Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029958/is6122sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029958/is6122Isup2.hkl |
CCDC reference: 287609
Toluene-2,4-bis(isocyanate) (TDI) was provided by Hebei Cangzhou Dahua Co. Ltd. The raw material was purified twice by a melt crystallization process. Compound (I) was prepared by the reaction of purified TDI with methanol (m.p. 446.5 K by differential scanning calorimetry). Colorless needle-like single crystals suitable for X-ray diffraction were obtained by slow evaporation from a methanol solution at room temperature for 3 d.
H atoms were placed in calculated positions and constrained to ride on their parent atoms, with distances C—H = 0.93–0.96 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N) and 1.5Ueq(Cmethyl)
Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
C11H14N2O4 | F(000) = 252 |
Mr = 238.24 | Dx = 1.371 Mg m−3 |
Triclinic, P1 | Melting point: 446.5 K |
a = 7.4223 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.1444 (16) Å | Cell parameters from 5473 reflections |
c = 10.642 (2) Å | θ = 3.1–27.5° |
α = 74.01 (3)° | µ = 0.11 mm−1 |
β = 71.64 (3)° | T = 293 K |
γ = 75.44 (3)° | Needle, colorless |
V = 577.3 (2) Å3 | 0.64 × 0.22 × 0.17 mm |
Z = 2 |
Rigaku R-AXIS RAPID IP area-detector diffractometer | 2630 independent reflections |
Radiation source: rotating | 2314 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
oscillation scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→9 |
Tmin = 0.936, Tmax = 0.982 | k = −10→10 |
5743 measured reflections | l = −13→13 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.1123P)2 + 0.3315P] where P = (Fo2 + 2Fc2)/3 |
2630 reflections | (Δ/σ)max = 0.036 |
154 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
C11H14N2O4 | γ = 75.44 (3)° |
Mr = 238.24 | V = 577.3 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.4223 (15) Å | Mo Kα radiation |
b = 8.1444 (16) Å | µ = 0.11 mm−1 |
c = 10.642 (2) Å | T = 293 K |
α = 74.01 (3)° | 0.64 × 0.22 × 0.17 mm |
β = 71.64 (3)° |
Rigaku R-AXIS RAPID IP area-detector diffractometer | 2630 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2314 reflections with I > 2σ(I) |
Tmin = 0.936, Tmax = 0.982 | Rint = 0.029 |
5743 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.53 e Å−3 |
2630 reflections | Δρmin = −0.57 e Å−3 |
154 parameters |
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 | ||
O1 | −0.33340 (17) | 0.73705 (15) | 1.20270 (12) | 0.0233 (3) | |
O2 | −0.37757 (17) | 0.91187 (16) | 1.34595 (12) | 0.0249 (3) | |
O3 | 0.00446 (19) | 0.87208 (15) | 0.69320 (12) | 0.0255 (3) | |
O4 | 0.08246 (19) | 0.62559 (15) | 0.61361 (12) | 0.0248 (3) | |
N1 | −0.0934 (2) | 0.87128 (17) | 1.19914 (13) | 0.0197 (3) | |
H1A | −0.0710 | 0.9405 | 1.2383 | 0.024* | |
N2 | 0.1690 (2) | 0.62084 (17) | 0.79504 (13) | 0.0213 (3) | |
H2A | 0.2115 | 0.5126 | 0.7941 | 0.026* | |
C1 | −0.5723 (3) | 0.8800 (3) | 1.4021 (2) | 0.0336 (4) | |
H1B | −0.6372 | 0.9418 | 1.4736 | 0.050* | |
H1C | −0.5700 | 0.7579 | 1.4377 | 0.050* | |
H1D | −0.6395 | 0.9192 | 1.3326 | 0.050* | |
C2 | −0.2716 (2) | 0.83156 (19) | 1.24363 (15) | 0.0185 (3) | |
C3 | 0.0603 (2) | 0.81108 (19) | 1.09499 (15) | 0.0183 (3) | |
C4 | 0.2441 (3) | 0.8301 (2) | 1.08909 (17) | 0.0242 (4) | |
H4A | 0.2612 | 0.8791 | 1.1529 | 0.029* | |
C5 | 0.4019 (2) | 0.7761 (2) | 0.98834 (18) | 0.0269 (4) | |
H5A | 0.5240 | 0.7887 | 0.9863 | 0.032* | |
C6 | 0.3826 (2) | 0.7037 (2) | 0.89026 (17) | 0.0237 (4) | |
C7 | 0.5543 (3) | 0.6479 (3) | 0.7805 (2) | 0.0334 (4) | |
H7A | 0.5133 | 0.6009 | 0.7228 | 0.050* | |
H7B | 0.6460 | 0.5610 | 0.8207 | 0.050* | |
H7C | 0.6132 | 0.7463 | 0.7279 | 0.050* | |
C8 | 0.1970 (2) | 0.68845 (19) | 0.89642 (15) | 0.0192 (3) | |
C9 | 0.0363 (2) | 0.73963 (19) | 0.99751 (15) | 0.0183 (3) | |
H9A | −0.0857 | 0.7263 | 1.0000 | 0.022* | |
C10 | 0.0790 (2) | 0.71934 (19) | 0.70128 (15) | 0.0187 (3) | |
C11 | −0.0015 (3) | 0.7180 (2) | 0.50313 (17) | 0.0271 (4) | |
H11A | 0.0088 | 0.6400 | 0.4471 | 0.041* | |
H11B | 0.0659 | 0.8112 | 0.4502 | 0.041* | |
H11C | −0.1350 | 0.7644 | 0.5385 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0246 (6) | 0.0224 (6) | 0.0266 (6) | −0.0026 (5) | −0.0078 (5) | −0.0115 (5) |
O2 | 0.0253 (6) | 0.0297 (6) | 0.0224 (6) | −0.0059 (5) | −0.0013 (5) | −0.0147 (5) |
O3 | 0.0360 (7) | 0.0185 (6) | 0.0267 (6) | −0.0014 (5) | −0.0151 (5) | −0.0075 (5) |
O4 | 0.0380 (7) | 0.0202 (6) | 0.0198 (6) | −0.0042 (5) | −0.0107 (5) | −0.0075 (4) |
N1 | 0.0261 (7) | 0.0188 (6) | 0.0168 (6) | −0.0049 (5) | −0.0053 (5) | −0.0073 (5) |
N2 | 0.0305 (7) | 0.0157 (6) | 0.0183 (7) | −0.0010 (5) | −0.0067 (5) | −0.0068 (5) |
C1 | 0.0245 (8) | 0.0467 (11) | 0.0325 (10) | −0.0085 (8) | 0.0010 (7) | −0.0210 (8) |
C2 | 0.0247 (7) | 0.0151 (7) | 0.0160 (7) | 0.0000 (5) | −0.0072 (6) | −0.0049 (5) |
C3 | 0.0239 (7) | 0.0144 (6) | 0.0160 (7) | −0.0021 (5) | −0.0061 (6) | −0.0025 (5) |
C4 | 0.0275 (8) | 0.0274 (8) | 0.0215 (8) | −0.0053 (6) | −0.0101 (6) | −0.0068 (6) |
C5 | 0.0219 (8) | 0.0339 (9) | 0.0267 (9) | −0.0049 (7) | −0.0081 (6) | −0.0075 (7) |
C6 | 0.0246 (8) | 0.0228 (8) | 0.0207 (8) | −0.0010 (6) | −0.0054 (6) | −0.0037 (6) |
C7 | 0.0254 (9) | 0.0389 (10) | 0.0300 (10) | 0.0000 (7) | −0.0013 (7) | −0.0105 (8) |
C8 | 0.0262 (8) | 0.0145 (7) | 0.0157 (7) | −0.0013 (6) | −0.0060 (6) | −0.0028 (5) |
C9 | 0.0215 (7) | 0.0166 (7) | 0.0173 (7) | −0.0034 (6) | −0.0059 (6) | −0.0035 (5) |
C10 | 0.0227 (7) | 0.0187 (7) | 0.0160 (7) | −0.0076 (6) | −0.0025 (5) | −0.0053 (5) |
C11 | 0.0367 (9) | 0.0280 (8) | 0.0211 (8) | −0.0088 (7) | −0.0115 (7) | −0.0057 (6) |
O1—C2 | 1.217 (2) | C3—C9 | 1.396 (2) |
O2—C2 | 1.3513 (19) | C4—C5 | 1.387 (2) |
O2—C1 | 1.439 (2) | C4—H4A | 0.9300 |
O3—C10 | 1.219 (2) | C5—C6 | 1.391 (2) |
O4—C10 | 1.3498 (18) | C5—H5A | 0.9300 |
O4—C11 | 1.440 (2) | C6—C8 | 1.394 (2) |
N1—C2 | 1.347 (2) | C6—C7 | 1.503 (2) |
N1—C3 | 1.411 (2) | C7—H7A | 0.9600 |
N1—H1A | 0.8600 | C7—H7B | 0.9600 |
N2—C10 | 1.339 (2) | C7—H7C | 0.9600 |
N2—C8 | 1.427 (2) | C8—C9 | 1.394 (2) |
N2—H2A | 0.8600 | C9—H9A | 0.9300 |
C1—H1B | 0.9600 | C11—H11A | 0.9600 |
C1—H1C | 0.9600 | C11—H11B | 0.9600 |
C1—H1D | 0.9600 | C11—H11C | 0.9600 |
C3—C4 | 1.391 (2) | ||
C2—O2—C1 | 114.85 (13) | C4—C5—H5A | 119.1 |
C10—O4—C11 | 116.20 (12) | C5—C6—C8 | 117.22 (15) |
C2—N1—C3 | 126.77 (13) | C5—C6—C7 | 121.28 (16) |
C2—N1—H1A | 116.6 | C8—C6—C7 | 121.49 (16) |
C3—N1—H1A | 116.6 | C6—C7—H7A | 109.5 |
C10—N2—C8 | 122.57 (13) | C6—C7—H7B | 109.5 |
C10—N2—H2A | 118.7 | H7A—C7—H7B | 109.5 |
C8—N2—H2A | 118.7 | C6—C7—H7C | 109.5 |
O2—C1—H1B | 109.5 | H7A—C7—H7C | 109.5 |
O2—C1—H1C | 109.5 | H7B—C7—H7C | 109.5 |
H1B—C1—H1C | 109.5 | C6—C8—C9 | 122.17 (15) |
O2—C1—H1D | 109.5 | C6—C8—N2 | 119.26 (14) |
H1B—C1—H1D | 109.5 | C9—C8—N2 | 118.57 (14) |
H1C—C1—H1D | 109.5 | C8—C9—C3 | 119.33 (15) |
O1—C2—N1 | 127.34 (15) | C8—C9—H9A | 120.3 |
O1—C2—O2 | 123.15 (15) | C3—C9—H9A | 120.3 |
N1—C2—O2 | 109.51 (13) | O3—C10—N2 | 126.19 (14) |
C4—C3—C9 | 119.32 (15) | O3—C10—O4 | 123.54 (14) |
C4—C3—N1 | 116.91 (14) | N2—C10—O4 | 110.27 (13) |
C9—C3—N1 | 123.75 (14) | O4—C11—H11A | 109.5 |
C3—C4—C5 | 120.18 (15) | O4—C11—H11B | 109.5 |
C3—C4—H4A | 119.9 | H11A—C11—H11B | 109.5 |
C5—C4—H4A | 119.9 | O4—C11—H11C | 109.5 |
C6—C5—C4 | 121.78 (16) | H11A—C11—H11C | 109.5 |
C6—C5—H5A | 119.1 | H11B—C11—H11C | 109.5 |
C3—N1—C2—O1 | −0.1 (3) | C5—C6—C8—N2 | 177.72 (14) |
C3—N1—C2—O2 | 178.99 (13) | C7—C6—C8—N2 | −1.0 (2) |
C1—O2—C2—O1 | −1.1 (2) | C10—N2—C8—C6 | −110.21 (18) |
C1—O2—C2—N1 | 179.77 (14) | C10—N2—C8—C9 | 68.8 (2) |
C2—N1—C3—C4 | −163.47 (15) | C6—C8—C9—C3 | 1.0 (2) |
C2—N1—C3—C9 | 18.4 (2) | N2—C8—C9—C3 | −178.01 (13) |
C9—C3—C4—C5 | −0.9 (2) | C4—C3—C9—C8 | 0.1 (2) |
N1—C3—C4—C5 | −179.12 (14) | N1—C3—C9—C8 | 178.20 (13) |
C3—C4—C5—C6 | 0.6 (3) | C8—N2—C10—O3 | −3.2 (3) |
C4—C5—C6—C8 | 0.5 (3) | C8—N2—C10—O4 | 176.39 (13) |
C4—C5—C6—C7 | 179.15 (16) | C11—O4—C10—O3 | 2.5 (2) |
C5—C6—C8—C9 | −1.3 (2) | C11—O4—C10—N2 | −177.14 (13) |
C7—C6—C8—C9 | −179.96 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.86 | 2.08 | 2.9339 (18) | 172 |
N2—H2A···O1ii | 0.86 | 2.00 | 2.8597 (19) | 174 |
Symmetry codes: (i) −x, −y+2, −z+2; (ii) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C11H14N2O4 |
Mr | 238.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.4223 (15), 8.1444 (16), 10.642 (2) |
α, β, γ (°) | 74.01 (3), 71.64 (3), 75.44 (3) |
V (Å3) | 577.3 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.64 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID IP area-detector diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.936, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5743, 2630, 2314 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.171, 1.01 |
No. of reflections | 2630 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.57 |
Computer programs: RAPID-AUTO (Rigaku, 2004), RAPID-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3i | 0.86 | 2.08 | 2.9339 (18) | 172 |
N2—H2A···O1ii | 0.86 | 2.00 | 2.8597 (19) | 174 |
Symmetry codes: (i) −x, −y+2, −z+2; (ii) −x, −y+1, −z+2. |
The title compound, (I), can be used as an intermediate for isocyanate (Uriz et al., 2002). Compound (I) was first prepared from toluene 2,4-bis(isocyanate) by reaction with methanol by Siefken (1949), but the single-crystal structure has not been reported until now.
The molecular structure of (I) is shown in Fig. 1. The crystal packing projected on to the bc face is shown in Fig. 2. There are two kinds of intermolecular N—H···O hydrogen bonds (Table 1). The N1—H1A···O3 and N2—H2A···O1 hydrogen bonds are approximately parallel to the ab face.