2-tert-Butyl-4,6-di­nitro­phenol

Lynch, D.E.; McClenaghan, I.

doi:10.1107/S1600536804015855

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 60| Part 8| August 2004| Pages o1288-o1289

https://doi.org/10.1107/S1600536804015855

2-tert-Butyl-4,6-dinitrophenol

Daniel E. Lynch ^a ^* and Ian McClenaghan ^b

^aSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, England, and ^bKey Organics Ltd, Highfield Industrial Estate, Camelford, Cornwall PL32 9QZ, England
^*Correspondence e-mail: apx106@coventry.ac.uk

(Received 10 June 2004; accepted 29 June 2004; online 9 July 2004)

The structure of the title compound, C₁₀H₁₂N₂O₅, has been determined and is found to have an intramolecular hydrogen bond between the phenol group and one of the 6-nitro O atoms. The molecule packs in a zigzag hydrogen-bonded chain, consisting of an intermolecular hydrogen bond, parallel to the c axis, between the phenol group and a 4-nitro O atom. The dihedral angle between adjacent molecules in the chain is 82 (3)°.

Comment

The title compound, (I), was first prepared in 1938 (Ipatieff et al., 1938 ) by the nitration of 2,4-di-tert-butylphenol, with cleavage of the 4-tert-butyl group. It was later found that (I) could also be prepared by the nitration of 2,6-di-tert-butylphenol, with cleavage of the 6-tert-butyl group (Hart & Cassis, 1951 ). Attempts by Hart and Cassis at nitration without cleavage yielded small quantities of 3,3′,5,5′-tetra-tert-butyl-p-diphenoquinone. The Cambridge Structural Database (Version of April 2004; Allen, 2002 ) reveals only one structure of a molecule similar to (I), that being musk ambrette, 4-tert-butyl-3-methoxy-2,6-dinitrotoluene (De Ridder et al., 1990 ). In a series of studies to prepare organic salts of 2,6-disubstituted phenols, such as the title compound and 2,6-di-tert-butyl-4-nitrophenol, with simple organic bases, we characterized the structure of the title compound and report it here.

Compound (I) exists with an intramolecular hydrogen bond between the phenol group and one of the 6-nitro O atoms (Fig. 1) and packs in a zigzag hydrogen-bonded chain, parallel to the c axis, consisting of an intermolecular hydrogen bond between the phenol group and a 4-nitro O atom (Fig. 2). Hydrogen-bonding associations are listed in Table 1 and the dihedral angle between adjacent molecules in the chain is 82 (3)°.

Figure 1
The molecular structure (ORTEP-3; Farrugia, 1997

) and atom-numbering scheme for (I

). Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate the intramolecular hydrogen bond.

Figure 2
Packing diagram for (I

). [Symmetry code: (i) x, ½ − y, z − ½.] Dashed lines indicate intermolecular hydrogen bonds.

Experimental

The title compound, (I), was obtained from Key Organics Ltd. Crystals of (I) were grown from a methanol solution.

Crystal data

C₁₀H₁₂N₂O₅
M_r = 240.22
Monoclinic, P2₁/c
a = 9.974 (2) Å
b = 10.575 (2) Å
c = 11.547 (2) Å
β = 112.90 (3)°
V = 1122.0 (4) Å³
Z = 4
D_x = 1.422 Mg m⁻³
Mo Kα radiation
Cell parameters from 52 reflections
θ = 4.3–18.1°
μ = 0.12 mm⁻¹
T = 120 (2) K
Needle, yellow
0.20 × 0.06 × 0.06 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: none
5908 measured reflections
5912 independent reflections
4502 reflections with I > 2σ(I)
R_int = 0.070
θ_max = 25.0°
h = −11 → 11
k = −12 → 12
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.165
S = 1.04
5912 reflections
160 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.1108P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.027
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.033 (5)

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11⋯O62	0.82	1.85	2.5743 (17)	146
O11—H11⋯O42ⁱ	0.82	2.42	2.8926 (19)	118
Symmetry code: (i) $[x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]$ .

All H atoms were included in the refinement at calculated positions in the riding-model approximation, with C—H distances of 0.93 (aromatic H atoms) and 0.96 Å (CH₃ H atoms), and O—H distance of 0.82 Å. The isotropic displacement parameters were set equal to 1.5U_eq of the carrier atom for the methyl groups and 1.2U_eq of the carrier for aromatic CH and hydroxyl OH groups. Crystals of (I) were twinned with two nearly equal components related by a 180° rotation about the [100] reciprocal lattice direction. Combined data with complete or no overlap were used for refinement, and the twinning prevented merging of equivalent reflections before refinement. The partially overlapped reflections were rejected, resulting in a low data-completeness value of 89.9%.

Data collection: DENZO (Otwinowski & Minor, 1997 ) and COLLECT (Hooft, 1998 ); cell refinement: DENZO and COLLECT; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997), and COLLECT; 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 ) and PLUTON94 (Spek, 1994 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536804015855/dn6148sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804015855/dn6148Isup2.hkl

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997), and COLLECT; 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) and PLUTON94 (Spek, 1994); software used to prepare material for publication: SHELXL97.

2-tert-Butyl-4,6-dinitrophenol top

Crystal data top

C₁₀H₁₂N₂O₅	F(000) = 504
M_r = 240.22	D_x = 1.422 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 52 reflections
a = 9.974 (2) Å	θ = 4.3–18.1°
b = 10.575 (2) Å	µ = 0.12 mm⁻¹
c = 11.547 (2) Å	T = 120 K
β = 112.90 (3)°	Plate, yellow
V = 1122.0 (4) Å³	0.20 × 0.06 × 0.06 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD area-detector diffractometer	4502 reflections with I > 2σ(I)
Radiation source: Bruker–Nonius FR591 rotating anode	R_int = 0.000
Graphite monochromator	θ_max = 25.0°, θ_min = 2.7°
Detector resolution: 9.091 pixels mm^-1	h = −11→11
φ and ω scans	k = −12→12
5908 measured reflections	l = −12→12
5912 independent 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)] = 0.056	H-atom parameters constrained
wR(F²) = 0.165	w = 1/[σ²(F_o²) + (0.1108P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.027
5912 reflections	Δρ_max = 0.36 e Å⁻³
160 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (5)

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.

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

	x	y	z	U_iso*/U_eq
C1	0.08422 (16)	0.24756 (16)	0.01103 (17)	0.0175 (4)
O11	0.08686 (12)	0.34527 (12)	−0.06166 (12)	0.0252 (4)
H11	0.0059	0.3778	−0.0918	0.038*
C2	0.21649 (17)	0.17828 (16)	0.07515 (17)	0.0167 (4)
C21	0.35876 (16)	0.21422 (16)	0.05852 (18)	0.0199 (5)
C22	0.33651 (18)	0.19937 (18)	−0.08108 (18)	0.0273 (5)
H22A	0.2582	0.2530	−0.1322	0.041*
H22B	0.3133	0.1129	−0.1064	0.041*
H22C	0.4242	0.2229	−0.0913	0.041*
C23	0.40487 (19)	0.35174 (18)	0.1040 (2)	0.0311 (5)
H23A	0.4939	0.3718	0.0944	0.047*
H23B	0.4193	0.3591	0.1909	0.047*
H23C	0.3299	0.4093	0.0547	0.047*
C24	0.48590 (18)	0.12544 (18)	0.1379 (2)	0.0291 (5)
H24A	0.4601	0.0393	0.1130	0.044*
H24B	0.5040	0.1349	0.2254	0.044*
H24C	0.5720	0.1474	0.1243	0.044*
C3	0.21111 (17)	0.07892 (16)	0.15038 (17)	0.0182 (4)
H3	0.2946	0.0313	0.1915	0.022*
C4	0.08200 (17)	0.04759 (15)	0.16662 (18)	0.0187 (4)
N41	0.08388 (15)	−0.05678 (14)	0.25181 (15)	0.0225 (4)
O41	0.18873 (14)	−0.13023 (13)	0.28710 (14)	0.0362 (4)
O42	−0.02105 (13)	−0.06679 (11)	0.28282 (13)	0.0284 (4)
C5	−0.04623 (18)	0.11166 (16)	0.10471 (17)	0.0176 (4)
H5	−0.1311	0.0898	0.1152	0.021*
C6	−0.04398 (16)	0.20999 (15)	0.02624 (17)	0.0179 (4)
N61	−0.18396 (15)	0.27369 (15)	−0.04410 (15)	0.0231 (4)
O61	−0.29647 (11)	0.22493 (13)	−0.04595 (12)	0.0320 (4)
O62	−0.18238 (12)	0.37669 (12)	−0.09758 (13)	0.0306 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0198 (9)	0.0146 (9)	0.0188 (12)	−0.0009 (9)	0.0085 (8)	−0.0030 (8)
O11	0.0178 (6)	0.0247 (8)	0.0322 (9)	0.0036 (6)	0.0087 (6)	0.0090 (6)
C2	0.0177 (9)	0.0173 (9)	0.0157 (12)	−0.0001 (8)	0.0071 (8)	−0.0029 (8)
C21	0.0120 (8)	0.0214 (10)	0.0258 (13)	0.0017 (8)	0.0067 (8)	−0.0004 (8)
C22	0.0183 (9)	0.0354 (12)	0.0305 (14)	0.0011 (9)	0.0122 (9)	0.0051 (9)
C23	0.0267 (10)	0.0317 (12)	0.0373 (15)	−0.0066 (10)	0.0151 (10)	−0.0009 (10)
C24	0.0185 (10)	0.0364 (12)	0.0338 (14)	0.0041 (9)	0.0118 (9)	0.0052 (9)
C3	0.0154 (9)	0.0186 (10)	0.0180 (12)	0.0030 (8)	0.0036 (8)	−0.0051 (7)
C4	0.0212 (9)	0.0140 (9)	0.0214 (12)	−0.0030 (8)	0.0088 (8)	−0.0044 (8)
N41	0.0255 (8)	0.0208 (8)	0.0196 (11)	−0.0044 (8)	0.0072 (8)	−0.0028 (7)
O41	0.0333 (8)	0.0328 (8)	0.0439 (11)	0.0107 (7)	0.0163 (7)	0.0148 (7)
O42	0.0298 (7)	0.0277 (7)	0.0330 (9)	−0.0074 (6)	0.0180 (7)	0.0012 (6)
C5	0.0168 (9)	0.0208 (10)	0.0159 (12)	−0.0030 (8)	0.0072 (8)	−0.0054 (8)
C6	0.0129 (8)	0.0181 (9)	0.0191 (12)	0.0056 (8)	0.0022 (8)	−0.0012 (8)
N61	0.0176 (8)	0.0264 (10)	0.0249 (11)	0.0027 (8)	0.0077 (7)	−0.0015 (7)
O61	0.0148 (6)	0.0453 (9)	0.0369 (10)	−0.0020 (7)	0.0113 (6)	0.0051 (7)
O62	0.0221 (7)	0.0243 (8)	0.0430 (10)	0.0055 (6)	0.0102 (7)	0.0087 (7)

Geometric parameters (Å, º) top

C1—O11	1.338 (2)	C24—H24A	0.96
C1—C6	1.414 (2)	C24—H24B	0.96
C1—C2	1.437 (2)	C24—H24C	0.96
O11—H11	0.82	C3—C4	1.411 (2)
C2—C3	1.378 (2)	C3—H3	0.93
C2—C21	1.551 (2)	C4—C5	1.376 (2)
C21—C22	1.547 (3)	C4—N41	1.474 (2)
C21—C23	1.554 (3)	N41—O42	1.2355 (18)
C21—C24	1.557 (3)	N41—O41	1.2375 (18)
C22—H22A	0.96	C5—C6	1.385 (2)
C22—H22B	0.96	C5—H5	0.93
C22—H22C	0.96	C6—N61	1.477 (2)
C23—H23A	0.96	N61—O61	1.2276 (16)
C23—H23B	0.96	N61—O62	1.2552 (18)
C23—H23C	0.96

O11—C1—C6	122.31 (14)	C21—C24—H24A	109.5
O11—C1—C2	118.60 (14)	C21—C24—H24B	109.5
C6—C1—C2	119.08 (15)	H24A—C24—H24B	109.5
C1—O11—H11	109.5	C21—C24—H24C	109.5
C3—C2—C1	117.42 (15)	H24A—C24—H24C	109.5
C3—C2—C21	121.79 (15)	H24B—C24—H24C	109.5
C1—C2—C21	120.79 (15)	C2—C3—C4	121.63 (16)
C22—C21—C2	109.68 (14)	C2—C3—H3	119.2
C22—C21—C23	110.52 (15)	C4—C3—H3	119.2
C2—C21—C23	110.63 (15)	C5—C4—C3	121.80 (16)
C22—C21—C24	107.82 (15)	C5—C4—N41	118.90 (15)
C2—C21—C24	110.72 (15)	C3—C4—N41	119.30 (15)
C23—C21—C24	107.41 (15)	O42—N41—O41	123.60 (15)
C21—C22—H22A	109.5	O42—N41—C4	117.74 (14)
C21—C22—H22B	109.5	O41—N41—C4	118.66 (14)
H22A—C22—H22B	109.5	C4—C5—C6	117.45 (16)
C21—C22—H22C	109.5	C4—C5—H5	121.3
H22A—C22—H22C	109.5	C6—C5—H5	121.3
H22B—C22—H22C	109.5	C5—C6—C1	122.54 (15)
C21—C23—H23A	109.5	C5—C6—N61	116.73 (15)
C21—C23—H23B	109.5	C1—C6—N61	120.72 (15)
H23A—C23—H23B	109.5	O61—N61—O62	122.85 (14)
C21—C23—H23C	109.5	O61—N61—C6	118.70 (15)
H23A—C23—H23C	109.5	O62—N61—C6	118.44 (14)
H23B—C23—H23C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O62	0.82	1.85	2.5743 (17)	146
O11—H11···O42ⁱ	0.82	2.42	2.8926 (19)	118

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

The authors thank the EPSRC National Crystallography Service (Southampton, England).

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