0055 (9)	−0.0249 (8)	−0.0143 (10)
N2	0.0660 (10)	0.0714 (10)	0.0511 (8)	0.0051 (8)	0.0087 (7)	−0.0005 (7)
C14	0.0456 (8)	0.0435 (8)	0.0533 (9)	0.0073 (6)	0.0119 (6)	−0.0005 (7)
C6	0.0458 (8)	0.0496 (9)	0.0482 (8)	0.0043 (6)	0.0132 (6)	−0.0018 (6)
C1	0.0406 (8)	0.0544 (9)	0.0515 (9)	0.0044 (7)	0.0056 (6)	−0.0099 (7)
C13	0.0444 (8)	0.0520 (9)	0.0602 (10)	−0.0030 (7)	0.0112 (7)	0.0025 (7)
C3	0.0553 (9)	0.0649 (11)	0.0485 (9)	0.0058 (8)	0.0093 (7)	0.0111 (8)
C10	0.0567 (10)	0.0480 (9)	0.0698 (11)	−0.0029 (7)	0.0224 (8)	0.0054 (8)
C5	0.0484 (8)	0.0584 (9)	0.0399 (8)	−0.0007 (7)	0.0047 (6)	0.0034 (7)
C4	0.0459 (8)	0.0555 (9)	0.0488 (9)	−0.0016 (7)	0.0078 (6)	0.0023 (7)
C11	0.0453 (9)	0.0537 (10)	0.0813 (13)	−0.0029 (7)	0.0069 (8)	−0.0095 (9)
C2	0.0508 (9)	0.0687 (11)	0.0422 (8)	0.0103 (8)	0.0001 (7)	−0.0002 (7)
O2	0.1045 (15)	0.1048 (15)	0.1303 (17)	−0.0483 (12)	−0.0155 (12)	0.0154 (13)
C12	0.0585 (10)	0.0538 (9)	0.0563 (10)	0.0064 (8)	0.0150 (8)	0.0068 (7)
C7	0.0666 (11)	0.0673 (12)	0.0613 (11)	−0.0061 (9)	0.0157 (9)	0.0084 (9)
C9	0.1090 (18)	0.0927 (16)	0.0549 (11)	0.0277 (14)	0.0273 (11)	0.0153 (11)
C8	0.0637 (12)	0.115 (2)	0.0667 (13)	0.0000 (12)	0.0009 (10)	−0.0245 (13)

Geometric parameters (Å, º) top

O3—C4	1.328 (2)	C3—C4	1.401 (2)
O3—H3	0.8200	C3—H3A	0.9300
N3—C12	1.331 (2)	C10—C11	1.367 (3)
N3—C11	1.335 (3)	C10—H10	0.9300
N1—O2	1.207 (3)	C5—C4	1.396 (2)
N1—O1	1.209 (2)	C5—H5	0.9300
N1—C1	1.456 (2)	C11—H11	0.9300
N2—C14	1.354 (2)	C2—H2	0.9300
N2—C8	1.439 (3)	C12—H12	0.9300
N2—C9	1.456 (3)	C7—H7A	0.9600
C14—C10	1.404 (2)	C7—H7B	0.9600
C14—C13	1.409 (2)	C7—H7C	0.9600
C6—C5	1.384 (2)	C9—H9A	0.9600
C6—C1	1.403 (2)	C9—H9B	0.9600
C6—C7	1.502 (3)	C9—H9C	0.9600
C1—C2	1.383 (3)	C8—H8A	0.9600
C13—C12	1.371 (3)	C8—H8B	0.9600
C13—H13	0.9300	C8—H8C	0.9600
C3—C2	1.359 (2)

C4—O3—H3	109.5	O3—C4—C3	118.28 (15)
C12—N3—C11	115.74 (15)	C5—C4—C3	118.74 (15)
O2—N1—O1	121.00 (19)	N3—C11—C10	124.75 (16)
O2—N1—C1	119.70 (17)	N3—C11—H11	117.6
O1—N1—C1	119.19 (19)	C10—C11—H11	117.6
C14—N2—C8	121.99 (18)	C3—C2—C1	120.37 (15)
C14—N2—C9	120.72 (18)	C3—C2—H2	119.8
C8—N2—C9	117.27 (18)	C1—C2—H2	119.8
N2—C14—C10	122.35 (17)	N3—C12—C13	124.50 (17)
N2—C14—C13	122.36 (16)	N3—C12—H12	117.8
C10—C14—C13	115.29 (15)	C13—C12—H12	117.8
C5—C6—C1	116.28 (15)	C6—C7—H7A	109.5
C5—C6—C7	118.45 (15)	C6—C7—H7B	109.5
C1—C6—C7	125.23 (16)	H7A—C7—H7B	109.5
C2—C1—C6	122.06 (15)	C6—C7—H7C	109.5
C2—C1—N1	116.10 (15)	H7A—C7—H7C	109.5
C6—C1—N1	121.85 (17)	H7B—C7—H7C	109.5
C12—C13—C14	119.88 (16)	N2—C9—H9A	109.5
C12—C13—H13	120.1	N2—C9—H9B	109.5
C14—C13—H13	120.1	H9A—C9—H9B	109.5
C2—C3—C4	119.98 (16)	N2—C9—H9C	109.5
C2—C3—H3A	120.0	H9A—C9—H9C	109.5
C4—C3—H3A	120.0	H9B—C9—H9C	109.5
C11—C10—C14	119.82 (17)	N2—C8—H8A	109.5
C11—C10—H10	120.1	N2—C8—H8B	109.5
C14—C10—H10	120.1	H8A—C8—H8B	109.5
C6—C5—C4	122.56 (14)	N2—C8—H8C	109.5
C6—C5—H5	118.7	H8A—C8—H8C	109.5
C4—C5—H5	118.7	H8B—C8—H8C	109.5
O3—C4—C5	122.98 (15)

C8—N2—C14—C10	−172.07 (18)	C13—C14—C10—C11	−1.7 (2)
C9—N2—C14—C10	6.4 (3)	C1—C6—C5—C4	−0.3 (2)
C8—N2—C14—C13	7.6 (3)	C7—C6—C5—C4	177.63 (17)
C9—N2—C14—C13	−174.00 (17)	C6—C5—C4—O3	179.17 (16)
C5—C6—C1—C2	1.3 (2)	C6—C5—C4—C3	−0.7 (3)
C7—C6—C1—C2	−176.47 (17)	C2—C3—C4—O3	−179.11 (17)
C5—C6—C1—N1	−178.98 (15)	C2—C3—C4—C5	0.7 (3)
C7—C6—C1—N1	3.2 (3)	C12—N3—C11—C10	−0.4 (3)
O2—N1—C1—C2	−156.9 (2)	C14—C10—C11—N3	1.8 (3)
O1—N1—C1—C2	19.3 (3)	C4—C3—C2—C1	0.2 (3)
O2—N1—C1—C6	23.4 (3)	C6—C1—C2—C3	−1.3 (3)
O1—N1—C1—C6	−160.43 (18)	N1—C1—C2—C3	178.99 (16)
N2—C14—C13—C12	−179.41 (16)	C11—N3—C12—C13	−1.2 (3)
C10—C14—C13—C12	0.3 (2)	C14—C13—C12—N3	1.2 (3)
N2—C14—C10—C11	178.01 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N3ⁱ	0.82	1.79	2.594 (2)	168

Symmetry code: (i) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₇H₇NO₃·C₇H₁₀N₂
M_r	275.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.4923 (9), 9.8362 (8), 12.7781 (10)
β (°)	103.870 (5)
V (Å³)	1402.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.968, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	13307, 3498, 2469
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.185, 1.03
No. of reflections	3498
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.27

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N3ⁱ	0.82	1.79	2.594 (2)	168

Symmetry code: (i) −x, y−1/2, −z+3/2.

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection. TS thanks the DST for an Inspire fellowship.

References

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