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The title compound, C9H8N2O7, possesses crystallographic twofold symmetry and displays an s-cis-s-cis conformation of the carbonate group. Bond lengths and angles (Å and °) involving this group are: C=O 1.175 (3), C-O 1.3669 (17), O-N 1.3876 (15); O=C-O 127.67 (8) and O-C-O 104.67 (17). The succin­imide ring subtends an angle of 73.92 (4)° with the carbonate plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803007803/bt6267sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803007803/bt6267Isup2.hkl
Contains datablock I

CCDC reference: 214626

Key indicators

  • Single-crystal X-ray study
  • T = 133 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.027
  • wR factor = 0.073
  • Data-to-parameter ratio = 9.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 29.97 From the CIF: _reflns_number_total 773 Count of symmetry unique reflns 773 Completeness (_total/calc) 100.00% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.

Comment top

We are interested in the structures and synthetic applications of organic carbonates and have recently published the structures of bis(o-nitrophenyl) carbonate and bis(p-nitrophenyl) carbonate (Simon et al., 2003a,b). Introductory material is presented in the first of these publications. Here we present the structure of N,N'-disuccinimidyl carbonate, (I), a versatile reagent for the preparation of active esters in peptide chemistry (Pearson & Roush, 2001; Ogura et al., 1979; Gooßen & Ghosh, 2001) and as a substitute for phosgene in reactions with various nucleophiles (Takeda & Ogura, 1982; Halstrøm & Kovács, 1986; Ghosh et al., 1992; Boeden et al., 1998).

The molecule of (I) is shown in Fig. 1. It displays crystallographic twofold symmetry, with the twofold axis (symmetry code: −x, 1 − y, z) passing along the bond C5O4. The carbonate moiety displays the usual s-cis-s-cis conformation (cf. torsion angles in Table 1). The N atom is essentially coplanar with the carbonate moiety, lying only 0.0174 (3) Å out of the exact carbonate plane. The succinimide ring is almost planar (r.m.s. deviation 0.040 Å) and subtends an interplanar angle of 73.92 (4)° to the carbonate group.

Bond lengths and angles of the carbonate moiety (Table 1) may be considered normal. A search of the Cambridge Structural Database (Allen, 2002; 2003 version) revealed no hit for the moiety N—O—C(O)—O—N; our earlier paper (Simon et al., 2003a) briefly presents database results for diaryl carbonates.

The molecular packing involves two weak C—H···O hydrogen bonds (Table 2), the effect of which is to link the molecules to form two interpenetrating networks, one of which is shown in Fig. 2. Short intramolecular contacts O1···C4i [2.991 (2) Å; symmetry code: (i) −1/4 + x, 5/4 − y, −1/4 + z] and O1···O4ii [2.975 (2) Å; symmetry code: (ii) 1/4 + x, 5/4 − y, 1/4 + z] are also observed. These are not shown in Fig. 2.

Experimental top

Triphosgene (bis(trichloromethyl) carbonate) was treated with six equivalents of N-hydroxysuccinimide and six equivalents of tri-n-butylamine in tetrahydrofuran (Pereira et al., 1998). The product was recrystallized from acetonitrile.

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 anomalous scattering was not sufficient to determine the absolute structure; Friedel opposite reflections were therefore merged.

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.
[Figure 2] Fig. 2. One of two interpenetrating networks of the title compound in the crystal. Hydrogen bonds are indicated by dashed lines. H atoms not involved in hydrogen bonding have been omitted.
N,N'-Disuccinimidyl carbonate top
Crystal data top
C9H8N2O7Dx = 1.696 Mg m3
Mr = 256.17Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2Cell parameters from 2400 reflections
a = 13.239 (2) Åθ = 2.8–30.5°
b = 14.629 (2) ŵ = 0.15 mm1
c = 10.3595 (12) ÅT = 133 K
V = 2006.3 (5) Å3Flattened octahedron, colourless
Z = 80.3 × 0.3 × 0.2 mm
F(000) = 1056
Data collection top
Bruker SMART 1000 CCD
diffractometer
723 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Graphite monochromatorθmax = 30.0°, θmin = 2.9°
Detector resolution: 8.192 pixels mm-1h = 918
ω scansk = 2020
3941 measured reflectionsl = 1314
773 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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0522P)2 + 0.2064P]
where P = (Fo2 + 2Fc2)/3
773 reflections(Δ/σ)max < 0.001
83 parametersΔρmax = 0.29 e Å3
1 restraintΔρmin = 0.19 e Å3
Crystal data top
C9H8N2O7V = 2006.3 (5) Å3
Mr = 256.17Z = 8
Orthorhombic, Fdd2Mo Kα radiation
a = 13.239 (2) ŵ = 0.15 mm1
b = 14.629 (2) ÅT = 133 K
c = 10.3595 (12) Å0.3 × 0.3 × 0.2 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
723 reflections with I > 2σ(I)
3941 measured reflectionsRint = 0.028
773 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0271 restraint
wR(F2) = 0.073H-atom parameters constrained
S = 1.06Δρmax = 0.29 e Å3
773 reflectionsΔρmin = 0.19 e Å3
83 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)

− 3.1027 (0.0140) x + 14.2215 (0.0043) y − 0.0000 (0.0000) z = 7.1107 (0.0022)

* 0.0000 (0.0000) C5 * 0.0000 (0.0000) O4 * 0.0000 (0.0000) O3 * 0.0000 (0.0000) O3_$3 0.0174 (0.0027) N

Rms deviation of fitted atoms = 0.0000

6.2463 (0.0073) x + 5.8329 (0.0050) y + 8.1466 (0.0041) z = 7.3393 (0.0024)

Angle to previous plane (with approximate e.s.d.) = 73.92 (0.04)

* 0.0593 (0.0011) N * 0.0100 (0.0013) C1 * −0.0545 (0.0009) O1 * 0.0001 (0.0013) C4 * −0.0193 (0.0008) O2 * 0.0466 (0.0011) C2 * −0.0422 (0.0011) C3

Rms deviation of fitted atoms = 0.0395

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.17245 (10)0.61778 (10)0.32759 (16)0.0178 (3)
C20.27273 (12)0.61235 (11)0.25907 (15)0.0205 (3)
H2A0.31970.65930.29280.025*
H2B0.26390.62210.16520.025*
C30.31397 (12)0.51550 (11)0.28590 (15)0.0201 (3)
H3A0.31800.47980.20490.024*
H3B0.38220.51880.32460.024*
C40.24056 (11)0.47177 (10)0.37868 (15)0.0181 (3)
C50.00000.50000.3899 (2)0.0164 (4)
N0.16454 (9)0.53712 (8)0.39746 (12)0.0183 (3)
O10.10865 (8)0.67660 (8)0.32646 (14)0.0236 (2)
O20.24114 (9)0.39780 (8)0.42883 (12)0.0249 (3)
O30.07945 (8)0.51733 (8)0.47052 (11)0.0194 (2)
O40.00000.50000.27643 (15)0.0238 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0175 (6)0.0190 (6)0.0168 (6)0.0038 (5)0.0024 (5)0.0000 (5)
C20.0180 (7)0.0230 (7)0.0204 (7)0.0028 (5)0.0019 (6)0.0025 (6)
C30.0162 (6)0.0232 (7)0.0210 (8)0.0000 (5)0.0024 (5)0.0006 (5)
C40.0147 (6)0.0209 (6)0.0187 (6)0.0009 (5)0.0037 (5)0.0016 (6)
C50.0133 (8)0.0178 (8)0.0182 (9)0.0013 (6)0.0000.000
N0.0116 (5)0.0229 (6)0.0206 (6)0.0014 (4)0.0015 (4)0.0036 (5)
O10.0207 (5)0.0210 (5)0.0291 (6)0.0020 (4)0.0014 (5)0.0016 (5)
O20.0252 (6)0.0198 (5)0.0297 (6)0.0009 (4)0.0025 (5)0.0018 (4)
O30.0124 (5)0.0294 (6)0.0162 (5)0.0035 (4)0.0002 (4)0.0015 (4)
O40.0209 (7)0.0335 (9)0.0168 (8)0.0067 (6)0.0000.000
Geometric parameters (Å, º) top
C1—O11.2058 (19)C3—H3A0.9900
C1—N1.3882 (18)C3—H3B0.9900
C1—C21.508 (2)C4—O21.200 (2)
C2—C31.544 (2)C4—N1.4017 (18)
C2—H2A0.9900C5—O41.175 (3)
C2—H2B0.9900C5—O31.3669 (17)
C3—C41.509 (2)N—O31.3876 (15)
O1—C1—N123.97 (14)C4—C3—H3B110.5
O1—C1—C2130.53 (15)C2—C3—H3B110.5
N—C1—C2105.50 (12)H3A—C3—H3B108.7
C1—C2—C3105.96 (12)O2—C4—N124.01 (14)
C1—C2—H2A110.5O2—C4—C3130.82 (14)
C3—C2—H2A110.5N—C4—C3105.17 (13)
C1—C2—H2B110.5O4—C5—O3127.67 (8)
C3—C2—H2B110.5O3—C5—O3i104.67 (17)
H2A—C2—H2B108.7O3—N—C1121.53 (11)
C4—C3—C2106.02 (12)O3—N—C4121.08 (12)
C4—C3—H3A110.5C1—N—C4116.95 (12)
C2—C3—H3A110.5C5—O3—N109.27 (11)
O1—C1—C2—C3173.32 (17)O2—C4—N—O34.5 (2)
N—C1—C2—C36.33 (15)C3—C4—N—O3175.03 (11)
C1—C2—C3—C45.02 (16)O2—C4—N—C1177.00 (14)
C2—C3—C4—O2178.71 (16)C3—C4—N—C12.51 (17)
C2—C3—C4—N1.82 (16)O4—C5—O3—N0.76 (12)
O1—C1—N—O31.4 (2)O3i—C5—O3—N179.24 (12)
C2—C1—N—O3178.25 (12)C1—N—O3—C569.98 (15)
O1—C1—N—C4173.91 (16)C4—N—O3—C5102.20 (14)
C2—C1—N—C45.77 (17)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1ii0.992.603.5334 (19)156
C2—H2B···O2iii0.992.473.429 (2)164
Symmetry codes: (ii) x+1/2, y+3/2, z; (iii) x+1/2, y+1, z1/2.

Experimental details

Crystal data
Chemical formulaC9H8N2O7
Mr256.17
Crystal system, space groupOrthorhombic, Fdd2
Temperature (K)133
a, b, c (Å)13.239 (2), 14.629 (2), 10.3595 (12)
V3)2006.3 (5)
Z8
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.3 × 0.3 × 0.2
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3941, 773, 723
Rint0.028
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.073, 1.06
No. of reflections773
No. of parameters83
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.19

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
C1—O11.2058 (19)C5—O31.3669 (17)
C1—N1.3882 (18)N—O31.3876 (15)
C5—O41.175 (3)
O4—C5—O3127.67 (8)O3—N—C4121.08 (12)
O3—C5—O3i104.67 (17)C1—N—C4116.95 (12)
O3—N—C1121.53 (11)C5—O3—N109.27 (11)
O3i—C5—O3—N179.24 (12)C1—N—O3—C569.98 (15)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1ii0.992.603.5334 (19)156
C2—H2B···O2iii0.992.473.429 (2)164
Symmetry codes: (ii) x+1/2, y+3/2, z; (iii) x+1/2, y+1, z1/2.
 

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