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Acta Cryst.(2002). E58, o1267±o1268 DOI: 10.1107/S1600536802018640 Tsonko Kolevet al. C11H10N2O3

o1267

organic papers

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

4-Dimethylaminopyridinium-1-squarate

Tsonko Kolev,aDenitsa

Yancheva,bMarkus SchuÈrmann,c

Dirk-Christian Kleb,cHans

Preutc* and Michael Spitellera

aInstitut fuÈr Umweltforschung, UniversitaÈt

Dortmund, Otto-Hahn-Straûe 6, 44221 Dortmund, Germany,bBulgarian Academy of Sciences, Institute of Organic Chemistry, 1113 Sofia, Bulgaria, andcFachbereich Chemie, UniversitaÈt Dortmund, Otto-Hahn-Straûe 6, 44221 Dortmund, Germany

Correspondence e-mail:

uch002@uxp1.hrz.uni-dortmund.de

Key indicators Single-crystal X-ray study

T= 291 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.037

wRfactor = 0.086

Data-to-parameter ratio = 15.0

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

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

The crystal structure of the title compound, alternatively known as 4-dimethylaminopyridinium-betaine of squaric acid or 4-dimethylaminopyridiniumtrioxocyclobutylide, C11H10

-N2O3, contains a half molecule in the asymmetric unit. The

nearly planar molecule [maximum deviation from planarity 0.077 (2) AÊ] is perpendicular to a mirror plane.

Comment

The title compound, (I), due to its negative solvatochromism, is supposed to be a good candidate for non-linear optical and electro-optical applications. The UV±vis spectra were measured in the following solvents: dichlorethane (368, 389, 445 nm), ethanol (357, 372, 422 nm), acetonitrile (364, 384, 440 nm), water (352, 364 nm) and 1-methylpyrrolidin-2-one (370, 389, 452 nm). The conversion of the N atom of 4-di-methylaminopyridine into the corresponding pyridinium betaine affords a way to enhance the charge-transfer transi-tion on the molecular level, a requisite for the design of ef®-cient second- and third-order non-linear optical materials.

The molecular geometry, determined by X-ray diffraction, lies between the two resonance structures shown in the chemical diagram.

There are no classical hydrogen bonds in the crystal, but there are some possible intra- and intermolecular non-classical hydrogen bonds. An intramolecular hydrogen bond connects

an aromatic CÐH group with an O atom [C4ÐH4 O2: CÐ

H = 0.93 AÊ, H O = 2.58 AÊ,D A= 3.223 (2) AÊ and C4Ð H4 O2 = 127]. The methyl groups are connected by

inter-molecular non-classical hydrogen bonds to O atoms [C7Ð H7A O2(ÿxÿ1, ÿy+ 2, ÿz): CÐH = 0.96 AÊ, H O = 2.58 AÊ,D A= 3.510 (2) AÊ and C7ÐH7A O2 = 162; C7Ð

H7B O1 (xÿ2,y, zÿ1): CÐH = 0.96 AÊ, H O = 2.48 AÊ,

D A= 3.417 (2) AÊ and C7ÐH7B O1 = 166.

Experimental

The title compound was synthesized according to a general procedure described by Schmidtet al.(1984). Squaric acid (1 g, 8.7 mmol) was dissolved in 30 ml acetic anhydride by continuous stirring and heating

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under re¯ux. A solution of 4-dimethylaminopyridine (1.36 g, 8.7 mmol) was added. After a few minutes the solution turned dark yellow. A yellow precipitate was obtained from the resulting dark-yellow solution after 30 min of heating and evaporation of half the solvent. The product was ®ltered off after cooling and recrystallized from ethanol (yield 90%, m.p. >600 K). The purity of the compound was con®rmed by elemental analysis, IR, UV±vis and mass spectro-metry. Yellow transparent crystals were grown from ethanol by slow evaporation at room temperature over a period of two weeks.

Crystal data

C11H10N2O3 Mr= 218.21

Monoclinic,P21=m a= 4.1031 (4) AÊ b= 12.1158 (12) AÊ c= 10.4553 (10) AÊ

= 95.171 (6)

V= 517.64 (9) AÊ3 Z= 2

Dx= 1.400 Mg mÿ3

MoKradiation Cell parameters from 4542

re¯ections

= 3.9±27.5

= 0.10 mmÿ1 T= 291 (1) K Plate, yellow

0.250.150.07 mm

Data collection

Nonius KappaCCD diffractometer

!scans

Absorption correction: none 4542 measured re¯ections 1243 independent re¯ections 514 re¯ections withI> 2(I)

Rint= 0.029

max= 27.5 h=ÿ5!5 k=ÿ15!15 l=ÿ13!13

Re®nement

Re®nement onF2 R[F2> 2(F2)] = 0.037 wR(F2) = 0.086 S= 0.91 1243 re¯ections 83 parameters

H-atom parameters constrained w= 1/[2(F

o2) + (0.0211P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.12 e AÊÿ3 min=ÿ0.15 e AÊÿ3

H atoms were placed in calculated positions, with Uiso values

constrained to be 1.5Ueqof the carrier atom for methyl H atoms and

1.2Ueqfor the remaining H atoms. The methyl groups were allowed to

rotate but not to tip.

Data collection: COLLECT (Nonius, 1998); cell re®nement:

DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction:DENZO and SCALEPACK; program(s) used to solve structure:SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL-Plus(Sheldrick, 1991); software used to prepare material for publication: SHELXL97, PARST95 (Nardelli, 1995) and

PLATON(Spek, 2001).

We thank the DAAD for a grant within the priority programme `Stability pact for South Eastern Europe' and the Alexander von Humboldt-Stiftung Bonn, Bad Godesberg (Germany).

References

Nardelli, M. (1995).J. Appl. Cryst.28, 659.

Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307±326. New York: Academic Press.

Schmidt, A. H., Becker, U. & Aimene, A. (1984).Tetrahedron Lett.25, 4475± 4478.

Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Sheldrick, G. M. (1991). SHELXTL-Plus.Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Spek, A. L. (2001).PLATON.University of Utrecht, The Netherlands.

Figure 1

View of the title compound, showing the labelling of all non-H atoms. Displacement ellipsoids are shown at the 50% probability level. H atoms are drawn as circles of arbitrary radii. The suf®xAdenotes a symmetry-generated atom (x,3

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supporting information

sup-1 Acta Cryst. (2002). E58, o1267–o1268

supporting information

Acta Cryst. (2002). E58, o1267–o1268 [https://doi.org/10.1107/S1600536802018640]

4-Dimethylaminopyridinium-1-squarate

Tsonko Kolev, Denitsa Yancheva, Markus Sch

ü

rmann, Dirk-Christian Kleb, Hans Preut and

Michael Spiteller

(I)

Crystal data C11H10N2O3 Mr = 218.21 Monoclinic, P21/m Hall symbol: -P 2yb a = 4.1031 (4) Å b = 12.1158 (12) Å c = 10.4553 (10) Å β = 95.171 (6)° V = 517.64 (9) Å3 Z = 2

F(000) = 228 Dx = 1.400 Mg m−3

Mo radiation, λ = 0.71073 Å Cell parameters from 4542 reflections θ = 3.9–27.5°

µ = 0.10 mm−1 T = 291 K Plate, yellow

0.25 × 0.15 × 0.07 mm

Data collection Nonius KappaCCD

diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 19 vertical, 18 horizontal pixels mm-1

139 frames via ω–rotation (Δω=1%) and two times 150 s per frame (3 sets at different κ– angles) scans

4542 measured reflections 1243 independent reflections 514 reflections with I > 2σ(I) Rint = 0.029

θmax = 27.5°, θmin = 3.9° h = −5→5

k = −15→15 l = −13→13

Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.037 wR(F2) = 0.086 S = 0.91 1243 reflections 83 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-atom parameters constrained w = 1/[σ2(F

o2) + (0.0211P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001

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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.

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)

x y z Uiso*/Ueq

O1 0.4582 (5) 0.7500 0.36682 (17) 0.0767 (6)

O2 0.1016 (3) 0.93849 (10) 0.18089 (11) 0.0818 (5)

N1 −0.2559 (4) 0.7500 −0.00459 (15) 0.0460 (5)

N2 −0.8737 (5) 0.7500 −0.33951 (17) 0.0554 (6)

C1 0.2719 (6) 0.7500 0.2706 (2) 0.0537 (7)

C2 0.1054 (4) 0.83689 (16) 0.18362 (15) 0.0552 (5)

C3 −0.0410 (6) 0.7500 0.10729 (19) 0.0462 (6)

C4 −0.3639 (4) 0.84697 (12) −0.06069 (15) 0.0517 (5)

H4 −0.2941 0.9134 −0.0229 0.062*

C5 −0.5679 (4) 0.84903 (13) −0.16889 (15) 0.0531 (5)

H5 −0.6370 0.9165 −0.2040 0.064*

C6 −0.6790 (6) 0.7500 −0.2301 (2) 0.0486 (6)

C7 −0.9754 (5) 0.85344 (14) −0.40475 (15) 0.0677 (6)

H7A −1.0595 0.9032 −0.3443 0.102*

H7B −1.1425 0.8382 −0.4727 0.102*

H7C −0.7905 0.8866 −0.4399 0.102*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

O1 0.0787 (15) 0.0849 (14) 0.0624 (10) 0.000 −0.0149 (11) 0.000

O2 0.1077 (12) 0.0455 (9) 0.0871 (9) −0.0061 (8) −0.0187 (8) −0.0044 (7)

N1 0.0478 (13) 0.0382 (12) 0.0511 (11) 0.000 −0.0012 (10) 0.000

N2 0.0559 (14) 0.0516 (14) 0.0567 (12) 0.000 −0.0066 (12) 0.000

C1 0.0497 (17) 0.0627 (17) 0.0477 (13) 0.000 −0.0012 (14) 0.000

C2 0.0583 (13) 0.0496 (12) 0.0570 (10) −0.0029 (10) 0.0017 (9) −0.0005 (10)

C3 0.0458 (16) 0.0457 (15) 0.0464 (12) 0.000 −0.0002 (13) 0.000

C4 0.0574 (12) 0.0378 (10) 0.0590 (10) 0.0017 (9) 0.0001 (10) −0.0013 (8)

C5 0.0571 (13) 0.0426 (11) 0.0581 (9) 0.0043 (9) −0.0032 (9) 0.0025 (8)

C6 0.0467 (17) 0.0471 (16) 0.0513 (13) 0.000 0.0004 (13) 0.000

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supporting information

sup-3 Acta Cryst. (2002). E58, o1267–o1268

N1—C4i 1.3688 (16) C4—C5 1.346 (2)

N1—C4 1.3688 (16) C4—H4 0.9300

N1—C3 1.400 (2) C5—C6 1.4156 (19)

N2—C6 1.335 (3) C5—H5 0.9300

N2—C7i 1.4692 (17) C6—C5i 1.4156 (19)

N2—C7 1.4692 (17) C7—H7A 0.9600

C1—C2i 1.513 (2) C7—H7B 0.9600

C1—C2 1.513 (2) C7—H7C 0.9600

C4i—N1—C4 118.25 (18) C5—C4—N1 121.93 (15)

C4i—N1—C3 120.87 (9) C5—C4—H4 119.0

C4—N1—C3 120.87 (9) N1—C4—H4 119.0

C6—N2—C7i 121.38 (9) C4—C5—C6 120.98 (16)

C6—N2—C7 121.38 (9) C4—C5—H5 119.5

C7i—N2—C7 117.08 (18) C6—C5—H5 119.5

O1—C1—C2i 135.91 (9) N2—C6—C5i 122.05 (11)

O1—C1—C2 135.91 (9) N2—C6—C5 122.05 (11)

C2i—C1—C2 88.17 (18) C5i—C6—C5 115.9 (2)

O2—C2—C3 136.36 (16) N2—C7—H7A 109.5

O2—C2—C1 135.52 (15) N2—C7—H7B 109.5

C3—C2—C1 88.12 (14) H7A—C7—H7B 109.5

N1—C3—C2 132.20 (10) N2—C7—H7C 109.5

N1—C3—C2i 132.20 (10) H7A—C7—H7C 109.5

C2—C3—C2i 95.59 (19) H7B—C7—H7C 109.5

O1—C1—C2—O2 −0.2 (5) C1—C2—C3—C2i −0.05 (19)

C2i—C1—C2—O2 −179.67 (16) C4i—N1—C4—C5 −0.7 (3)

O1—C1—C2—C3 179.5 (3) C3—N1—C4—C5 179.36 (18)

C2i—C1—C2—C3 0.04 (18) N1—C4—C5—C6 −0.3 (3)

C4i—N1—C3—C2 −179.9 (2) C7i—N2—C6—C5i −1.9 (3)

C4—N1—C3—C2 0.0 (3) C7—N2—C6—C5i −177.32 (17)

C4i—N1—C3—C2i 0.0 (3) C7i—N2—C6—C5 177.32 (17)

C4—N1—C3—C2i 179.9 (2) C7—N2—C6—C5 1.9 (3)

O2—C2—C3—N1 −0.4 (4) C4—C5—C6—N2 −177.98 (19)

C1—C2—C3—N1 179.9 (2) C4—C5—C6—C5i 1.3 (3)

O2—C2—C3—C2i 179.66 (15)

References

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