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Crystals of the title compound, C8H7NO6, were obtained by the reaction of methyl 2,6-dihydroxy­benzoate with nitric acid and crystallization of the product from ethyl acetate. In the mol­ecule, the nitro group is essentially coplanar with the attached benzene ring [O—N—C—C = 5.2 (3)°] indicating conjugation with the π-electron system. The meth­oxy group of the ester group is cis with respect to the ortho-nitro­hydroxyl group. The crystal structure is stabilized by intra- and inter­molecular hydrogen bonds. The ortho-nitro­hydr­oxy group forms an intra­molecular hydrogen bond with the nitro group and the para-nitro­hydr­oxy group forms an intra­molecular hydrogen bond with the ester carbonyl function. In addition, there is inter­molecular hydrogen bonding between the ortho-nitro­hydroxyl of one mol­ecule and the O atom of para-nitro­hydroxyl of another mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028589/lh2413sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028589/lh2413Isup2.hkl
Contains datablock I

CCDC reference: 654969

Key indicators

  • Single-crystal X-ray study
  • T = 210 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.050
  • wR factor = 0.146
  • Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.14
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

X-ray crystallography confirmed the molecular structure and atom connectivity as illustrated in Fig. 1. In the title molecule the nitro group shows normal geometrical parameters. The torsion angles [O1—N1—C1—C6 = 5.2 (3)° and O2—N1—C1—C2 = 4.5 (3)°] indicate that there is not much deviation of the plane of the nitro group from the plane of phenyl ring, facilitating conjugation with the π electrons of the phenyl ring. Furthermore, the observed length of the N1—C1 bond [1.435 (2) Å] is shorter than the theoretical length for a Car—NO2 bond of [1.468 (14) Å; Wilson, 1992], which indicates the formation of a conjugated π-electron system along this bond. There is an asymmetry of the exocyclic angles at the C1, C2, C3, and C4 atoms.

The mode of packing of along the b direction is illustrated in Fig.2. In addition to O—H···O intra- and intermolecular hydrogen bonding, C—H···O interactions contribute to the stabilization of the crystal structure.

Related literature top

For related literature, see: Wilson (1992).

Experimental top

The title compound, methyl 2,6-dihydroxy-3-nitrobenzoate was prepared by nitration of methyl 2,6-dihydroxybenzoate and recrystallization of the resultant product from ethyl acetate to afford yellow colored crystals. 1H NMR (DMSO-d6, p.p.m.): δ 3.80 (s, 3H), 6.59 (d, 1H), 8.04 (d, 1H), 10.91 (s, 1H), 11.73 (s, 1H).

Refinement top

H atoms were found in difference Fourier maps and subsequently placed in idealized positions with constrained C—H distances of 0.94 Å (Car—H), 0.97 Å (CH3) and 0.83 Å (O—H). Uiso(H) values were set to 1.2Ueq(CarH only) or 1.5eq of the attached atom.

Structure description top

X-ray crystallography confirmed the molecular structure and atom connectivity as illustrated in Fig. 1. In the title molecule the nitro group shows normal geometrical parameters. The torsion angles [O1—N1—C1—C6 = 5.2 (3)° and O2—N1—C1—C2 = 4.5 (3)°] indicate that there is not much deviation of the plane of the nitro group from the plane of phenyl ring, facilitating conjugation with the π electrons of the phenyl ring. Furthermore, the observed length of the N1—C1 bond [1.435 (2) Å] is shorter than the theoretical length for a Car—NO2 bond of [1.468 (14) Å; Wilson, 1992], which indicates the formation of a conjugated π-electron system along this bond. There is an asymmetry of the exocyclic angles at the C1, C2, C3, and C4 atoms.

The mode of packing of along the b direction is illustrated in Fig.2. In addition to O—H···O intra- and intermolecular hydrogen bonding, C—H···O interactions contribute to the stabilization of the crystal structure.

For related literature, see: Wilson (1992).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and local procedures.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title compound, with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing of the title compound, viewed along the a axis; showing hydrogen-bonding interactions (dashed lines).
Methyl 2,6-dihydroxy-3-nitrobenzoate top
Crystal data top
C8H7NO6F(000) = 440
Mr = 213.15Dx = 1.659 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3726 reflections
a = 3.8681 (2) Åθ = 1.0–27.5°
b = 18.3596 (5) ŵ = 0.15 mm1
c = 12.0186 (9) ÅT = 210 K
β = 91.682 (2)°Cut wedge, yellow
V = 853.15 (8) Å30.25 × 0.22 × 0.05 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
1922 independent reflections
Radiation source: fine-focus sealed tube1277 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
Detector resolution: 18 pixels mm-1θmax = 27.4°, θmin = 2.0°
ω scans at fixed χ = 55°h = 55
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
k = 2323
Tmin = 0.965, Tmax = 0.993l = 1515
7208 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0907P)2]
where P = (Fo2 + 2Fc2)/3
1922 reflections(Δ/σ)max = 0.002
139 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C8H7NO6V = 853.15 (8) Å3
Mr = 213.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 3.8681 (2) ŵ = 0.15 mm1
b = 18.3596 (5) ÅT = 210 K
c = 12.0186 (9) Å0.25 × 0.22 × 0.05 mm
β = 91.682 (2)°
Data collection top
Nonius KappaCCD
diffractometer
1922 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
1277 reflections with I > 2σ(I)
Tmin = 0.965, Tmax = 0.993Rint = 0.045
7208 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.146H-atom parameters constrained
S = 1.03Δρmax = 0.37 e Å3
1922 reflectionsΔρmin = 0.22 e Å3
139 parameters
Special details top

Experimental. The crystals shattered on cooling to 90 K, 150 K 180 K but were stable at 210 K.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.1783 (4)0.09134 (8)0.62514 (12)0.0410 (4)
O10.2648 (4)0.02998 (7)0.59892 (13)0.0726 (6)
O20.0072 (4)0.10261 (7)0.70927 (11)0.0494 (4)
O30.0305 (3)0.24073 (6)0.67916 (9)0.0384 (4)
H30.02070.20280.71230.058*
O40.5981 (3)0.31416 (7)0.35145 (9)0.0424 (4)
H40.55870.35510.37760.064*
O50.3713 (3)0.40744 (7)0.48250 (11)0.0480 (4)
O60.1204 (3)0.37470 (6)0.63917 (10)0.0431 (4)
C10.2763 (4)0.15166 (9)0.55705 (14)0.0330 (4)
C20.2024 (4)0.22407 (9)0.58833 (13)0.0299 (4)
C30.3148 (4)0.28084 (9)0.51908 (13)0.0296 (4)
C40.4839 (4)0.26314 (9)0.42013 (14)0.0327 (4)
C50.5425 (4)0.19083 (10)0.39009 (13)0.0381 (5)
H50.65010.18000.32290.046*
C60.4435 (5)0.13631 (10)0.45810 (15)0.0381 (5)
H60.48750.08770.43860.046*
C70.2707 (4)0.35928 (9)0.54468 (14)0.0331 (4)
C80.0837 (6)0.45169 (10)0.66481 (18)0.0508 (5)
H8A0.30850.47500.66360.076*
H8B0.01180.45710.73810.076*
H8C0.07020.47430.60980.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0555 (10)0.0268 (9)0.0413 (9)0.0013 (7)0.0126 (7)0.0011 (6)
O10.1201 (14)0.0253 (8)0.0751 (11)0.0110 (8)0.0504 (10)0.0036 (7)
O20.0724 (9)0.0349 (8)0.0423 (8)0.0001 (6)0.0246 (7)0.0034 (6)
O30.0526 (8)0.0294 (7)0.0341 (7)0.0010 (6)0.0166 (6)0.0004 (5)
O40.0549 (8)0.0333 (8)0.0399 (7)0.0008 (6)0.0171 (6)0.0045 (6)
O50.0657 (9)0.0287 (7)0.0506 (8)0.0012 (6)0.0175 (7)0.0038 (6)
O60.0600 (9)0.0269 (7)0.0432 (8)0.0044 (6)0.0157 (6)0.0038 (5)
C10.0398 (10)0.0260 (9)0.0334 (9)0.0016 (7)0.0074 (7)0.0015 (7)
C20.0316 (9)0.0300 (9)0.0284 (8)0.0020 (7)0.0042 (7)0.0015 (7)
C30.0319 (9)0.0260 (9)0.0311 (8)0.0013 (7)0.0033 (7)0.0006 (7)
C40.0341 (10)0.0319 (10)0.0325 (9)0.0008 (7)0.0047 (7)0.0023 (7)
C50.0441 (10)0.0376 (11)0.0331 (9)0.0050 (8)0.0102 (7)0.0027 (8)
C60.0449 (10)0.0296 (10)0.0403 (10)0.0056 (8)0.0079 (8)0.0040 (8)
C70.0360 (9)0.0287 (10)0.0348 (9)0.0002 (7)0.0053 (7)0.0003 (7)
C80.0679 (13)0.0267 (11)0.0588 (12)0.0040 (9)0.0170 (10)0.0077 (9)
Geometric parameters (Å, º) top
N1—O11.2192 (19)C1—C21.413 (2)
N1—O21.2420 (17)C2—C31.410 (2)
N1—C11.435 (2)C3—C41.412 (2)
O3—C21.3306 (19)C3—C71.483 (2)
O3—H30.8300C4—C51.396 (2)
O4—C41.3323 (19)C5—C61.355 (2)
O4—H40.8300C5—H50.9400
O5—C71.228 (2)C6—H60.9400
O6—C71.322 (2)C8—H8A0.9700
O6—C81.455 (2)C8—H8B0.9700
C1—C61.399 (2)C8—H8C0.9700
O1—N1—O2121.40 (15)C5—C4—C3121.29 (15)
O1—N1—C1119.13 (15)C6—C5—C4119.73 (15)
O2—N1—C1119.47 (14)C6—C5—H5120.1
C2—O3—H3109.5C4—C5—H5120.1
C4—O4—H4109.5C5—C6—C1120.65 (16)
C7—O6—C8116.01 (14)C5—C6—H6119.7
C6—C1—C2121.19 (15)C1—C6—H6119.7
C6—C1—N1117.76 (15)O5—C7—O6121.58 (16)
C2—C1—N1121.04 (14)O5—C7—C3122.15 (15)
O3—C2—C3118.97 (14)O6—C7—C3116.27 (14)
O3—C2—C1122.98 (14)O6—C8—H8A109.5
C3—C2—C1118.04 (14)O6—C8—H8B109.5
C2—C3—C4119.04 (15)H8A—C8—H8B109.5
C2—C3—C7123.75 (14)O6—C8—H8C109.5
C4—C3—C7117.20 (15)H8A—C8—H8C109.5
O4—C4—C5116.69 (14)H8B—C8—H8C109.5
O4—C4—C3122.02 (15)
O1—N1—C1—C65.2 (3)C2—C3—C4—C50.2 (2)
O2—N1—C1—C6174.73 (15)C7—C3—C4—C5178.90 (15)
O1—N1—C1—C2175.62 (16)O4—C4—C5—C6177.77 (15)
O2—N1—C1—C24.5 (3)C3—C4—C5—C61.7 (3)
C6—C1—C2—O3176.93 (16)C4—C5—C6—C11.4 (3)
N1—C1—C2—O32.3 (3)C2—C1—C6—C50.7 (3)
C6—C1—C2—C32.6 (3)N1—C1—C6—C5179.95 (16)
N1—C1—C2—C3178.25 (15)C8—O6—C7—O50.3 (3)
O3—C2—C3—C4177.25 (14)C8—O6—C7—C3178.90 (14)
C1—C2—C3—C42.3 (2)C2—C3—C7—O5179.95 (16)
O3—C2—C3—C73.7 (2)C4—C3—C7—O51.0 (3)
C1—C2—C3—C7176.80 (15)C2—C3—C7—O60.9 (2)
C2—C3—C4—O4179.62 (15)C4—C3—C7—O6178.18 (14)
C7—C3—C4—O40.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.831.842.5636 (16)145
O3—H3···O4i0.832.282.8816 (15)129
O3—H3···N10.832.432.8797 (19)115
O4—H4···O50.831.762.5028 (16)148
Symmetry code: (i) x1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC8H7NO6
Mr213.15
Crystal system, space groupMonoclinic, P21/c
Temperature (K)210
a, b, c (Å)3.8681 (2), 18.3596 (5), 12.0186 (9)
β (°) 91.682 (2)
V3)853.15 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.25 × 0.22 × 0.05
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.965, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
7208, 1922, 1277
Rint0.045
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.146, 1.03
No. of reflections1922
No. of parameters139
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.22

Computer programs: COLLECT (Nonius, 1999), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1995), SHELXL97 (Sheldrick, 1997) and local procedures.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.831.842.5636 (16)144.5
O3—H3···O4i0.832.282.8816 (15)129.4
O3—H3···N10.832.432.8797 (19)114.6
O4—H4···O50.831.762.5028 (16)148.3
Symmetry code: (i) x1, y+1/2, z+1/2.
 

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