tert-Butyl 2-(4-nitro­phen­oxy)acetate

Ali, Q.; Anis, I.; Raza Shah, M.; Ng, S.W.

doi:10.1107/S1600536811003229

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o532

doi:10.1107/S1600536811003229

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tert-Butyl 2-(4-nitrophenoxy)acetate

Qamar Ali,^a Itrat Anis,^a M. Raza Shah ^a and Seik Weng Ng ^b ^*

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 7527, Pakistan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 22 January 2011; accepted 25 January 2011; online 29 January 2011)

In the title molecule, C₁₂H₁₅NO₅, the nitrophenoxy portion is approximately planar (r.m.s. deviation = 0.034 Å) and makes an angle of 84.8 (1)° with respect to the –CH₂–C(=O)–O–C fragment. In the crystal, π–π stacking is observed between nearly parallel benzene rings of adjacent molecules, the centroid–centroid distance being 3.6806 (10) Å. Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For a study of the biopotency of the title compound, see: Arfan et al. (2010 ). For related structures, see: Ali et al. (2010 ); Mustafa et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₅NO₅
M_r = 253.25
Monoclinic, C 2/c
a = 19.2761 (7) Å
b = 12.1131 (4) Å
c = 11.7267 (5) Å
β = 111.682 (4)°
V = 2544.38 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.664, T_max = 1.000
5580 measured reflections
2824 independent reflections
2075 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.120
S = 1.06
2824 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O4ⁱ	0.95	2.50	3.201 (2)	130
C12—H12C⋯O2ⁱⁱ	0.98	2.55	3.489 (3)	161
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003229/xu5151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003229/xu5151Isup2.hkl

checkCIF report

Comment top

The C₁₂H₁₅NO₅ compound (Scheme I) was synthesized for evaluation of its potency against urease enzymes (Arfan et al., 2010); we have also synthesized other t-butyl esters of phenols (Ali et al., 2010; Mustafa et al., 2010). The nitrophenoxy portion is approximately planar (r.m.s. deviation 0.034 Å) this makes an angle of 84.8 (1)° with respect to the –CH₂–C(═O)–O–C fragment (Fig. 1). π-π stacking is observed between nearly parallel C1-benzene and C1ⁱ-benzene rings of adjacent molecules (symmetry code: (i) 1-x, y, 1/2-z), centroids distance being 3.6806 (10) Å. Intermolecular weak C—H···O hydrogen bonding is present in the crystal structure (Table 1).

Related literature top

For a study of the biopotency of the title compound, see: Arfan et al. (2010). For related structures, see: Ali et al. (2010); Mustafa et al. (2009).

Experimental top

4-Nitrophenol (1 g, 7 mmol) was dissolved in acetone (25 ml). To the solution was added potassium carbonate (2 g, 14 mmol). t-Butyl bromoacetate (2 ml, 14 mmol) was added amd the mixture heated for 3 hurs. The solvent was evaporated and the residue was dissolved in a mixture of water (50 ml) and ethyl acetate (50 ml). The aqueous layer was extracted three times with ethyl acetate. The combined organic phases were evaporated under reduced pressure and the solid material was recrystallized from n-hexane to give the produce in 80% yield.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of at C₁₂H₁₅NO₅ the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

tert-Butyl 2-(4-nitrophenoxy)acetate top

Crystal data top

C₁₂H₁₅NO₅	F(000) = 1072
M_r = 253.25	D_x = 1.322 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1942 reflections
a = 19.2761 (7) Å	θ = 2.3–28.5°
b = 12.1131 (4) Å	µ = 0.10 mm⁻¹
c = 11.7267 (5) Å	T = 100 K
β = 111.682 (4)°	Plate, colorless
V = 2544.38 (17) Å³	0.30 × 0.20 × 0.05 mm
Z = 8

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2824 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2075 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −17→24
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −13→15
T_min = 0.664, T_max = 1.000	l = −14→14
5580 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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0444P)² + 0.6948P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2824 reflections	Δρ_max = 0.27 e Å⁻³
164 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (4)

Crystal data top

C₁₂H₁₅NO₅	V = 2544.38 (17) Å³
M_r = 253.25	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.2761 (7) Å	µ = 0.10 mm⁻¹
b = 12.1131 (4) Å	T = 100 K
c = 11.7267 (5) Å	0.30 × 0.20 × 0.05 mm
β = 111.682 (4)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2824 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2075 reflections with I > 2σ(I)
T_min = 0.664, T_max = 1.000	R_int = 0.029
5580 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.06	Δρ_max = 0.27 e Å⁻³
2824 reflections	Δρ_min = −0.21 e Å⁻³
164 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.37259 (7)	0.48179 (13)	0.04938 (14)	0.0505 (4)
O2	0.41306 (9)	0.58588 (13)	0.21067 (16)	0.0581 (5)
O3	0.44798 (6)	0.11669 (9)	0.44903 (11)	0.0251 (3)
O4	0.59965 (6)	0.13203 (9)	0.53127 (11)	0.0279 (3)
O5	0.60685 (5)	0.11686 (9)	0.72849 (10)	0.0233 (3)
N1	0.39810 (8)	0.49483 (14)	0.16138 (17)	0.0387 (4)
C1	0.41151 (9)	0.39685 (14)	0.23939 (17)	0.0275 (4)
C2	0.43579 (9)	0.41028 (15)	0.36502 (17)	0.0287 (4)
H2	0.4428	0.4821	0.4001	0.034*
C3	0.44980 (8)	0.31747 (14)	0.43918 (16)	0.0258 (4)
H3	0.4666	0.3249	0.5258	0.031*
C4	0.43901 (8)	0.21342 (13)	0.38562 (15)	0.0221 (4)
C5	0.41454 (8)	0.20196 (14)	0.25872 (15)	0.0240 (4)
H5	0.4076	0.1304	0.2231	0.029*
C6	0.40040 (8)	0.29378 (15)	0.18461 (16)	0.0275 (4)
H6	0.3834	0.2866	0.0979	0.033*
C7	0.48824 (8)	0.11660 (14)	0.57817 (15)	0.0250 (4)
H7A	0.4768	0.0482	0.6141	0.030*
H7B	0.4723	0.1803	0.6155	0.030*
C8	0.57178 (8)	0.12344 (13)	0.60739 (16)	0.0223 (4)
C9	0.69011 (8)	0.12075 (13)	0.78688 (16)	0.0241 (4)
C10	0.72379 (9)	0.02283 (15)	0.74544 (17)	0.0312 (4)
H10A	0.7142	0.0297	0.6576	0.047*
H10B	0.7012	−0.0455	0.7602	0.047*
H10C	0.7778	0.0210	0.7917	0.047*
C11	0.70230 (9)	0.11251 (16)	0.92190 (16)	0.0352 (5)
H11A	0.6833	0.0415	0.9379	0.053*
H11B	0.6757	0.1727	0.9440	0.053*
H11C	0.7558	0.1180	0.9711	0.053*
C12	0.71824 (9)	0.23046 (15)	0.75805 (18)	0.0341 (5)
H12A	0.7088	0.2344	0.6701	0.051*
H12B	0.7720	0.2367	0.8049	0.051*
H12C	0.6921	0.2910	0.7806	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0487 (8)	0.0646 (11)	0.0413 (10)	0.0150 (7)	0.0201 (7)	0.0271 (8)
O2	0.0813 (11)	0.0317 (9)	0.0778 (13)	0.0110 (7)	0.0485 (10)	0.0148 (9)
O3	0.0243 (6)	0.0262 (7)	0.0213 (6)	−0.0002 (4)	0.0044 (5)	0.0025 (5)
O4	0.0270 (6)	0.0348 (7)	0.0239 (7)	−0.0001 (5)	0.0118 (5)	0.0043 (6)
O5	0.0185 (6)	0.0303 (7)	0.0201 (6)	−0.0014 (4)	0.0059 (5)	0.0008 (5)
N1	0.0367 (9)	0.0391 (10)	0.0513 (12)	0.0145 (7)	0.0290 (8)	0.0197 (9)
C1	0.0242 (8)	0.0314 (10)	0.0315 (10)	0.0087 (7)	0.0159 (7)	0.0098 (8)
C2	0.0289 (9)	0.0263 (9)	0.0348 (11)	0.0030 (7)	0.0162 (8)	−0.0010 (8)
C3	0.0269 (8)	0.0295 (10)	0.0220 (9)	0.0017 (7)	0.0100 (7)	−0.0013 (8)
C4	0.0165 (7)	0.0269 (9)	0.0233 (9)	0.0020 (6)	0.0078 (6)	0.0037 (7)
C5	0.0196 (8)	0.0305 (9)	0.0221 (9)	0.0020 (6)	0.0079 (6)	−0.0023 (7)
C6	0.0189 (8)	0.0424 (11)	0.0226 (9)	0.0052 (7)	0.0093 (7)	0.0036 (8)
C7	0.0224 (8)	0.0321 (10)	0.0188 (9)	−0.0002 (6)	0.0057 (7)	0.0043 (8)
C8	0.0237 (8)	0.0203 (8)	0.0223 (9)	−0.0002 (6)	0.0078 (7)	0.0019 (7)
C9	0.0171 (8)	0.0275 (9)	0.0247 (9)	−0.0023 (6)	0.0043 (7)	−0.0019 (7)
C10	0.0232 (8)	0.0327 (10)	0.0357 (11)	0.0011 (7)	0.0086 (7)	−0.0032 (9)
C11	0.0242 (9)	0.0523 (13)	0.0250 (10)	−0.0014 (8)	0.0044 (7)	−0.0021 (9)
C12	0.0261 (9)	0.0323 (10)	0.0422 (12)	−0.0054 (7)	0.0105 (8)	−0.0013 (9)

Geometric parameters (Å, º) top

O1—N1	1.231 (2)	C6—H6	0.9500
O2—N1	1.229 (2)	C7—C8	1.520 (2)
O3—C4	1.3641 (19)	C7—H7A	0.9900
O3—C7	1.424 (2)	C7—H7B	0.9900
O4—C8	1.2044 (19)	C9—C10	1.516 (2)
O5—C8	1.3307 (19)	C9—C11	1.516 (2)
O5—C9	1.4949 (18)	C9—C12	1.520 (2)
N1—C1	1.462 (2)	C10—H10A	0.9800
C1—C2	1.381 (3)	C10—H10B	0.9800
C1—C6	1.384 (2)	C10—H10C	0.9800
C2—C3	1.386 (2)	C11—H11A	0.9800
C2—H2	0.9500	C11—H11B	0.9800
C3—C4	1.389 (2)	C11—H11C	0.9800
C3—H3	0.9500	C12—H12A	0.9800
C4—C5	1.392 (2)	C12—H12B	0.9800
C5—C6	1.375 (2)	C12—H12C	0.9800
C5—H5	0.9500

C4—O3—C7	119.34 (12)	H7A—C7—H7B	108.1
C8—O5—C9	121.54 (12)	O4—C8—O5	127.32 (14)
O2—N1—O1	123.29 (17)	O4—C8—C7	124.28 (15)
O2—N1—C1	118.53 (18)	O5—C8—C7	108.39 (14)
O1—N1—C1	118.17 (18)	O5—C9—C10	110.06 (12)
C2—C1—C6	122.33 (16)	O5—C9—C11	101.67 (12)
C2—C1—N1	118.94 (17)	C10—C9—C11	111.34 (15)
C6—C1—N1	118.72 (17)	O5—C9—C12	109.67 (13)
C1—C2—C3	119.00 (17)	C10—C9—C12	112.49 (14)
C1—C2—H2	120.5	C11—C9—C12	111.08 (15)
C3—C2—H2	120.5	C9—C10—H10A	109.5
C2—C3—C4	119.37 (16)	C9—C10—H10B	109.5
C2—C3—H3	120.3	H10A—C10—H10B	109.5
C4—C3—H3	120.3	C9—C10—H10C	109.5
O3—C4—C3	124.42 (15)	H10A—C10—H10C	109.5
O3—C4—C5	114.94 (14)	H10B—C10—H10C	109.5
C3—C4—C5	120.59 (15)	C9—C11—H11A	109.5
C6—C5—C4	120.30 (16)	C9—C11—H11B	109.5
C6—C5—H5	119.8	H11A—C11—H11B	109.5
C4—C5—H5	119.8	C9—C11—H11C	109.5
C5—C6—C1	118.40 (16)	H11A—C11—H11C	109.5
C5—C6—H6	120.8	H11B—C11—H11C	109.5
C1—C6—H6	120.8	C9—C12—H12A	109.5
O3—C7—C8	110.82 (14)	C9—C12—H12B	109.5
O3—C7—H7A	109.5	H12A—C12—H12B	109.5
C8—C7—H7A	109.5	C9—C12—H12C	109.5
O3—C7—H7B	109.5	H12A—C12—H12C	109.5
C8—C7—H7B	109.5	H12B—C12—H12C	109.5

O2—N1—C1—C2	4.2 (2)	C3—C4—C5—C6	−0.3 (2)
O1—N1—C1—C2	−176.09 (15)	C4—C5—C6—C1	0.4 (2)
O2—N1—C1—C6	−174.92 (15)	C2—C1—C6—C5	−0.3 (2)
O1—N1—C1—C6	4.8 (2)	N1—C1—C6—C5	178.73 (13)
C6—C1—C2—C3	0.2 (2)	C4—O3—C7—C8	−76.68 (17)
N1—C1—C2—C3	−178.85 (13)	C9—O5—C8—O4	0.6 (2)
C1—C2—C3—C4	−0.1 (2)	C9—O5—C8—C7	179.79 (12)
C7—O3—C4—C3	−16.7 (2)	O3—C7—C8—O4	2.6 (2)
C7—O3—C4—C5	165.91 (13)	O3—C7—C8—O5	−176.57 (12)
C2—C3—C4—O3	−177.12 (14)	C8—O5—C9—C10	−62.81 (18)
C2—C3—C4—C5	0.1 (2)	C8—O5—C9—C11	179.09 (14)
O3—C4—C5—C6	177.24 (12)	C8—O5—C9—C12	61.45 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O4ⁱ	0.95	2.50	3.201 (2)	130
C12—H12C···O2ⁱⁱ	0.98	2.55	3.489 (3)	161

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO₅
M_r	253.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	19.2761 (7), 12.1131 (4), 11.7267 (5)
β (°)	111.682 (4)
V (Å³)	2544.38 (17)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.664, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5580, 2824, 2075
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.120, 1.06
No. of reflections	2824
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.21

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O4ⁱ	0.95	2.50	3.201 (2)	130
C12—H12C···O2ⁱⁱ	0.98	2.55	3.489 (3)	161

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y+1, −z+1.

Acknowledgements

We thank the Higher Education Commission of Pakistan and the University of Malaya for supporting this study.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Ali, Q., Yousuf, S., Raza Shah, M. & Ng, S. W. (2010). Acta Cryst. E66, o1739. Web of Science CSD CrossRef IUCr Journals Google Scholar
Arfan, M., Ali, M., Anis, I., Ahmad, H., Choudhary, M. I., Khan, A. & Shan, M. R. (2010). J. Enzym. Inhib. Med. Chem. 25, 296–299. Web of Science CrossRef CAS Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Mustafa, A., Shah, M. R., Khatoon, M. & Ng, S. W. (2009). Acta Cryst. E65, o912. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar