Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006797/om6087sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006797/om6087Isup2.hkl |
CCDC reference: 185796
Key indicators
- Single-crystal X-ray study
- T = 300 K
- Mean (C-C) = 0.003 Å
- R factor = 0.054
- wR factor = 0.139
- Data-to-parameter ratio = 17.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was synthesized as described by Ralph et al. (1959). Recrystallization from benzene yielded colorless rectangular planar crystals with a melting point of 348–350 K suitable for X-ray analysis. The crystal used for the structure determination was trimmed from a larger crystal using a sharp scalpel. No correction for crystal decay during the data collection (7 h) was made.
H atoms on C atoms were constrained to ride on the parent atom with usual bond lengths. The H atomn on the amide N atom was not constrained in the refinement and the final N—H bond length was 0.85 (2) Å.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL-NT (Bruker, 2001); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.
C7H11NO4 | F(000) = 368 |
Mr = 173.17 | Dx = 1.335 Mg m−3 Dm = 1.33 Mg m−3 Dm measured by Flotation |
Monoclinic, P21/n | Melting point: 350 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 11.366 (2) Å | Cell parameters from 300 reflections |
b = 5.7345 (13) Å | θ = 2.2–24.5° |
c = 13.327 (3) Å | µ = 0.11 mm−1 |
β = 97.388 (5)° | T = 300 K |
V = 861.4 (3) Å3 | Plate, colorless |
Z = 4 | 0.40 × 0.35 × 0.15 mm |
Bruker CCD area-detector diffractometer | 2044 independent reflections |
Radiation source: fine-focus sealed tube | 1489 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −14→11 |
Tmin = 0.87, Tmax = 0.98 | k = −7→7 |
5292 measured reflections | l = −13→17 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.061P)2 + 0.2379P] where P = (Fo2 + 2Fc2)/3 |
2044 reflections | (Δ/σ)max = 0.001 |
115 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C7H11NO4 | V = 861.4 (3) Å3 |
Mr = 173.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.366 (2) Å | µ = 0.11 mm−1 |
b = 5.7345 (13) Å | T = 300 K |
c = 13.327 (3) Å | 0.40 × 0.35 × 0.15 mm |
β = 97.388 (5)° |
Bruker CCD area-detector diffractometer | 2044 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1489 reflections with I > 2σ(I) |
Tmin = 0.87, Tmax = 0.98 | Rint = 0.022 |
5292 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.21 e Å−3 |
2044 reflections | Δρmin = −0.15 e Å−3 |
115 parameters |
Geometry. All e.s.d.'s 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 | 0.01782 (11) | 0.2523 (2) | 1.07166 (11) | 0.0488 (4) | |
O3 | 0.31358 (13) | 0.2499 (3) | 1.19422 (12) | 0.0578 (4) | |
O5 | 0.34333 (12) | 0.2470 (2) | 0.96508 (11) | 0.0537 (4) | |
O6 | 0.27470 (11) | −0.0992 (2) | 0.90452 (11) | 0.0533 (4) | |
N1 | 0.15821 (13) | 0.1108 (3) | 0.98660 (12) | 0.0403 (4) | |
H1 | 0.1097 (17) | 0.001 (4) | 0.9693 (14) | 0.040 (5)* | |
C1 | 0.11611 (15) | 0.2777 (3) | 1.04676 (13) | 0.0366 (4) | |
C2 | 0.19073 (15) | 0.4857 (3) | 1.07814 (14) | 0.0396 (4) | |
H2A | 0.1432 | 0.5967 | 1.1103 | 0.048* | |
H2B | 0.2135 | 0.5594 | 1.0180 | 0.048* | |
C3 | 0.30163 (15) | 0.4327 (3) | 1.14977 (14) | 0.0402 (4) | |
C4 | 0.39148 (17) | 0.6213 (4) | 1.16260 (17) | 0.0569 (6) | |
H4A | 0.4458 | 0.5931 | 1.2227 | 0.085* | |
H4B | 0.3526 | 0.7684 | 1.1685 | 0.085* | |
H4C | 0.4342 | 0.6245 | 1.1050 | 0.085* | |
C5 | 0.26749 (16) | 0.1014 (3) | 0.95289 (13) | 0.0395 (4) | |
C6 | 0.38486 (19) | −0.1467 (4) | 0.86308 (18) | 0.0602 (6) | |
H6A | 0.3993 | −0.3134 | 0.8639 | 0.072* | |
H6B | 0.4503 | −0.0726 | 0.9052 | 0.072* | |
C7 | 0.3797 (2) | −0.0600 (6) | 0.75944 (19) | 0.0775 (8) | |
H7A | 0.3113 | −0.1236 | 0.7189 | 0.116* | |
H7B | 0.4501 | −0.1065 | 0.7319 | 0.116* | |
H7C | 0.3744 | 0.1071 | 0.7595 | 0.116* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0351 (7) | 0.0546 (8) | 0.0588 (9) | −0.0060 (6) | 0.0140 (6) | −0.0116 (6) |
O3 | 0.0575 (9) | 0.0560 (9) | 0.0576 (9) | 0.0001 (7) | −0.0013 (7) | 0.0109 (7) |
O5 | 0.0416 (8) | 0.0606 (9) | 0.0615 (9) | −0.0149 (7) | 0.0164 (7) | −0.0108 (7) |
O6 | 0.0466 (8) | 0.0519 (8) | 0.0655 (9) | −0.0038 (6) | 0.0224 (7) | −0.0126 (7) |
N1 | 0.0333 (8) | 0.0410 (8) | 0.0480 (9) | −0.0083 (7) | 0.0104 (7) | −0.0063 (7) |
C1 | 0.0334 (9) | 0.0382 (9) | 0.0379 (9) | 0.0000 (7) | 0.0038 (7) | 0.0029 (7) |
C2 | 0.0360 (9) | 0.0355 (9) | 0.0474 (10) | −0.0003 (8) | 0.0059 (8) | −0.0016 (8) |
C3 | 0.0385 (10) | 0.0437 (10) | 0.0391 (10) | −0.0011 (8) | 0.0084 (7) | −0.0062 (8) |
C4 | 0.0439 (11) | 0.0606 (13) | 0.0657 (14) | −0.0126 (10) | 0.0055 (10) | −0.0130 (11) |
C5 | 0.0367 (9) | 0.0445 (10) | 0.0382 (9) | −0.0027 (8) | 0.0079 (7) | −0.0004 (8) |
C6 | 0.0472 (12) | 0.0670 (14) | 0.0700 (15) | 0.0080 (11) | 0.0216 (10) | −0.0084 (12) |
C7 | 0.0589 (14) | 0.117 (2) | 0.0601 (14) | −0.0085 (15) | 0.0206 (11) | −0.0080 (15) |
O1—C1 | 1.214 (2) | C2—H2B | 0.9700 |
O3—C3 | 1.203 (2) | C3—C4 | 1.482 (3) |
O5—C5 | 1.196 (2) | C4—H4A | 0.9600 |
O6—C5 | 1.327 (2) | C4—H4B | 0.9600 |
O6—C6 | 1.457 (2) | C4—H4C | 0.9600 |
N1—C1 | 1.373 (2) | C6—C7 | 1.462 (3) |
N1—C5 | 1.375 (2) | C6—H6A | 0.9700 |
N1—H1 | 0.85 (2) | C6—H6B | 0.9700 |
C1—C2 | 1.492 (2) | C7—H7A | 0.9600 |
C2—C3 | 1.511 (3) | C7—H7B | 0.9600 |
C2—H2A | 0.9700 | C7—H7C | 0.9600 |
C5—O6—C6 | 117.11 (16) | C3—C4—H4C | 109.5 |
C1—N1—C5 | 127.96 (16) | H4A—C4—H4C | 109.5 |
C1—N1—H1 | 114.4 (13) | H4B—C4—H4C | 109.5 |
C5—N1—H1 | 117.6 (13) | O5—C5—O6 | 125.66 (17) |
O1—C1—N1 | 118.55 (16) | O5—C5—N1 | 126.43 (18) |
O1—C1—C2 | 121.93 (16) | O6—C5—N1 | 107.91 (15) |
N1—C1—C2 | 119.50 (15) | O6—C6—C7 | 111.27 (19) |
C1—C2—C3 | 114.48 (15) | O6—C6—H6A | 109.4 |
C1—C2—H2A | 108.6 | C7—C6—H6A | 109.4 |
C3—C2—H2A | 108.6 | O6—C6—H6B | 109.4 |
C1—C2—H2B | 108.6 | C7—C6—H6B | 109.4 |
C3—C2—H2B | 108.6 | H6A—C6—H6B | 108.0 |
H2A—C2—H2B | 107.6 | C6—C7—H7A | 109.5 |
O3—C3—C4 | 123.12 (18) | C6—C7—H7B | 109.5 |
O3—C3—C2 | 121.22 (17) | H7A—C7—H7B | 109.5 |
C4—C3—C2 | 115.65 (17) | C6—C7—H7C | 109.5 |
C3—C4—H4A | 109.5 | H7A—C7—H7C | 109.5 |
C3—C4—H4B | 109.5 | H7B—C7—H7C | 109.5 |
H4A—C4—H4B | 109.5 | ||
C5—N1—C1—O1 | −177.59 (17) | C6—O6—C5—O5 | 0.3 (3) |
C5—N1—C1—C2 | 3.4 (3) | C6—O6—C5—N1 | −179.38 (16) |
O1—C1—C2—C3 | 113.35 (19) | C1—N1—C5—O5 | −5.2 (3) |
N1—C1—C2—C3 | −67.7 (2) | C1—N1—C5—O6 | 174.53 (17) |
C1—C2—C3—O3 | −15.7 (3) | C5—O6—C6—C7 | −90.1 (2) |
C1—C2—C3—C4 | 165.63 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.85 (2) | 2.07 (2) | 2.923 (2) | 176 (1) |
Symmetry code: (i) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C7H11NO4 |
Mr | 173.17 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 300 |
a, b, c (Å) | 11.366 (2), 5.7345 (13), 13.327 (3) |
β (°) | 97.388 (5) |
V (Å3) | 861.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.40 × 0.35 × 0.15 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.87, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5292, 2044, 1489 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.139, 1.04 |
No. of reflections | 2044 |
No. of parameters | 115 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.15 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXTL-NT (Bruker, 2001), SHELXTL-NT.
O1—C1 | 1.214 (2) | N1—C1 | 1.373 (2) |
O3—C3 | 1.203 (2) | N1—C5 | 1.375 (2) |
O5—C5 | 1.196 (2) | N1—H1 | 0.85 (2) |
O6—C5 | 1.327 (2) | C1—C2 | 1.492 (2) |
O6—C6 | 1.457 (2) | C2—C3 | 1.511 (3) |
C5—O6—C6 | 117.11 (16) | O3—C3—C4 | 123.12 (18) |
C1—N1—C5 | 127.96 (16) | O3—C3—C2 | 121.22 (17) |
C1—N1—H1 | 114.4 (13) | C4—C3—C2 | 115.65 (17) |
C5—N1—H1 | 117.6 (13) | O5—C5—O6 | 125.66 (17) |
O1—C1—N1 | 118.55 (16) | O5—C5—N1 | 126.43 (18) |
O1—C1—C2 | 121.93 (16) | O6—C5—N1 | 107.91 (15) |
N1—C1—C2 | 119.50 (15) | O6—C6—C7 | 111.27 (19) |
C1—C2—C3 | 114.48 (15) | ||
C5—N1—C1—O1 | −177.59 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.85 (2) | 2.07 (2) | 2.923 (2) | 176 (1) |
Symmetry code: (i) −x, −y, −z+2. |
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The preparation of N-acetoacetylurethane, (I), was first described by Ralph et al. (1959) in pursuit of orotic acids. Dewar & Shaw (1961) subsequently reacted this compound with triethyl orthoformate to give 2-acetyl-3-ethoxy-N-ethoxycarbonylacrylamide which was then treated with ammonia to finally give 5-acetyluracil. While the crystal structure of several carbamates has been reported, the structure of this 3-ketoacyl carbamate has not been described.
N-Acetoacetylurethane is easily prepared from diketene and urethane in refluxing acetic acid. Unlike Ralph et al. (1959), who stated that the compound could be isolated from benzene as fine crystals, we found that slow recrystallization of the compound from several solvents, including benzene, afforded large planar crystals in the P21/n space group. The molecule of (I) and the associated numbering scheme are shown in Fig. 1.
In the crystal, the molecules are arranged as hydrogen-bonded dimers through the amide moiety of the acyl carbamate (Fig. 2). It is interesting that the molecule evidently adopts exclusively the keto rather than the enol form in the crystal, despite the fact that the latter would permit a substantial hydrogen-bonding network. All bond lengths are consistent with anticipated values.