N Hydro­xy­succin­imide

Acta Cryst.(2003). E59, o1951±o1952 DOI: 10.1107/S1600536803025704 Peter G. Jones C₄H₅NO₃

o1951

organic papers

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

N

-Hydroxysuccinimide

Peter G. Jones

Institut fuÈr Anorganische und Analytische Chemie, Technische UniversitaÈt Braunschweig, Postfach 3329, 38023 Braunschweig, Germany

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 133 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.041

wRfactor = 0.108

Data-to-parameter ratio = 11.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved

The molecule of the title compound, C4H5NO3, is planar

(mean deviation of non-H atoms 0.03 AÊ). The NÐC bond lengths are signi®cantly different [1.365 (2) and 1.392 (2) AÊ]. The C O group associated with the shorter NÐC bond accepts a classical intermolecular hydrogen bond from the hydroxy H atom.

Comment

N-Hydroxysuccinimide, (I), has found applications in the analysis of amines, with which it readily forms crystalline adducts. The structure of one of these, withp -chlorobenzyl-amine, was determined (Reck & Adam, 1977), and it was established that the amine is in the protonated form, while the hydroxy group is deprotonated. However, the structure of

N-hydroxysuccinimide itself has not previously been deter-mined; it is presented here.

The molecule is shown in Fig. 1; it is planar within a mean deviation (non-H atoms) of 0.03 AÊ. The most striking feature of the molecular dimensions is the large difference between the chemically equivalent bond lengths NÐC1 [1.365 (2) AÊ] and NÐC4 [1.392 (2) AÊ]. If this is accepted as genuine, one possible explanation would be delocalization of the lone pair at nitrogen preferentially in the direction of O1 [cf. the corresponding C O bond lengths of 1.224 (2) and 1.207 (2) AÊ]. This would be consistent with the fact that atom O1 accepts a classical intermolecular hydrogen bond from the OH group. The structures of the above-mentioned adduct and ofN-hydroxyphthalimide (Miaoet al., 1995) are available for comparison; in the former, the corresponding NÐC bond

Received 5 November 2003 Accepted 6 November 2003 Online 15 November 2003

Figure 1

lengths are 1.365 and 1.376 AÊ, and in the latter 1.384 (6) and 1.397 (8) AÊ. In each case, the ®rst bond length involves the C O group that accepts a classical hydrogen bond, whereas the latter C O group does not. The differences are, however, not signi®cant.

The classical hydrogen bond and one short CÐH O interaction connect the molecules to form ribbons parallel to theaaxis (Fig. 2).

Experimental

A commercial sample of the title compound (Aldrich) proved to contain single crystals.

Crystal data

C4H5NO3

Mr= 115.09

Orthorhombic,P212121

a= 5.4266 (8) AÊ

b= 7.2419 (12) AÊ

c= 12.445 (2) AÊ

V= 489.09 (13) AÊ3

Z= 4

Dx= 1.563 Mg mÿ3

MoKradiation Cell parameters from 3627

re¯ections

= 2.8±30.5

= 0.14 mmÿ1

T= 133 (2) K

Irregular tablet, colourless 0.300.250.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer

!scans

Absorption correction: none 5566 measured re¯ections 860 independent re¯ections

803 re¯ections withI> 2(I)

Rint= 0.071

max= 30.0

h=ÿ7!7

k=ÿ10!10

l=ÿ17!17

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.041}

wR(F2_{) = 0.109}

S= 1.05 860 re¯ections 77 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F

o2) + (0.0857P)2

+ 0.0226P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.48 e AÊÿ3

min=ÿ0.20 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

C1ÐO1 1.224 (2) C1ÐN 1.365 (2) C1ÐC2 1.507 (2) C2ÐC3 1.539 (2)

C3ÐC4 1.502 (2) C4ÐO2 1.207 (2) C4ÐN 1.392 (2) NÐO3 1.3769 (16)

O1ÐC1ÐN 124.65 (13) O1ÐC1ÐC2 127.90 (13) NÐC1ÐC2 107.44 (12) C1ÐC2ÐC3 105.01 (13) C4ÐC3ÐC2 105.20 (12) O2ÐC4ÐN 123.54 (14)

O2ÐC4ÐC3 129.80 (14) NÐC4ÐC3 106.65 (13) C1ÐNÐO3 121.03 (12) C1ÐNÐC4 115.22 (12) O3ÐNÐC4 123.17 (12)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O3ÐH0 O1i _{0.97 (3) 1.71 (3) 2.6442 (16) 161 (3)}

The hydroxy H atom was re®ned freely. Other H atoms were included using a riding model with ®xed CÐH bond lengths of 0.99 AÊ;Uiso(H) values were ®xed at 1.2 timesUeqof the parent atom.

The absolute structure could not be determined because the anom-alous scattering effects were too small, and Friedel opposite re¯ec-tions were therefore merged. The Flack (1983) parameter is meaningless in such cases. The compound is not chiral, and the concept of absolute con®guration does not apply. A rigid-body libration correction (Schomaker & Trueblood, 1968) led to the following corrected bond lengths (AÊ): C1ÐC2 1.510, C2ÐC3 1.544, C3ÐC4 1.506, C1ÐN 1.369, C4ÐN 1.395, C1ÐO1 1.227, C4ÐO2 1.210 and NÐO3 1.380.

Data collection:SMART(Bruker, 1998); cell re®nement:SAINT

(Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP

(Siemens, 1994); software used to prepare material for publication:

SHELXL97.

The problem was suggested by Professor C. Csunderlik and Ms M. Simon, Polytechnical University of Timisoara, Romania. Financial support from the Fonds der Chemischen Industrie is gratefully acknowledged. The author thanks Mr A. Weinkauf for technical assistance.

References

Bruker (1998).SMART(Version 5.0) andSAINT(Version 4.0). Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Miao, F.-M., Wang, J.-L. & Miao, X.-S. (1995).Acta Cryst.C51, 712±713. Reck, G. & Adam, G. (1977).Z. Chem.17, 338±339.

Schomaker, V. & Trueblood, K. N. (1968).Acta Cryst.B24, 63±76. Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Figure 2

supporting information

sup-1 Acta Cryst. (2003). E59, o1951–o1952

supporting information

Acta Cryst. (2003). E59, o1951–o1952 [https://doi.org/10.1107/S1600536803025704]

N

-Hydroxysuccinimide

Peter G. Jones

(I)

Crystal data

C4H5NO3 Mr = 115.09

Orthorhombic, P212121 a = 5.4266 (8) Å

b = 7.2419 (12) Å

c = 12.445 (2) Å

V = 489.09 (13) Å3 Z = 4

F(000) = 240

Dx = 1.563 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3627 reflections

θ = 2.8–30.5°

µ = 0.14 mm−1 T = 133 K

Irregular tablet, colourless 0.30 × 0.25 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 8.192 pixels mm-1 ω scans

5566 measured reflections

860 independent reflections 803 reflections with I > 2σ(I)

Rint = 0.071

θmax = 30.0°, θmin = 3.3° h = −7→7

k = −10→10

l = −17→17

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.041} wR(F2_{) = 0.109} S = 1.05 860 reflections 77 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0857P)2 + 0.0226P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.48 e Å−3

Δρmin = −0.20 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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 anomalous dispersion effects were not significant and Friedel opposite reflections were therefore merged. The Flack parameter is meaningless in such cases.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

C1 0.3418 (3) 0.45792 (19) 0.36706 (11) 0.0183 (3) C2 0.4766 (3) 0.5929 (2) 0.29615 (11) 0.0210 (3)

H2A 0.3675 0.6966 0.2755 0.025*

H2B 0.5367 0.5314 0.2301 0.025*

C3 0.6938 (3) 0.6623 (2) 0.36469 (12) 0.0222 (3)

H3A 0.8527 0.6213 0.3337 0.027*

H3B 0.6934 0.7988 0.3689 0.027*

C4 0.6549 (3) 0.5788 (2) 0.47386 (13) 0.0210 (3) N 0.4578 (2) 0.45687 (16) 0.46436 (10) 0.0189 (3) O1 0.1590 (2) 0.36643 (15) 0.34513 (9) 0.0232 (3) O2 0.7672 (3) 0.60296 (19) 0.55634 (10) 0.0321 (3) O3 0.3621 (2) 0.36006 (16) 0.54995 (9) 0.0237 (3)

H0 0.494 (7) 0.282 (4) 0.575 (2) 0.063 (8)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

C1 0.0211 (6) 0.0130 (6) 0.0208 (6) 0.0023 (5) 0.0012 (5) −0.0006 (5) C2 0.0271 (7) 0.0155 (6) 0.0203 (6) −0.0023 (6) 0.0009 (6) 0.0007 (5) C3 0.0209 (6) 0.0181 (6) 0.0277 (7) −0.0007 (6) 0.0006 (6) 0.0036 (5) C4 0.0208 (6) 0.0147 (6) 0.0274 (7) 0.0000 (6) −0.0018 (6) 0.0018 (5) N 0.0209 (6) 0.0149 (5) 0.0208 (6) −0.0008 (5) −0.0006 (5) 0.0037 (4) O1 0.0240 (5) 0.0220 (5) 0.0236 (5) −0.0038 (5) −0.0010 (5) 0.0013 (4) O2 0.0356 (7) 0.0299 (7) 0.0307 (6) −0.0073 (5) −0.0109 (6) 0.0037 (5) O3 0.0254 (6) 0.0231 (6) 0.0227 (5) 0.0005 (5) 0.0017 (5) 0.0081 (4)

Geometric parameters (Å, º)

C1—O1 1.224 (2) N—O3 1.3769 (16)

C1—N 1.365 (2) C2—H2A 0.9900

C1—C2 1.507 (2) C2—H2B 0.9900

C2—C3 1.539 (2) C3—H3A 0.9900

C3—C4 1.502 (2) C3—H3B 0.9900

C4—O2 1.207 (2) O3—H0 0.97 (3)

C4—N 1.392 (2)

supporting information

sup-3 Acta Cryst. (2003). E59, o1951–o1952

C1—C2—C3 105.01 (13) C3—C2—H2B 110.7

C4—C3—C2 105.20 (12) H2A—C2—H2B 108.8

O2—C4—N 123.54 (14) C4—C3—H3A 110.7

O2—C4—C3 129.80 (14) C2—C3—H3A 110.7

N—C4—C3 106.65 (13) C4—C3—H3B 110.7

C1—N—O3 121.03 (12) C2—C3—H3B 110.7

C1—N—C4 115.22 (12) H3A—C3—H3B 108.8

O3—N—C4 123.17 (12) N—O3—H0 105.7 (18)

O1—C1—C2—C3 −178.69 (15) O1—C1—N—C4 −176.73 (14)

N—C1—C2—C3 2.65 (16) C2—C1—N—C4 1.98 (17)

C1—C2—C3—C4 −5.83 (16) O2—C4—N—C1 175.34 (16)

C2—C3—C4—O2 −174.31 (18) C3—C4—N—C1 −5.86 (17)

C2—C3—C4—N 6.99 (16) O2—C4—N—O3 4.0 (2)

O1—C1—N—O3 −5.2 (2) C3—C4—N—O3 −177.16 (12)

C2—C1—N—O3 173.48 (12)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O3—H0···O1i _{0.97 (3) 1.71 (3) 2.6442 (16) 161 (3)}

C3—H3A···O1ii _{0.99 2.49 3.320 (2) 142}

C2—H2B···O2iii _{0.99 2.60 3.585 (2) 174}