N-Acetyl-5-chloro-3-nitro-l-tyrosine ethyl ester.

The title compound, C(13)H(15)ClN(2)O(6), was synthesized by hypochlorous acid-mediated chlorination of N-acetyl-3-nitro-l-tyrosine ethyl ester. The OH group forms an intra-molecular O-H⋯O hydrogen bond to the nitro group and the N-H group forms an inter-molecular N-H⋯O hydrogen bonds to an amide O atom, linking the mol-ecules into chains along [100]. The crystal studied was a non-merohedral twin, with a 0.907 (4):0.093 (4) domain ratio.

Related literature

For background to per­oxy­nitrite and its reactions with amino acids, see: Alvarez et al. (1999 ▶); Beckman (2009 ▶); Ceriello (2002 ▶); Crow (1999 ▶); Dahaoui et al. (1999 ▶); Darwish et al. 2007 ▶; Janik et al. (2007 ▶, 2008 ▶); Koszelak & van der Helm (1981 ▶); Pieret et al. (1972 ▶); Pitt & Spickett (2008 ▶); Soriano-García (1993) ▶; Stout et al. (2000 ▶); Uppu & Pryor (1999 ▶); Uppu et al. (1996 ▶); Whiteman & Halliwell (1999 ▶); Winter­bourn (2002 ▶).

Experimental

Crystal data

C13H15ClN2O6

M = 330.72

Monoclinic,

a = 5.1513 (4) Å

b = 10.6761 (9) Å

c = 13.2849 (8) Å

β = 93.689 (4)°

V = 729.10 (9) Å3

Z = 2

Cu Kα radiation

μ = 2.63 mm−1

T = 90 K

0.34 × 0.11 × 0.03 mm

Data collection

Bruker Kappa APEXII DUO area-detector diffractometer

Absorption correction: multi-scan (TWINABS; Sheldrick, 2002 ▶) T min = 0.468, T max = 0.925

7589 measured reflections

2307 independent reflections

2299 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.091

S = 1.07

2307 reflections

208 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.20 e Å−3

Absolute structure: Flack (1983 ▶), 961 Friedel pairs

Flack parameter: 0.078 (17)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); 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 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812036380/hb6933sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036380/hb6933Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H15ClN2O6	F(000) = 344
Mr = 330.72	Dx = 1.506 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2yb	Cell parameters from 1900 reflections
a = 5.1513 (4) Å	θ = 7.9–67.6°
b = 10.6761 (9) Å	µ = 2.63 mm−1
c = 13.2849 (8) Å	T = 90 K
β = 93.689 (4)°	Lath, yellow
V = 729.10 (9) Å3	0.34 × 0.11 × 0.03 mm
Z = 2

Bruker Kappa APEXII DUO area-detector diffractometer	2307 independent reflections
Radiation source: IµS microfocus	2299 reflections with I > 2σ(I)
QUAZAR multilayer optics monochromator	Rint = 0.058
φ and ω scans	θmax = 68.2°, θmin = 6.7°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2002)	h = −6→6
Tmin = 0.468, Tmax = 0.925	k = −12→12
7589 measured reflections	l = −15→15

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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.029P)2 + 0.4076P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2307 reflections	Δρmax = 0.32 e Å−3
208 parameters	Δρmin = −0.20 e Å−3
2 restraints	Absolute structure: Flack (1983), 961 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.078 (17)

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. The crystal not single, and was treated as a nonmerohedral twin by rotation of 4.6 degrees about reciprocal axis 0.070 1.000 - 0.042 and real axis 0.300 1.000 - 0.019 The twin law is: (0.991, 0.000, -0.032, 0.006, 1.000, 0.014, 0.215, -0.021, 1.002)The structure was refined versus. TWIN5 data, yielding BASF=0.093 (4).

	x	y	z	Uiso*/Ueq
Cl1	0.24004 (11)	0.34934 (7)	0.34487 (4)	0.02854 (18)
O1	0.6456 (4)	0.53157 (19)	0.31400 (14)	0.0267 (4)
H1O	0.792 (8)	0.585 (4)	0.330 (3)	0.040*
O2	1.0367 (4)	0.66367 (19)	0.38081 (15)	0.0331 (5)
O3	1.1791 (4)	0.65600 (18)	0.53520 (16)	0.0286 (5)
O4	0.2148 (4)	0.23412 (19)	0.84645 (13)	0.0267 (4)
O5	0.4182 (4)	0.37138 (19)	0.95279 (13)	0.0316 (5)
O6	0.0002 (3)	0.58322 (18)	0.81904 (14)	0.0245 (4)
N1	1.0294 (4)	0.6262 (2)	0.46967 (16)	0.0248 (5)
N2	0.4220 (4)	0.5472 (2)	0.79647 (15)	0.0175 (4)
H2N	0.568 (4)	0.579 (3)	0.797 (2)	0.021*
C1	0.4584 (5)	0.4103 (3)	0.43817 (19)	0.0220 (6)
C2	0.6440 (5)	0.4968 (2)	0.41110 (19)	0.0215 (5)
C3	0.8183 (5)	0.5385 (2)	0.4902 (2)	0.0216 (5)
C4	0.8039 (5)	0.4991 (2)	0.58960 (18)	0.0175 (5)
H4	0.9214	0.5319	0.6410	0.021*
C5	0.6194 (4)	0.4125 (2)	0.61350 (18)	0.0163 (5)
C6	0.4450 (5)	0.3693 (2)	0.53587 (18)	0.0190 (5)
H6	0.3147	0.3105	0.5510	0.023*
C7	0.6044 (4)	0.3609 (2)	0.71852 (17)	0.0175 (5)
H7A	0.7695	0.3792	0.7581	0.021*
H7B	0.5847	0.2688	0.7146	0.021*
C8	0.3772 (4)	0.4158 (2)	0.77388 (18)	0.0166 (5)
H8	0.2149	0.4085	0.7287	0.020*
C9	0.3412 (4)	0.3398 (3)	0.86964 (18)	0.0202 (5)
C10	0.2262 (5)	0.6225 (2)	0.81958 (18)	0.0194 (5)
C11	0.2946 (6)	0.7547 (3)	0.8436 (2)	0.0266 (6)
H11A	0.2472	0.8076	0.7849	0.040*
H11B	0.4822	0.7612	0.8605	0.040*
H11C	0.1998	0.7827	0.9011	0.040*
C12	0.1647 (7)	0.1488 (3)	0.9296 (2)	0.0381 (7)
H12A	0.1447	0.1969	0.9923	0.046*
H12B	0.3119	0.0899	0.9414	0.046*
C13	−0.0777 (7)	0.0789 (3)	0.9011 (3)	0.0415 (8)
H13A	−0.2226	0.1379	0.8908	0.062*
H13B	−0.1142	0.0202	0.9551	0.062*
H13C	−0.0565	0.0323	0.8386	0.062*

	U11	U22	U33	U12	U13	U23
Cl1	0.0268 (3)	0.0336 (3)	0.0250 (3)	−0.0030 (3)	0.0000 (2)	−0.0031 (3)
O1	0.0312 (11)	0.0286 (10)	0.0207 (9)	0.0023 (9)	0.0058 (8)	0.0033 (7)
O2	0.0380 (12)	0.0302 (11)	0.0321 (11)	−0.0054 (9)	0.0103 (9)	0.0044 (8)
O3	0.0221 (10)	0.0241 (10)	0.0401 (12)	−0.0107 (8)	0.0066 (9)	−0.0074 (8)
O4	0.0307 (10)	0.0265 (10)	0.0234 (9)	−0.0079 (8)	0.0060 (7)	0.0089 (8)
O5	0.0478 (12)	0.0295 (11)	0.0175 (9)	0.0062 (10)	0.0015 (8)	−0.0004 (8)
O6	0.0149 (9)	0.0286 (10)	0.0303 (10)	0.0014 (8)	0.0026 (7)	−0.0090 (8)
N1	0.0261 (12)	0.0275 (12)	0.0221 (12)	0.0139 (10)	0.0115 (10)	0.0057 (9)
N2	0.0139 (10)	0.0191 (10)	0.0196 (10)	−0.0005 (8)	0.0027 (8)	−0.0019 (8)
C1	0.0225 (12)	0.0236 (13)	0.0200 (12)	0.0036 (11)	0.0024 (10)	−0.0037 (10)
C2	0.0221 (12)	0.0219 (12)	0.0209 (13)	0.0097 (10)	0.0058 (9)	−0.0001 (10)
C3	0.0183 (13)	0.0170 (12)	0.0306 (14)	0.0038 (10)	0.0113 (10)	0.0040 (10)
C4	0.0160 (12)	0.0157 (11)	0.0210 (12)	0.0033 (9)	0.0030 (9)	0.0010 (9)
C5	0.0148 (11)	0.0151 (11)	0.0196 (12)	0.0035 (10)	0.0051 (9)	−0.0009 (9)
C6	0.0200 (11)	0.0150 (12)	0.0223 (11)	0.0043 (10)	0.0034 (8)	−0.0009 (9)
C7	0.0158 (10)	0.0185 (12)	0.0188 (11)	0.0015 (10)	0.0049 (8)	0.0011 (10)
C8	0.0150 (11)	0.0163 (11)	0.0188 (12)	−0.0002 (10)	0.0018 (9)	−0.0004 (9)
C9	0.0178 (11)	0.0210 (12)	0.0225 (12)	0.0088 (11)	0.0063 (9)	0.0025 (11)
C10	0.0181 (13)	0.0257 (13)	0.0143 (11)	0.0049 (10)	−0.0001 (9)	0.0001 (9)
C11	0.0296 (14)	0.0239 (14)	0.0264 (13)	0.0019 (12)	0.0012 (10)	−0.0039 (11)
C12	0.0403 (18)	0.0433 (18)	0.0317 (16)	−0.0048 (15)	0.0093 (13)	0.0229 (14)
C13	0.050 (2)	0.0364 (17)	0.0398 (17)	−0.0137 (16)	0.0147 (14)	0.0072 (15)

Cl1—C1	1.745 (3)	C5—C6	1.402 (3)
O1—C2	1.343 (3)	C5—C7	1.507 (3)
O1—H1O	0.96 (4)	C6—H6	0.9500
O2—N1	1.249 (3)	C7—C8	1.538 (3)
O3—N1	1.169 (3)	C7—H7A	0.9900
O4—C9	1.329 (4)	C7—H7B	0.9900
O4—C12	1.467 (3)	C8—C9	1.530 (3)
O5—C9	1.198 (3)	C8—H8	1.0000
O6—C10	1.237 (3)	C10—C11	1.485 (4)
N1—C3	1.473 (4)	C11—H11A	0.9800
N2—C10	1.341 (3)	C11—H11B	0.9800
N2—C8	1.449 (3)	C11—H11C	0.9800
N2—H2N	0.823 (18)	C12—C13	1.483 (5)
C1—C6	1.375 (4)	C12—H12A	0.9900
C1—C2	1.393 (4)	C12—H12B	0.9900
C2—C3	1.409 (4)	C13—H13A	0.9800
C3—C4	1.393 (4)	C13—H13B	0.9800
C4—C5	1.377 (4)	C13—H13C	0.9800
C4—H4	0.9500
C2—O1—H1O	91 (2)	H7A—C7—H7B	107.8
C9—O4—C12	117.4 (2)	N2—C8—C9	111.5 (2)
O3—N1—O2	123.9 (2)	N2—C8—C7	110.6 (2)
O3—N1—C3	119.6 (2)	C9—C8—C7	109.38 (19)
O2—N1—C3	116.5 (2)	N2—C8—H8	108.4
C10—N2—C8	121.0 (2)	C9—C8—H8	108.4
C10—N2—H2N	117 (2)	C7—C8—H8	108.4
C8—N2—H2N	122 (2)	O5—C9—O4	125.5 (2)
C6—C1—C2	122.1 (2)	O5—C9—C8	124.5 (3)
C6—C1—Cl1	118.9 (2)	O4—C9—C8	110.0 (2)
C2—C1—Cl1	119.0 (2)	O6—C10—N2	121.1 (2)
O1—C2—C1	118.5 (2)	O6—C10—C11	122.3 (2)
O1—C2—C3	125.9 (2)	N2—C10—C11	116.6 (2)
C1—C2—C3	115.6 (2)	C10—C11—H11A	109.5
C4—C3—C2	122.8 (2)	C10—C11—H11B	109.5
C4—C3—N1	116.9 (2)	H11A—C11—H11B	109.5
C2—C3—N1	120.3 (2)	C10—C11—H11C	109.5
C5—C4—C3	120.1 (2)	H11A—C11—H11C	109.5
C5—C4—H4	120.0	H11B—C11—H11C	109.5
C3—C4—H4	120.0	O4—C12—C13	107.8 (2)
C4—C5—C6	118.1 (2)	O4—C12—H12A	110.1
C4—C5—C7	122.4 (2)	C13—C12—H12A	110.1
C6—C5—C7	119.5 (2)	O4—C12—H12B	110.1
C1—C6—C5	121.4 (2)	C13—C12—H12B	110.1
C1—C6—H6	119.3	H12A—C12—H12B	108.5
C5—C6—H6	119.3	C12—C13—H13A	109.5
C5—C7—C8	112.9 (2)	C12—C13—H13B	109.5
C5—C7—H7A	109.0	H13A—C13—H13B	109.5
C8—C7—H7A	109.0	C12—C13—H13C	109.5
C5—C7—H7B	109.0	H13A—C13—H13C	109.5
C8—C7—H7B	109.0	H13B—C13—H13C	109.5
C6—C1—C2—O1	179.6 (2)	C4—C5—C6—C1	0.9 (3)
Cl1—C1—C2—O1	0.9 (3)	C7—C5—C6—C1	−177.4 (2)
C6—C1—C2—C3	0.6 (4)	C4—C5—C7—C8	105.2 (3)
Cl1—C1—C2—C3	−178.02 (18)	C6—C5—C7—C8	−76.6 (3)
O1—C2—C3—C4	179.5 (2)	C10—N2—C8—C9	−75.9 (3)
C1—C2—C3—C4	−1.6 (4)	C10—N2—C8—C7	162.1 (2)
O1—C2—C3—N1	−1.3 (4)	C5—C7—C8—N2	−68.5 (3)
C1—C2—C3—N1	177.5 (2)	C5—C7—C8—C9	168.3 (2)
O3—N1—C3—C4	2.3 (4)	C12—O4—C9—O5	0.1 (4)
O2—N1—C3—C4	−178.1 (2)	C12—O4—C9—C8	179.6 (2)
O3—N1—C3—C2	−176.9 (2)	N2—C8—C9—O5	−22.1 (3)
O2—N1—C3—C2	2.6 (3)	C7—C8—C9—O5	100.6 (3)
C2—C3—C4—C5	2.3 (4)	N2—C8—C9—O4	158.4 (2)
N1—C3—C4—C5	−176.9 (2)	C7—C8—C9—O4	−78.9 (2)
C3—C4—C5—C6	−1.9 (3)	C8—N2—C10—O6	−2.4 (4)
C3—C4—C5—C7	176.4 (2)	C8—N2—C10—C11	178.7 (2)
C2—C1—C6—C5	−0.3 (4)	C9—O4—C12—C13	150.8 (3)
Cl1—C1—C6—C5	178.34 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2	0.96 (4)	1.63 (4)	2.570 (3)	168 (3)
N2—H2N···O6i	0.82 (2)	2.23 (2)	2.999 (3)	156 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2	0.96 (4)	1.63 (4)	2.570 (3)	168 (3)
N2—H2N⋯O6i	0.82 (2)	2.23 (2)	2.999 (3)	156 (3)

Symmetry code: (i) .