Methyl 5-chloro-2-nitro-benzoate.

In the title compound, C(8)H(6)ClNO(4), the nitro and acet-oxy groups attached to the benzene ring at neighbouring positions are twisted from its plane by 29.4 (1) and 49.7 (1)°, respectively. In the crystal, weak C-H⋯O hydrogen bonds link mol-ecules into layers parallel to (101). The crystal packing exhibits short inter-molecular C⋯O distances of 2.925 (3) Å.

Related literature

The title compound is an inter­mediate of the oral vasopressin V2-receptor antagonist tolvaptan. For applications of tolvaptan, see: Nemerovski & Hutchinson (2010 ▶). For the synthesis of the title compound, see: Kondo et al. (1999 ▶). For a related structure, see: Liu et al. (2008 ▶).

Experimental

Crystal data

C8H6ClNO4

M = 215.59

Monoclinic,

a = 4.2616 (9) Å

b = 22.470 (5) Å

c = 9.3894 (19) Å

β = 90.64 (3)°

V = 899.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.41 mm−1

T = 113 K

0.16 × 0.14 × 0.12 mm

Data collection

Rigaku Saturn diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.937, T max = 0.952

5007 measured reflections

1564 independent reflections

1400 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.116

S = 1.07

1564 reflections

128 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811044072/cv5162sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044072/cv5162Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811044072/cv5162Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811044072/cv5162Isup4.cml

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

C8H6ClNO4	F(000) = 440
Mr = 215.59	Dx = 1.593 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2662 reflections
a = 4.2616 (9) Å	θ = 1.8–27.5°
b = 22.470 (5) Å	µ = 0.41 mm−1
c = 9.3894 (19) Å	T = 113 K
β = 90.64 (3)°	Prism, colorless
V = 899.1 (3) Å3	0.16 × 0.14 × 0.12 mm
Z = 4

Rigaku Saturn diffractometer	1564 independent reflections
Radiation source: rotating anode	1400 reflections with I > 2σ(I)
confocal	Rint = 0.031
ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −4→5
Tmin = 0.937, Tmax = 0.952	k = −26→20
5007 measured reflections	l = −11→11

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0708P)2 + 0.3934P] where P = (Fo2 + 2Fc2)/3
1564 reflections	(Δ/σ)max = 0.001
128 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.83432 (12)	0.09111 (2)	1.09984 (5)	0.0272 (2)
O1	0.1416 (4)	0.05968 (8)	0.42100 (17)	0.0423 (5)
O2	−0.1876 (4)	0.12282 (9)	0.48951 (17)	0.0409 (5)
O3	0.1575 (4)	0.22747 (7)	0.57507 (16)	0.0364 (4)
O4	−0.0357 (3)	0.22861 (6)	0.78230 (15)	0.0263 (4)
N1	0.0553 (5)	0.09256 (8)	0.51178 (19)	0.0282 (5)
C1	0.2555 (5)	0.09452 (9)	0.6557 (2)	0.0224 (5)
C2	0.4194 (5)	0.04329 (9)	0.7038 (2)	0.0273 (5)
H2	0.4148	0.0092	0.6478	0.033*
C3	0.6002 (5)	0.04214 (9)	0.8420 (2)	0.0263 (5)
H3	0.7041	0.0077	0.8707	0.032*
C4	0.6111 (5)	0.09270 (8)	0.9265 (2)	0.0215 (5)
C5	0.4463 (5)	0.14420 (9)	0.8781 (2)	0.0224 (5)
H5	0.4519	0.1783	0.9342	0.027*
C6	0.2642 (5)	0.14566 (9)	0.7406 (2)	0.0218 (5)
C7	0.1199 (5)	0.20438 (9)	0.6857 (2)	0.0228 (5)
C8	−0.1662 (6)	0.28749 (10)	0.7466 (2)	0.0323 (5)
H8A	0.0017	0.3157	0.7373	0.049*
H8B	−0.3039	0.3001	0.8209	0.049*
H8C	−0.2814	0.2850	0.6584	0.049*

	U11	U22	U33	U12	U13	U23
Cl1	0.0369 (4)	0.0243 (3)	0.0204 (3)	0.0011 (2)	−0.0024 (2)	0.00056 (18)
O1	0.0641 (13)	0.0388 (10)	0.0241 (9)	0.0017 (8)	0.0011 (8)	−0.0105 (7)
O2	0.0322 (10)	0.0596 (12)	0.0308 (9)	0.0044 (8)	0.0003 (7)	0.0013 (8)
O3	0.0481 (10)	0.0359 (9)	0.0256 (9)	0.0124 (7)	0.0201 (7)	0.0125 (7)
O4	0.0334 (9)	0.0244 (8)	0.0215 (8)	0.0032 (6)	0.0139 (6)	0.0031 (6)
N1	0.0335 (11)	0.0305 (10)	0.0206 (10)	−0.0064 (8)	0.0023 (8)	0.0002 (8)
C1	0.0231 (11)	0.0270 (11)	0.0174 (11)	−0.0047 (8)	0.0048 (8)	−0.0011 (8)
C2	0.0352 (12)	0.0223 (10)	0.0246 (11)	−0.0058 (9)	0.0087 (9)	−0.0063 (8)
C3	0.0331 (12)	0.0209 (10)	0.0252 (12)	−0.0008 (9)	0.0071 (9)	0.0024 (8)
C4	0.0255 (11)	0.0217 (10)	0.0176 (10)	−0.0033 (8)	0.0055 (8)	0.0018 (8)
C5	0.0280 (11)	0.0215 (10)	0.0178 (10)	−0.0035 (8)	0.0100 (8)	−0.0003 (8)
C6	0.0229 (11)	0.0252 (10)	0.0175 (10)	−0.0030 (8)	0.0099 (8)	0.0020 (8)
C7	0.0242 (10)	0.0258 (10)	0.0186 (11)	−0.0017 (8)	0.0049 (8)	−0.0004 (8)
C8	0.0416 (14)	0.0250 (11)	0.0307 (13)	0.0076 (10)	0.0123 (10)	0.0038 (9)

Cl1—C4	1.876 (2)	C2—H2	0.9300
O1—N1	1.189 (2)	C3—C4	1.386 (3)
O2—N1	1.254 (3)	C3—H3	0.9300
O3—C7	1.174 (2)	C4—C5	1.425 (3)
O4—C7	1.254 (2)	C5—C6	1.500 (3)
O4—C8	1.472 (3)	C5—H5	0.9300
N1—C1	1.590 (3)	C6—C7	1.542 (3)
C1—C6	1.399 (3)	C8—H8A	0.9600
C1—C2	1.418 (3)	C8—H8B	0.9600
C2—C3	1.502 (3)	C8—H8C	0.9600
C7—O4—C8	115.29 (16)	C4—C5—C6	122.73 (18)
O1—N1—O2	118.6 (2)	C4—C5—H5	118.6
O1—N1—C1	117.30 (18)	C6—C5—H5	118.6
O2—N1—C1	124.10 (17)	C1—C6—C5	118.89 (18)
C6—C1—C2	118.4 (2)	C1—C6—C7	120.30 (18)
C6—C1—N1	121.16 (18)	C5—C6—C7	120.47 (17)
C2—C1—N1	120.40 (17)	O3—C7—O4	121.8 (2)
C1—C2—C3	122.38 (18)	O3—C7—C6	128.04 (18)
C1—C2—H2	118.8	O4—C7—C6	110.01 (16)
C3—C2—H2	118.8	O4—C8—H8A	109.5
C4—C3—C2	119.62 (19)	O4—C8—H8B	109.5
C4—C3—H3	120.2	H8A—C8—H8B	109.5
C2—C3—H3	120.2	O4—C8—H8C	109.5
C3—C4—C5	118.0 (2)	H8A—C8—H8C	109.5
C3—C4—Cl1	119.63 (16)	H8B—C8—H8C	109.5
C5—C4—Cl1	122.36 (15)
O1—N1—C1—C6	152.58 (19)	N1—C1—C6—C5	177.54 (15)
O2—N1—C1—C6	−28.3 (3)	C2—C1—C6—C7	173.45 (17)
O1—N1—C1—C2	−30.1 (3)	N1—C1—C6—C7	−9.2 (3)
O2—N1—C1—C2	149.0 (2)	C4—C5—C6—C1	−0.1 (3)
C6—C1—C2—C3	0.1 (3)	C4—C5—C6—C7	−173.43 (18)
N1—C1—C2—C3	−177.31 (16)	C8—O4—C7—O3	0.0 (3)
C1—C2—C3—C4	−0.4 (3)	C8—O4—C7—C6	175.57 (17)
C2—C3—C4—C5	0.4 (3)	C1—C6—C7—O3	−48.6 (3)
C2—C3—C4—Cl1	179.53 (14)	C5—C6—C7—O3	124.6 (2)
C3—C4—C5—C6	−0.1 (3)	C1—C6—C7—O4	136.20 (19)
Cl1—C4—C5—C6	−179.27 (14)	C5—C6—C7—O4	−50.6 (2)
C2—C1—C6—C5	0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.93	2.53	3.206 (3)	130.
C8—H8B···O3ii	0.96	2.47	3.200 (3)	132.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.93	2.53	3.206 (3)	130
C8—H8B⋯O3ii	0.96	2.47	3.200 (3)	132

Symmetry codes: (i) ; (ii) .