Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007815/bt6268sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007815/bt62683sup2.hkl |
CCDC reference: 214627
Key indicators
- Single-crystal X-ray study
- T = 133 K
- Mean (C-C) = 0.002 Å
- R factor = 0.034
- wR factor = 0.090
- Data-to-parameter ratio = 18.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
A solution of triphosgene (Cotarcǎ et al., 1996; 0.107 g, 0.36 mmol) in 10 ml dichloromethane was added at 278 K to a solution of succinimide (0.2138 g, 2.16 mmol) and triethylamine (0.3 ml, 2.16 mmol) in 10 ml dichloromethane. The solution was allowed to stand at room temperature for 1 h. The precipitate was filtered off and washed with dichloromethane (2 × 2.5 ml), yielding 0.1037 g (66%) product as a white solid. Single crystals were obtained from acetonitrile. M.p. 564–566 K; IR(KBr) 1824, 1754 cm−1 (C═O).
H atoms were included using a riding model with fixed C—H bond lengths of 0.99 Å; Uiso(H) values were fixed at 1.2 times the Ueq of the parent atom. The structure was refined as a pseudo-merohedral twin with components 0.451, 0.549 (2), twin matrix −1 0 0 / 0 − 1 0 / 0 0 1.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecule of the title compound in the crystal. Ellipsoids are shown at the the 50% probability level and H-atom radii are arbitrary. |
C9H8N2O5 | F(000) = 464 |
Mr = 224.17 | Dx = 1.608 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2372 (11) Å | Cell parameters from 5487 reflections |
b = 13.396 (2) Å | θ = 2.6–30.4° |
c = 9.5519 (12) Å | µ = 0.13 mm−1 |
β = 90.01 (2)° | T = 133 K |
V = 926.1 (2) Å3 | Tablet, colourless |
Z = 4 | 0.30 × 0.15 × 0.10 mm |
Bruker SMART 1000 CCD diffractometer | 2463 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 30.0°, θmin = 1.5° |
Detector resolution: 8.192 pixels mm-1 | h = −10→10 |
ω scans | k = −18→18 |
10780 measured reflections | l = −13→13 |
2707 independent 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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0616P)2] where P = (Fo2 + 2Fc2)/3 |
2707 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C9H8N2O5 | V = 926.1 (2) Å3 |
Mr = 224.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.2372 (11) Å | µ = 0.13 mm−1 |
b = 13.396 (2) Å | T = 133 K |
c = 9.5519 (12) Å | 0.30 × 0.15 × 0.10 mm |
β = 90.01 (2)° |
Bruker SMART 1000 CCD diffractometer | 2463 reflections with I > 2σ(I) |
10780 measured reflections | Rint = 0.032 |
2707 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.36 e Å−3 |
2707 reflections | Δρmin = −0.18 e Å−3 |
146 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 5.6002 (0.0034) x + 3.8236 (0.0079) y + 5.3997 (0.0052) z = 5.5512 (0.0030) * −0.0057 (0.0007) N1 * −0.0062 (0.0007) C1 * 0.0149 (0.0008) C2 * −0.0179 (0.0008) C3 * 0.0149 (0.0007) C4 Rms deviation of fitted atoms = 0.0129 5.0869 (0.0032) x + 9.5228 (0.0060) y + 0.2390 (0.0061) z = 6.0810 (0.0036) Angle to previous plane (with approximate e.s.d.) = 40.44 (0.06) * −0.0008 (0.0003) N1 * −0.0008 (0.0003) N2 * 0.0025 (0.0011) C9 * −0.0010 (0.0004) O5 Rms deviation of fitted atoms = 0.0014 5.6509 (0.0034) x + 4.8032 (0.0079) y − 4.8888 (0.0052) z = 1.7698 (0.0052) Angle to previous plane (with approximate e.s.d.) = 37.74 (0.06) * 0.0164 (0.0007) N2 * 0.0114 (0.0007) C5 * −0.0326 (0.0008) C6 * 0.0414 (0.0008) C7 * −0.0365 (0.0007) C8 Rms deviation of fitted atoms = 0.0301 |
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. The structure was refined as a pseudo-merohedral twin with components 0.451, 0.549 (2), twin matrix −1 0 0 / 0 − 1 0 / 0 0 1. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.41164 (16) | 0.32990 (8) | 0.36638 (12) | 0.0183 (2) | |
C2 | 0.54508 (17) | 0.29243 (8) | 0.25841 (12) | 0.0208 (2) | |
H2A | 0.4927 | 0.2343 | 0.2081 | 0.025* | |
H2B | 0.6627 | 0.2720 | 0.3030 | 0.025* | |
C3 | 0.57723 (17) | 0.37883 (8) | 0.15781 (13) | 0.0219 (2) | |
H3A | 0.7103 | 0.3955 | 0.1529 | 0.026* | |
H3B | 0.5337 | 0.3613 | 0.0627 | 0.026* | |
C4 | 0.46894 (17) | 0.46550 (8) | 0.21485 (13) | 0.0181 (2) | |
C5 | 0.09495 (17) | 0.65256 (8) | 0.38654 (12) | 0.0200 (2) | |
C6 | −0.03924 (17) | 0.69540 (8) | 0.28252 (13) | 0.0215 (2) | |
H6A | 0.0086 | 0.7588 | 0.2436 | 0.026* | |
H6B | −0.1600 | 0.7085 | 0.3276 | 0.026* | |
C7 | −0.05975 (18) | 0.61750 (8) | 0.16713 (13) | 0.0217 (2) | |
H7A | −0.1915 | 0.6006 | 0.1525 | 0.026* | |
H7B | −0.0079 | 0.6426 | 0.0779 | 0.026* | |
C8 | 0.04637 (17) | 0.52753 (8) | 0.21734 (13) | 0.0186 (2) | |
C9 | 0.25744 (19) | 0.49079 (8) | 0.41943 (11) | 0.0178 (2) | |
N1 | 0.37242 (13) | 0.43113 (7) | 0.33546 (10) | 0.0169 (2) | |
N2 | 0.14044 (14) | 0.55489 (7) | 0.34214 (10) | 0.01756 (19) | |
O1 | 0.34308 (13) | 0.28462 (7) | 0.46152 (10) | 0.0268 (2) | |
O2 | 0.46206 (13) | 0.54986 (6) | 0.17273 (10) | 0.0259 (2) | |
O3 | 0.15995 (15) | 0.69204 (7) | 0.48906 (10) | 0.0315 (2) | |
O4 | 0.05253 (13) | 0.44548 (6) | 0.16693 (10) | 0.0258 (2) | |
O5 | 0.25761 (15) | 0.48718 (7) | 0.54497 (8) | 0.0251 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0171 (5) | 0.0208 (5) | 0.0170 (5) | −0.0003 (4) | −0.0030 (4) | 0.0022 (4) |
C2 | 0.0222 (6) | 0.0203 (5) | 0.0198 (5) | 0.0035 (4) | −0.0001 (5) | 0.0015 (4) |
C3 | 0.0256 (6) | 0.0194 (5) | 0.0208 (5) | −0.0011 (4) | 0.0065 (5) | −0.0010 (4) |
C4 | 0.0192 (5) | 0.0198 (5) | 0.0154 (5) | −0.0025 (4) | 0.0011 (4) | 0.0006 (4) |
C5 | 0.0197 (5) | 0.0184 (5) | 0.0219 (5) | −0.0004 (4) | 0.0034 (4) | −0.0046 (4) |
C6 | 0.0228 (6) | 0.0187 (5) | 0.0228 (5) | 0.0024 (4) | 0.0030 (5) | −0.0025 (4) |
C7 | 0.0263 (6) | 0.0180 (5) | 0.0208 (5) | 0.0019 (4) | −0.0042 (5) | 0.0008 (4) |
C8 | 0.0205 (6) | 0.0183 (5) | 0.0169 (5) | −0.0015 (4) | −0.0010 (5) | −0.0008 (4) |
C9 | 0.0158 (5) | 0.0211 (5) | 0.0165 (4) | −0.0010 (4) | −0.0005 (5) | 0.0005 (4) |
N1 | 0.0177 (4) | 0.0173 (4) | 0.0157 (4) | 0.0001 (3) | 0.0026 (4) | 0.0022 (3) |
N2 | 0.0191 (5) | 0.0178 (4) | 0.0158 (4) | 0.0008 (3) | −0.0001 (4) | −0.0030 (3) |
O1 | 0.0299 (5) | 0.0263 (4) | 0.0243 (4) | 0.0011 (4) | 0.0039 (4) | 0.0086 (4) |
O2 | 0.0340 (5) | 0.0201 (4) | 0.0235 (5) | −0.0001 (3) | 0.0064 (4) | 0.0045 (3) |
O3 | 0.0362 (5) | 0.0297 (5) | 0.0287 (5) | 0.0027 (4) | −0.0066 (4) | −0.0135 (4) |
O4 | 0.0339 (5) | 0.0191 (4) | 0.0244 (5) | 0.0028 (3) | −0.0071 (4) | −0.0057 (3) |
O5 | 0.0274 (4) | 0.0332 (5) | 0.0148 (4) | 0.0006 (4) | 0.0012 (4) | 0.0003 (3) |
C1—O1 | 1.2001 (14) | C5—C6 | 1.5031 (17) |
C1—N1 | 1.4167 (14) | C6—C7 | 1.5250 (16) |
C1—C2 | 1.4996 (16) | C6—H6A | 0.9900 |
C2—C3 | 1.5223 (16) | C6—H6B | 0.9900 |
C2—H2A | 0.9900 | C7—C8 | 1.5075 (16) |
C2—H2B | 0.9900 | C7—H7A | 0.9900 |
C3—C4 | 1.5031 (16) | C7—H7B | 0.9900 |
C3—H3A | 0.9900 | C8—O4 | 1.2007 (14) |
C3—H3B | 0.9900 | C8—N2 | 1.4207 (15) |
C4—O2 | 1.2006 (14) | C9—O5 | 1.2001 (13) |
C4—N1 | 1.4239 (15) | C9—N1 | 1.4052 (15) |
C5—O3 | 1.2082 (14) | C9—N2 | 1.4139 (15) |
C5—N2 | 1.4143 (14) | ||
O1—C1—N1 | 123.98 (11) | C7—C6—H6A | 110.5 |
O1—C1—C2 | 128.17 (10) | C5—C6—H6B | 110.5 |
N1—C1—C2 | 107.82 (9) | C7—C6—H6B | 110.5 |
C1—C2—C3 | 106.15 (9) | H6A—C6—H6B | 108.7 |
C1—C2—H2A | 110.5 | C8—C7—C6 | 105.53 (10) |
C3—C2—H2A | 110.5 | C8—C7—H7A | 110.6 |
C1—C2—H2B | 110.5 | C6—C7—H7A | 110.6 |
C3—C2—H2B | 110.5 | C8—C7—H7B | 110.6 |
H2A—C2—H2B | 108.7 | C6—C7—H7B | 110.6 |
C4—C3—C2 | 106.18 (10) | H7A—C7—H7B | 108.8 |
C4—C3—H3A | 110.5 | O4—C8—N2 | 123.69 (11) |
C2—C3—H3A | 110.5 | O4—C8—C7 | 128.55 (11) |
C4—C3—H3B | 110.5 | N2—C8—C7 | 107.74 (9) |
C2—C3—H3B | 110.5 | O5—C9—N1 | 123.16 (12) |
H3A—C3—H3B | 108.7 | O5—C9—N2 | 123.14 (12) |
O2—C4—N1 | 123.72 (11) | N1—C9—N2 | 113.70 (9) |
O2—C4—C3 | 128.84 (11) | C9—N1—C1 | 122.96 (10) |
N1—C4—C3 | 107.43 (9) | C9—N1—C4 | 124.65 (9) |
O3—C5—N2 | 123.88 (11) | C1—N1—C4 | 112.33 (9) |
O3—C5—C6 | 128.32 (11) | C9—N2—C5 | 123.00 (9) |
N2—C5—C6 | 107.78 (9) | C9—N2—C8 | 124.63 (9) |
C5—C6—C7 | 106.22 (9) | C5—N2—C8 | 112.26 (9) |
C5—C6—H6A | 110.5 | ||
O1—C1—C2—C3 | 176.48 (12) | C2—C1—N1—C4 | −0.04 (13) |
N1—C1—C2—C3 | −1.80 (13) | O2—C4—N1—C9 | 0.26 (18) |
C1—C2—C3—C4 | 2.86 (13) | C3—C4—N1—C9 | 179.14 (11) |
C2—C3—C4—O2 | 175.89 (13) | O2—C4—N1—C1 | −176.99 (12) |
C2—C3—C4—N1 | −2.91 (13) | C3—C4—N1—C1 | 1.89 (13) |
O3—C5—C6—C7 | 174.57 (12) | O5—C9—N2—C5 | 37.12 (19) |
N2—C5—C6—C7 | −3.72 (13) | N1—C9—N2—C5 | −143.37 (10) |
C5—C6—C7—C8 | 6.42 (13) | O5—C9—N2—C8 | −138.71 (13) |
C6—C7—C8—O4 | 171.75 (13) | N1—C9—N2—C8 | 40.80 (16) |
C6—C7—C8—N2 | −6.91 (13) | O3—C5—N2—C9 | 4.64 (18) |
O5—C9—N1—C1 | 39.17 (18) | C6—C5—N2—C9 | −176.98 (11) |
N2—C9—N1—C1 | −140.34 (11) | O3—C5—N2—C8 | −179.07 (11) |
O5—C9—N1—C4 | −137.79 (14) | C6—C5—N2—C8 | −0.69 (13) |
N2—C9—N1—C4 | 42.70 (15) | O4—C8—N2—C9 | 2.37 (19) |
O1—C1—N1—C9 | 4.30 (18) | C7—C8—N2—C9 | −178.89 (11) |
C2—C1—N1—C9 | −177.34 (10) | O4—C8—N2—C5 | −173.85 (12) |
O1—C1—N1—C4 | −178.40 (12) | C7—C8—N2—C5 | 4.89 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O1i | 0.99 | 2.60 | 3.3530 (15) | 132 |
C6—H6B···O1ii | 0.99 | 3.23 | 3.4198 (16) | 93 |
C3—H3B···O1i | 0.99 | 2.58 | 3.3436 (15) | 134 |
C3—H3B···O2iii | 0.99 | 2.54 | 3.3108 (16) | 134 |
C7—H7A···O2iv | 0.99 | 2.60 | 3.5779 (17) | 168 |
C2—H2B···O3v | 0.99 | 2.41 | 3.2274 (16) | 139 |
C7—H7B···O3vi | 0.99 | 2.66 | 3.4543 (15) | 137 |
C7—H7B···O4vii | 0.99 | 2.64 | 3.3011 (16) | 124 |
C3—H3A···O4viii | 0.99 | 2.57 | 3.5548 (16) | 174 |
C6—H6A···O4ii | 0.99 | 2.68 | 3.3862 (15) | 129 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1; (vi) x, −y+3/2, z−1/2; (vii) −x, −y+1, −z; (viii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C9H8N2O5 |
Mr | 224.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 133 |
a, b, c (Å) | 7.2372 (11), 13.396 (2), 9.5519 (12) |
β (°) | 90.01 (2) |
V (Å3) | 926.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.30 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10780, 2707, 2463 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.091, 1.06 |
No. of reflections | 2707 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.18 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
C9—O5 | 1.2001 (13) | C9—N2 | 1.4139 (15) |
C9—N1 | 1.4052 (15) | ||
O5—C9—N1 | 123.16 (12) | N1—C9—N2 | 113.70 (9) |
O5—C9—N2 | 123.14 (12) | ||
O5—C9—N1—C1 | 39.17 (18) | N2—C9—N1—C4 | 42.70 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O1i | 0.99 | 2.60 | 3.3530 (15) | 132 |
C6—H6B···O1ii | 0.99 | 3.23 | 3.4198 (16) | 93 |
C3—H3B···O1i | 0.99 | 2.58 | 3.3436 (15) | 134 |
C3—H3B···O2iii | 0.99 | 2.54 | 3.3108 (16) | 134 |
C7—H7A···O2iv | 0.99 | 2.60 | 3.5779 (17) | 168 |
C2—H2B···O3v | 0.99 | 2.41 | 3.2274 (16) | 139 |
C7—H7B···O3vi | 0.99 | 2.66 | 3.4543 (15) | 137 |
C7—H7B···O4vii | 0.99 | 2.64 | 3.3011 (16) | 124 |
C3—H3A···O4viii | 0.99 | 2.57 | 3.5548 (16) | 174 |
C6—H6A···O4ii | 0.99 | 2.68 | 3.3862 (15) | 129 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1; (vi) x, −y+3/2, z−1/2; (vii) −x, −y+1, −z; (viii) x+1, y, z. |
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N,N'-Carbonyldisuccinimide, (3), is a new compound that has considerable potential in organic synthesis. We were motivated to prepare it by literature reports that N-trifluoroacetylsuccinimide displays enhanced reactivity towards N– and O-nucleophiles (Katritzky et al., 1999). We are interested in compounds of higher reactivity that can be used instead of phosgene (Ryan et al., 1996; Senet, 1997). In this connection, we have studied the reactivity and structures of organic carbonates such as N,N'-disuccinimidyl carbonate (preceding paper; Simon, Csunderlik et al., 2003, and references therein; Simon, Csunderlik & Medeleanu, 2003). Here we report the synthesis (see Experimental) of the title compound (3) from triphosgene (2) and succinimide (1), together with its structure.
The molecule of (3) is shown in Fig. 1. It displays non-crystallographic twofold symmetry to a good approximation (r.m.s. deviation 0.022 Å), with the twofold axis passing along the bond C9═O5. The central CN2O moiety is planar (r.m.s. deviation 0.0014 Å) and subtends angles of 40.44 (6) and 37.74 (6)° with the succinimide rings. Bond lengths and angles may be regarded as normal (Table 1).
Each H atom is involved in weak C—H···O hydrogen bonds, H3B and H7B in three-centre systems. The net effect is to link the molecules in a complex three-dimensional network.