Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028589/lh2413sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028589/lh2413Isup2.hkl |
CCDC reference: 654969
Key indicators
- Single-crystal X-ray study
- T = 210 K
- Mean (C-C) = 0.002 Å
- R factor = 0.050
- wR factor = 0.146
- Data-to-parameter ratio = 13.8
checkCIF/PLATON results
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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
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).
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.
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).
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.
C8H7NO6 | F(000) = 440 |
Mr = 213.15 | Dx = 1.659 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3726 reflections |
a = 3.8681 (2) Å | θ = 1.0–27.5° |
b = 18.3596 (5) Å | µ = 0.15 mm−1 |
c = 12.0186 (9) Å | T = 210 K |
β = 91.682 (2)° | Cut wedge, yellow |
V = 853.15 (8) Å3 | 0.25 × 0.22 × 0.05 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 1922 independent reflections |
Radiation source: fine-focus sealed tube | 1277 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 18 pixels mm-1 | θmax = 27.4°, θmin = 2.0° |
ω scans at fixed χ = 55° | h = −5→5 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −23→23 |
Tmin = 0.965, Tmax = 0.993 | l = −15→15 |
7208 measured reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H-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 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C8H7NO6 | V = 853.15 (8) Å3 |
Mr = 213.15 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 3.8681 (2) Å | µ = 0.15 mm−1 |
b = 18.3596 (5) Å | T = 210 K |
c = 12.0186 (9) Å | 0.25 × 0.22 × 0.05 mm |
β = 91.682 (2)° |
Nonius KappaCCD diffractometer | 1922 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 1277 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.993 | Rint = 0.045 |
7208 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.37 e Å−3 |
1922 reflections | Δρmin = −0.22 e Å−3 |
139 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1783 (4) | 0.09134 (8) | 0.62514 (12) | 0.0410 (4) | |
O1 | 0.2648 (4) | 0.02998 (7) | 0.59892 (13) | 0.0726 (6) | |
O2 | 0.0072 (4) | 0.10261 (7) | 0.70927 (11) | 0.0494 (4) | |
O3 | 0.0305 (3) | 0.24073 (6) | 0.67916 (9) | 0.0384 (4) | |
H3 | −0.0207 | 0.2028 | 0.7123 | 0.058* | |
O4 | 0.5981 (3) | 0.31416 (7) | 0.35145 (9) | 0.0424 (4) | |
H4 | 0.5587 | 0.3551 | 0.3776 | 0.064* | |
O5 | 0.3713 (3) | 0.40744 (7) | 0.48250 (11) | 0.0480 (4) | |
O6 | 0.1204 (3) | 0.37470 (6) | 0.63917 (10) | 0.0431 (4) | |
C1 | 0.2763 (4) | 0.15166 (9) | 0.55705 (14) | 0.0330 (4) | |
C2 | 0.2024 (4) | 0.22407 (9) | 0.58833 (13) | 0.0299 (4) | |
C3 | 0.3148 (4) | 0.28084 (9) | 0.51908 (13) | 0.0296 (4) | |
C4 | 0.4839 (4) | 0.26314 (9) | 0.42013 (14) | 0.0327 (4) | |
C5 | 0.5425 (4) | 0.19083 (10) | 0.39009 (13) | 0.0381 (5) | |
H5 | 0.6501 | 0.1800 | 0.3229 | 0.046* | |
C6 | 0.4435 (5) | 0.13631 (10) | 0.45810 (15) | 0.0381 (5) | |
H6 | 0.4875 | 0.0877 | 0.4386 | 0.046* | |
C7 | 0.2707 (4) | 0.35928 (9) | 0.54468 (14) | 0.0331 (4) | |
C8 | 0.0837 (6) | 0.45169 (10) | 0.66481 (18) | 0.0508 (5) | |
H8A | 0.3085 | 0.4750 | 0.6636 | 0.076* | |
H8B | −0.0118 | 0.4571 | 0.7381 | 0.076* | |
H8C | −0.0702 | 0.4743 | 0.6098 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0555 (10) | 0.0268 (9) | 0.0413 (9) | 0.0013 (7) | 0.0126 (7) | 0.0011 (6) |
O1 | 0.1201 (14) | 0.0253 (8) | 0.0751 (11) | 0.0110 (8) | 0.0504 (10) | 0.0036 (7) |
O2 | 0.0724 (9) | 0.0349 (8) | 0.0423 (8) | 0.0001 (6) | 0.0246 (7) | 0.0034 (6) |
O3 | 0.0526 (8) | 0.0294 (7) | 0.0341 (7) | 0.0010 (6) | 0.0166 (6) | 0.0004 (5) |
O4 | 0.0549 (8) | 0.0333 (8) | 0.0399 (7) | −0.0008 (6) | 0.0171 (6) | 0.0045 (6) |
O5 | 0.0657 (9) | 0.0287 (7) | 0.0506 (8) | −0.0012 (6) | 0.0175 (7) | 0.0038 (6) |
O6 | 0.0600 (9) | 0.0269 (7) | 0.0432 (8) | 0.0044 (6) | 0.0157 (6) | −0.0038 (5) |
C1 | 0.0398 (10) | 0.0260 (9) | 0.0334 (9) | 0.0016 (7) | 0.0074 (7) | 0.0015 (7) |
C2 | 0.0316 (9) | 0.0300 (9) | 0.0284 (8) | 0.0020 (7) | 0.0042 (7) | −0.0015 (7) |
C3 | 0.0319 (9) | 0.0260 (9) | 0.0311 (8) | 0.0013 (7) | 0.0033 (7) | −0.0006 (7) |
C4 | 0.0341 (10) | 0.0319 (10) | 0.0325 (9) | −0.0008 (7) | 0.0047 (7) | 0.0023 (7) |
C5 | 0.0441 (10) | 0.0376 (11) | 0.0331 (9) | 0.0050 (8) | 0.0102 (7) | −0.0027 (8) |
C6 | 0.0449 (10) | 0.0296 (10) | 0.0403 (10) | 0.0056 (8) | 0.0079 (8) | −0.0040 (8) |
C7 | 0.0360 (9) | 0.0287 (10) | 0.0348 (9) | 0.0002 (7) | 0.0053 (7) | 0.0003 (7) |
C8 | 0.0679 (13) | 0.0267 (11) | 0.0588 (12) | 0.0040 (9) | 0.0170 (10) | −0.0077 (9) |
N1—O1 | 1.2192 (19) | C1—C2 | 1.413 (2) |
N1—O2 | 1.2420 (17) | C2—C3 | 1.410 (2) |
N1—C1 | 1.435 (2) | C3—C4 | 1.412 (2) |
O3—C2 | 1.3306 (19) | C3—C7 | 1.483 (2) |
O3—H3 | 0.8300 | C4—C5 | 1.396 (2) |
O4—C4 | 1.3323 (19) | C5—C6 | 1.355 (2) |
O4—H4 | 0.8300 | C5—H5 | 0.9400 |
O5—C7 | 1.228 (2) | C6—H6 | 0.9400 |
O6—C7 | 1.322 (2) | C8—H8A | 0.9700 |
O6—C8 | 1.455 (2) | C8—H8B | 0.9700 |
C1—C6 | 1.399 (2) | C8—H8C | 0.9700 |
O1—N1—O2 | 121.40 (15) | C5—C4—C3 | 121.29 (15) |
O1—N1—C1 | 119.13 (15) | C6—C5—C4 | 119.73 (15) |
O2—N1—C1 | 119.47 (14) | C6—C5—H5 | 120.1 |
C2—O3—H3 | 109.5 | C4—C5—H5 | 120.1 |
C4—O4—H4 | 109.5 | C5—C6—C1 | 120.65 (16) |
C7—O6—C8 | 116.01 (14) | C5—C6—H6 | 119.7 |
C6—C1—C2 | 121.19 (15) | C1—C6—H6 | 119.7 |
C6—C1—N1 | 117.76 (15) | O5—C7—O6 | 121.58 (16) |
C2—C1—N1 | 121.04 (14) | O5—C7—C3 | 122.15 (15) |
O3—C2—C3 | 118.97 (14) | O6—C7—C3 | 116.27 (14) |
O3—C2—C1 | 122.98 (14) | O6—C8—H8A | 109.5 |
C3—C2—C1 | 118.04 (14) | O6—C8—H8B | 109.5 |
C2—C3—C4 | 119.04 (15) | H8A—C8—H8B | 109.5 |
C2—C3—C7 | 123.75 (14) | O6—C8—H8C | 109.5 |
C4—C3—C7 | 117.20 (15) | H8A—C8—H8C | 109.5 |
O4—C4—C5 | 116.69 (14) | H8B—C8—H8C | 109.5 |
O4—C4—C3 | 122.02 (15) | ||
O1—N1—C1—C6 | 5.2 (3) | C2—C3—C4—C5 | −0.2 (2) |
O2—N1—C1—C6 | −174.73 (15) | C7—C3—C4—C5 | 178.90 (15) |
O1—N1—C1—C2 | −175.62 (16) | O4—C4—C5—C6 | 177.77 (15) |
O2—N1—C1—C2 | 4.5 (3) | C3—C4—C5—C6 | −1.7 (3) |
C6—C1—C2—O3 | 176.93 (16) | C4—C5—C6—C1 | 1.4 (3) |
N1—C1—C2—O3 | −2.3 (3) | C2—C1—C6—C5 | 0.7 (3) |
C6—C1—C2—C3 | −2.6 (3) | N1—C1—C6—C5 | 179.95 (16) |
N1—C1—C2—C3 | 178.25 (15) | C8—O6—C7—O5 | −0.3 (3) |
O3—C2—C3—C4 | −177.25 (14) | C8—O6—C7—C3 | 178.90 (14) |
C1—C2—C3—C4 | 2.3 (2) | C2—C3—C7—O5 | −179.95 (16) |
O3—C2—C3—C7 | 3.7 (2) | C4—C3—C7—O5 | 1.0 (3) |
C1—C2—C3—C7 | −176.80 (15) | C2—C3—C7—O6 | 0.9 (2) |
C2—C3—C4—O4 | −179.62 (15) | C4—C3—C7—O6 | −178.18 (14) |
C7—C3—C4—O4 | −0.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.83 | 1.84 | 2.5636 (16) | 145 |
O3—H3···O4i | 0.83 | 2.28 | 2.8816 (15) | 129 |
O3—H3···N1 | 0.83 | 2.43 | 2.8797 (19) | 115 |
O4—H4···O5 | 0.83 | 1.76 | 2.5028 (16) | 148 |
Symmetry code: (i) x−1, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H7NO6 |
Mr | 213.15 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 210 |
a, b, c (Å) | 3.8681 (2), 18.3596 (5), 12.0186 (9) |
β (°) | 91.682 (2) |
V (Å3) | 853.15 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.25 × 0.22 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.965, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7208, 1922, 1277 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.146, 1.03 |
No. of reflections | 1922 |
No. of parameters | 139 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.83 | 1.84 | 2.5636 (16) | 144.5 |
O3—H3···O4i | 0.83 | 2.28 | 2.8816 (15) | 129.4 |
O3—H3···N1 | 0.83 | 2.43 | 2.8797 (19) | 114.6 |
O4—H4···O5 | 0.83 | 1.76 | 2.5028 (16) | 148.3 |
Symmetry code: (i) x−1, −y+1/2, z+1/2. |
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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.