N,N'-Disuccinimidyl carbonate

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.

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.

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S1. Comment

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 C5═O4. 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.

S2. Experimental

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.

S3. Refinement

H atoms were included using a riding model with fixed C—H bond lengths of 0.99 Å; U_iso(H) values were fixed at 1.2 times the U_eq of the parent atom. The anomalous scattering was not sufficient to determine the absolute structure; Friedel opposite reflections were therefore merged.

Computing details

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

	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.
	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

Crystal data

C9H8N2O7	Dx = 1.696 Mg m^−3
Mr = 256.17	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 2400 reflections
a = 13.239 (2) Å	θ = 2.8–30.5°
b = 14.629 (2) Å	µ = 0.15 mm^−1
c = 10.3595 (12) Å	T = 133 K
V = 2006.3 (5) Å^3	Flattened octahedron, colourless
Z = 8	0.3 × 0.3 × 0.2 mm
F(000) = 1056

Data collection

Bruker SMART 1000 CCD diffractometer	723 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 30.0°, θmin = 2.9°
Detector resolution: 8.192 pixels mm^-1	h = −9→18
ω scans	k = −20→20
3941 measured reflections	l = −13→14
773 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0522P)^2 + 0.2064P] where P = (Fo^2 + 2Fc^2)/3
773 reflections	(Δ/σ)max < 0.001
83 parameters	Δρmax = 0.29 e Å^−3
1 restraint	Δρmin = −0.19 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.17245 (10)	0.61778 (10)	0.32759 (16)	0.0178 (3)
C2	0.27273 (12)	0.61235 (11)	0.25907 (15)	0.0205 (3)
H2A	0.3197	0.6593	0.2928	0.025*
H2B	0.2639	0.6221	0.1652	0.025*
C3	0.31397 (12)	0.51550 (11)	0.28590 (15)	0.0201 (3)
H3A	0.3180	0.4798	0.2049	0.024*
H3B	0.3822	0.5188	0.3246	0.024*
C4	0.24056 (11)	0.47177 (10)	0.37868 (15)	0.0181 (3)
C5	0.0000	0.5000	0.3899 (2)	0.0164 (4)
N	0.16454 (9)	0.53712 (8)	0.39746 (12)	0.0183 (3)
O1	0.10865 (8)	0.67660 (8)	0.32646 (14)	0.0236 (2)
O2	0.24114 (9)	0.39780 (8)	0.42883 (12)	0.0249 (3)
O3	0.07945 (8)	0.51733 (8)	0.47052 (11)	0.0194 (2)
O4	0.0000	0.5000	0.27643 (15)	0.0238 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0175 (6)	0.0190 (6)	0.0168 (6)	−0.0038 (5)	−0.0024 (5)	0.0000 (5)
C2	0.0180 (7)	0.0230 (7)	0.0204 (7)	−0.0028 (5)	0.0019 (6)	0.0025 (6)
C3	0.0162 (6)	0.0232 (7)	0.0210 (8)	0.0000 (5)	0.0024 (5)	−0.0006 (5)
C4	0.0147 (6)	0.0209 (6)	0.0187 (6)	−0.0009 (5)	−0.0037 (5)	−0.0016 (6)
C5	0.0133 (8)	0.0178 (8)	0.0182 (9)	−0.0013 (6)	0.000	0.000
N	0.0116 (5)	0.0229 (6)	0.0206 (6)	−0.0014 (4)	0.0015 (4)	0.0036 (5)
O1	0.0207 (5)	0.0210 (5)	0.0291 (6)	0.0020 (4)	−0.0014 (5)	0.0016 (5)
O2	0.0252 (6)	0.0198 (5)	0.0297 (6)	−0.0009 (4)	−0.0025 (5)	0.0018 (4)
O3	0.0124 (5)	0.0294 (6)	0.0162 (5)	−0.0035 (4)	−0.0002 (4)	0.0015 (4)
O4	0.0209 (7)	0.0335 (9)	0.0168 (8)	−0.0067 (6)	0.000	0.000

Geometric parameters (Å, º)

C1—O1	1.2058 (19)	C3—H3A	0.9900
C1—N	1.3882 (18)	C3—H3B	0.9900
C1—C2	1.508 (2)	C4—O2	1.200 (2)
C2—C3	1.544 (2)	C4—N	1.4017 (18)
C2—H2A	0.9900	C5—O4	1.175 (3)
C2—H2B	0.9900	C5—O3	1.3669 (17)
C3—C4	1.509 (2)	N—O3	1.3876 (15)
O1—C1—N	123.97 (14)	C4—C3—H3B	110.5
O1—C1—C2	130.53 (15)	C2—C3—H3B	110.5
N—C1—C2	105.50 (12)	H3A—C3—H3B	108.7
C1—C2—C3	105.96 (12)	O2—C4—N	124.01 (14)
C1—C2—H2A	110.5	O2—C4—C3	130.82 (14)
C3—C2—H2A	110.5	N—C4—C3	105.17 (13)
C1—C2—H2B	110.5	O4—C5—O3	127.67 (8)
C3—C2—H2B	110.5	O3—C5—O3^i	104.67 (17)
H2A—C2—H2B	108.7	O3—N—C1	121.53 (11)
C4—C3—C2	106.02 (12)	O3—N—C4	121.08 (12)
C4—C3—H3A	110.5	C1—N—C4	116.95 (12)
C2—C3—H3A	110.5	C5—O3—N	109.27 (11)
O1—C1—C2—C3	−173.32 (17)	O2—C4—N—O3	−4.5 (2)
N—C1—C2—C3	6.33 (15)	C3—C4—N—O3	175.03 (11)
C1—C2—C3—C4	−5.02 (16)	O2—C4—N—C1	−177.00 (14)
C2—C3—C4—O2	−178.71 (16)	C3—C4—N—C1	2.51 (17)
C2—C3—C4—N	1.82 (16)	O4—C5—O3—N	0.76 (12)
O1—C1—N—O3	1.4 (2)	O3^i—C5—O3—N	−179.24 (12)
C2—C1—N—O3	−178.25 (12)	C1—N—O3—C5	69.98 (15)
O1—C1—N—C4	173.91 (16)	C4—N—O3—C5	−102.20 (14)
C2—C1—N—C4	−5.77 (17)

Symmetry code: (i) −x, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1^ii	0.99	2.60	3.5334 (19)	156
C2—H2B···O2^iii	0.99	2.47	3.429 (2)	164

Symmetry codes: (ii) −x+1/2, −y+3/2, z; (iii) −x+1/2, −y+1, z−1/2.