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The title compound, C9H8N2O5, displays twofold symmetry to a good approximation. Bond lengths and angles (Å and °) at the central carbonyl group are: C=O 1.2001 (13), C-N 1.4052 (15) and 1.4139 (15), O=C-N 123.14 (12) and 123.16 (12), and N-C-N 113.70 (9). The succin­imide rings subtend angles of 40.44 (6) and 37.74 (6)° with the carbonyl plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007815/bt6268sup1.cif
Contains datablocks 3, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007815/bt62683sup2.hkl
Contains datablock 3

CCDC reference: 214627

Key indicators

  • Single-crystal X-ray study
  • T = 133 K
  • Mean [sigma](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








Comment top

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 C9O5. 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.

Experimental top

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 (CO).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] 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.
N,N'-Carbonyldisuccinimide top
Crystal data top
C9H8N2O5F(000) = 464
Mr = 224.17Dx = 1.608 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.2372 (11) ÅCell parameters from 5487 reflections
b = 13.396 (2) Åθ = 2.6–30.4°
c = 9.5519 (12) ŵ = 0.13 mm1
β = 90.01 (2)°T = 133 K
V = 926.1 (2) Å3Tablet, colourless
Z = 40.30 × 0.15 × 0.10 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
2463 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Graphite monochromatorθmax = 30.0°, θmin = 1.5°
Detector resolution: 8.192 pixels mm-1h = 1010
ω scansk = 1818
10780 measured reflectionsl = 1313
2707 independent 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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-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 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C9H8N2O5V = 926.1 (2) Å3
Mr = 224.17Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.2372 (11) ŵ = 0.13 mm1
b = 13.396 (2) ÅT = 133 K
c = 9.5519 (12) Å0.30 × 0.15 × 0.10 mm
β = 90.01 (2)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
2463 reflections with I > 2σ(I)
10780 measured reflectionsRint = 0.032
2707 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.06Δρmax = 0.36 e Å3
2707 reflectionsΔρmin = 0.18 e Å3
146 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.41164 (16)0.32990 (8)0.36638 (12)0.0183 (2)
C20.54508 (17)0.29243 (8)0.25841 (12)0.0208 (2)
H2A0.49270.23430.20810.025*
H2B0.66270.27200.30300.025*
C30.57723 (17)0.37883 (8)0.15781 (13)0.0219 (2)
H3A0.71030.39550.15290.026*
H3B0.53370.36130.06270.026*
C40.46894 (17)0.46550 (8)0.21485 (13)0.0181 (2)
C50.09495 (17)0.65256 (8)0.38654 (12)0.0200 (2)
C60.03924 (17)0.69540 (8)0.28252 (13)0.0215 (2)
H6A0.00860.75880.24360.026*
H6B0.16000.70850.32760.026*
C70.05975 (18)0.61750 (8)0.16713 (13)0.0217 (2)
H7A0.19150.60060.15250.026*
H7B0.00790.64260.07790.026*
C80.04637 (17)0.52753 (8)0.21734 (13)0.0186 (2)
C90.25744 (19)0.49079 (8)0.41943 (11)0.0178 (2)
N10.37242 (13)0.43113 (7)0.33546 (10)0.0169 (2)
N20.14044 (14)0.55489 (7)0.34214 (10)0.01756 (19)
O10.34308 (13)0.28462 (7)0.46152 (10)0.0268 (2)
O20.46206 (13)0.54986 (6)0.17273 (10)0.0259 (2)
O30.15995 (15)0.69204 (7)0.48906 (10)0.0315 (2)
O40.05253 (13)0.44548 (6)0.16693 (10)0.0258 (2)
O50.25761 (15)0.48718 (7)0.54497 (8)0.0251 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0171 (5)0.0208 (5)0.0170 (5)0.0003 (4)0.0030 (4)0.0022 (4)
C20.0222 (6)0.0203 (5)0.0198 (5)0.0035 (4)0.0001 (5)0.0015 (4)
C30.0256 (6)0.0194 (5)0.0208 (5)0.0011 (4)0.0065 (5)0.0010 (4)
C40.0192 (5)0.0198 (5)0.0154 (5)0.0025 (4)0.0011 (4)0.0006 (4)
C50.0197 (5)0.0184 (5)0.0219 (5)0.0004 (4)0.0034 (4)0.0046 (4)
C60.0228 (6)0.0187 (5)0.0228 (5)0.0024 (4)0.0030 (5)0.0025 (4)
C70.0263 (6)0.0180 (5)0.0208 (5)0.0019 (4)0.0042 (5)0.0008 (4)
C80.0205 (6)0.0183 (5)0.0169 (5)0.0015 (4)0.0010 (5)0.0008 (4)
C90.0158 (5)0.0211 (5)0.0165 (4)0.0010 (4)0.0005 (5)0.0005 (4)
N10.0177 (4)0.0173 (4)0.0157 (4)0.0001 (3)0.0026 (4)0.0022 (3)
N20.0191 (5)0.0178 (4)0.0158 (4)0.0008 (3)0.0001 (4)0.0030 (3)
O10.0299 (5)0.0263 (4)0.0243 (4)0.0011 (4)0.0039 (4)0.0086 (4)
O20.0340 (5)0.0201 (4)0.0235 (5)0.0001 (3)0.0064 (4)0.0045 (3)
O30.0362 (5)0.0297 (5)0.0287 (5)0.0027 (4)0.0066 (4)0.0135 (4)
O40.0339 (5)0.0191 (4)0.0244 (5)0.0028 (3)0.0071 (4)0.0057 (3)
O50.0274 (4)0.0332 (5)0.0148 (4)0.0006 (4)0.0012 (4)0.0003 (3)
Geometric parameters (Å, º) top
C1—O11.2001 (14)C5—C61.5031 (17)
C1—N11.4167 (14)C6—C71.5250 (16)
C1—C21.4996 (16)C6—H6A0.9900
C2—C31.5223 (16)C6—H6B0.9900
C2—H2A0.9900C7—C81.5075 (16)
C2—H2B0.9900C7—H7A0.9900
C3—C41.5031 (16)C7—H7B0.9900
C3—H3A0.9900C8—O41.2007 (14)
C3—H3B0.9900C8—N21.4207 (15)
C4—O21.2006 (14)C9—O51.2001 (13)
C4—N11.4239 (15)C9—N11.4052 (15)
C5—O31.2082 (14)C9—N21.4139 (15)
C5—N21.4143 (14)
O1—C1—N1123.98 (11)C7—C6—H6A110.5
O1—C1—C2128.17 (10)C5—C6—H6B110.5
N1—C1—C2107.82 (9)C7—C6—H6B110.5
C1—C2—C3106.15 (9)H6A—C6—H6B108.7
C1—C2—H2A110.5C8—C7—C6105.53 (10)
C3—C2—H2A110.5C8—C7—H7A110.6
C1—C2—H2B110.5C6—C7—H7A110.6
C3—C2—H2B110.5C8—C7—H7B110.6
H2A—C2—H2B108.7C6—C7—H7B110.6
C4—C3—C2106.18 (10)H7A—C7—H7B108.8
C4—C3—H3A110.5O4—C8—N2123.69 (11)
C2—C3—H3A110.5O4—C8—C7128.55 (11)
C4—C3—H3B110.5N2—C8—C7107.74 (9)
C2—C3—H3B110.5O5—C9—N1123.16 (12)
H3A—C3—H3B108.7O5—C9—N2123.14 (12)
O2—C4—N1123.72 (11)N1—C9—N2113.70 (9)
O2—C4—C3128.84 (11)C9—N1—C1122.96 (10)
N1—C4—C3107.43 (9)C9—N1—C4124.65 (9)
O3—C5—N2123.88 (11)C1—N1—C4112.33 (9)
O3—C5—C6128.32 (11)C9—N2—C5123.00 (9)
N2—C5—C6107.78 (9)C9—N2—C8124.63 (9)
C5—C6—C7106.22 (9)C5—N2—C8112.26 (9)
C5—C6—H6A110.5
O1—C1—C2—C3176.48 (12)C2—C1—N1—C40.04 (13)
N1—C1—C2—C31.80 (13)O2—C4—N1—C90.26 (18)
C1—C2—C3—C42.86 (13)C3—C4—N1—C9179.14 (11)
C2—C3—C4—O2175.89 (13)O2—C4—N1—C1176.99 (12)
C2—C3—C4—N12.91 (13)C3—C4—N1—C11.89 (13)
O3—C5—C6—C7174.57 (12)O5—C9—N2—C537.12 (19)
N2—C5—C6—C73.72 (13)N1—C9—N2—C5143.37 (10)
C5—C6—C7—C86.42 (13)O5—C9—N2—C8138.71 (13)
C6—C7—C8—O4171.75 (13)N1—C9—N2—C840.80 (16)
C6—C7—C8—N26.91 (13)O3—C5—N2—C94.64 (18)
O5—C9—N1—C139.17 (18)C6—C5—N2—C9176.98 (11)
N2—C9—N1—C1140.34 (11)O3—C5—N2—C8179.07 (11)
O5—C9—N1—C4137.79 (14)C6—C5—N2—C80.69 (13)
N2—C9—N1—C442.70 (15)O4—C8—N2—C92.37 (19)
O1—C1—N1—C94.30 (18)C7—C8—N2—C9178.89 (11)
C2—C1—N1—C9177.34 (10)O4—C8—N2—C5173.85 (12)
O1—C1—N1—C4178.40 (12)C7—C8—N2—C54.89 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1i0.992.603.3530 (15)132
C6—H6B···O1ii0.993.233.4198 (16)93
C3—H3B···O1i0.992.583.3436 (15)134
C3—H3B···O2iii0.992.543.3108 (16)134
C7—H7A···O2iv0.992.603.5779 (17)168
C2—H2B···O3v0.992.413.2274 (16)139
C7—H7B···O3vi0.992.663.4543 (15)137
C7—H7B···O4vii0.992.643.3011 (16)124
C3—H3A···O4viii0.992.573.5548 (16)174
C6—H6A···O4ii0.992.683.3862 (15)129
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1/2, z+1/2; (iii) x+1, y+1, z; (iv) x1, y, z; (v) x+1, y+1, z+1; (vi) x, y+3/2, z1/2; (vii) x, y+1, z; (viii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC9H8N2O5
Mr224.17
Crystal system, space groupMonoclinic, P21/c
Temperature (K)133
a, b, c (Å)7.2372 (11), 13.396 (2), 9.5519 (12)
β (°) 90.01 (2)
V3)926.1 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.30 × 0.15 × 0.10
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10780, 2707, 2463
Rint0.032
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.091, 1.06
No. of reflections2707
No. of parameters146
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.36, 0.18

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) top
C9—O51.2001 (13)C9—N21.4139 (15)
C9—N11.4052 (15)
O5—C9—N1123.16 (12)N1—C9—N2113.70 (9)
O5—C9—N2123.14 (12)
O5—C9—N1—C139.17 (18)N2—C9—N1—C442.70 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1i0.992.603.3530 (15)132
C6—H6B···O1ii0.993.233.4198 (16)93
C3—H3B···O1i0.992.583.3436 (15)134
C3—H3B···O2iii0.992.543.3108 (16)134
C7—H7A···O2iv0.992.603.5779 (17)168
C2—H2B···O3v0.992.413.2274 (16)139
C7—H7B···O3vi0.992.663.4543 (15)137
C7—H7B···O4vii0.992.643.3011 (16)124
C3—H3A···O4viii0.992.573.5548 (16)174
C6—H6A···O4ii0.992.683.3862 (15)129
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y+1/2, z+1/2; (iii) x+1, y+1, z; (iv) x1, y, z; (v) x+1, y+1, z+1; (vi) x, y+3/2, z1/2; (vii) x, y+1, z; (viii) x+1, y, z.
 

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