Ethopropazinium picrate

organic papers

o1792

19H25N2S+C6H2N3O7 doi:10.1107/S1600536807011543 Acta Cryst.(2007). E63, o1792–o1794

Acta Crystallographica Section E

Structure Reports

Online

ISSN 1600-5368

Ethopropazinium picrate

H. S. Yathirajan,aM. A. Ashok,a B. Narayana Acharaand Michael Bolteb*

a_{Department of Studies in Chemistry, University}

of Mysore, Manasagangotri, Mysore 570 006, India, andb

Institut fu¨r Anorganische Chemie, J. W. Goethe-Universita¨t Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 173 K

Mean(C–C) = 0.005 A˚

Rfactor = 0.077

wRfactor = 0.212

Data-to-parameter ratio = 12.7

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

Received 21 February 2007 Accepted 12 March 2007

#2007 International Union of Crystallography All rights reserved

The title compound [systematic name:

10-[2-(diethylamino)-propyl]phenothiazinium 2,4,6-trinitrophenolate], C19H25

-N2S +

C6H2N3O7

, is a pharmacologially active compound. The dihedral angle between the two outer aromatic rings of the phenothiazine unit is 38.64 (12)_{. The crystal packing is}

stabilized by N—H O hydrogen bonds and several weak

C—H O contacts. The molecular conformation of the cation

does not change significantly when it is crystallized with chloride or perrhenate as the anion.

Comment

Ethopropazine is an anticholinergic agent with some anti-histaminic and ganglionic blocking activity (Bratfos & Haug, 1979). The present work results in the formation of a salt by the interaction between ethopropazinium hydrochloride and 2,4,6-trinitrophenol in an aqueous medium.

A perspective view of the title compound, (I), is shown in Fig. 1. Bond lengths and angles can be regarded as normal (Cambridge Structural Database, Version 5.28, November

2006; MOGUL, Version 1.1; Allen, 2002; Brunoet al., 2004).

The dihedral angle between the two aromatic rings of the

phenothiazine unit is 38.64 (12)_{. Crystallographic data for}

ethopropazinium chloride, (Ia) (Marsau & Calas, 1971; Klein

et al., 1994), and ethopropazinium perrhenate, (Ib) (Gowdaet al., 1994), have been published, but since there is a coordinate error in the report by Marsau & Calas (1971), the structure given by Kleinet al.(1994) is employed for comparison. Least-squares overlays of the ethopropazinium cations of (I) and (Ia) (r.m.s. deviation 0.066 A˚ ) as well as of (I) and (Ib) (r.m.s. deviation 0.120 A˚ ), fitting only the phenothiazine units, are shown in Figs. 2 and 3. As can be seen, the molecular conformation is not significantly different in the compared

structures. The crystal packing is stabilized by N—H O

hydrogen bonds and several weak C—H O contacts

Experimental

Profenamine hydrochloride (0.7010 g, 0.02 M) and picric acid (0.4610 g, 0.02M) were dissolved in distilled water (100 ml), mixed and stirred in a beaker at room temperature. The separated yellow salt was washed well with distilled water, filtered and dried in a vacuum desiccator over phosphorus pentoxide. The complex was recrystallized from acetonitrile (m.p. 378 K).

Crystal data

C19H25N2S+C6H2N3O7

Mr= 541.58

Monoclinic,C2=c a= 36.876 (3) A˚

b= 8.4622 (4) A˚

c= 16.5727 (11) A˚

= 104.163 (6)

V= 5014.3 (6) A˚3

Z= 8

MoKradiation

= 0.19 mm1

T= 173 (2) K 0.290.260.25 mm

Data collection

Stoe IPDS-II two-circle diffractometer

Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)

Tmin= 0.938,Tmax= 0.945

22001 measured reflections 4421 independent reflections 3505 reflections withI> 2(I)

Rint= 0.081

Refinement

R[F2_{> 2(F}2_{)] = 0.077}

wR(F2) = 0.212

S= 1.06 4421 reflections 347 parameters

H atoms treated by a mixture of independent and constrained refinement

max= 0.46 e A˚ 3

min=0.55 e A˚ 3

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N2—H2 O31i

0.95 (5) 1.92 (5) 2.841 (4) 161 (4) C1—H1A O31i

0.99 2.45 3.234 (4) 136 C23—H23 O31i 0.95 2.37 3.316 (4) 175

Symmetry code: (i)x;yþ1;z1 2.

H atoms were found in a difference map, but the C-bound H atoms were refined using a riding model, with C—H ranging from 0.95 to 0.99 A˚ and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). The H atom

bonded to N was freely refined.

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:XPin SHELXTL-Plus(Sheldrick, 1991); software used to prepare material for publication:SHELXL97.

MAA thanks the University of Mysore for research facil-ities.

References

Allen, F. H. (2002).Acta Cryst.B58, 380–388. Blessing, R. H. (1995).Acta Cryst.A51, 33–38.

Bratfos, O. & Haug, J. O. (1979).Acta Psychiatr. Scand.60, 1–9.

organic papers

Acta Cryst.(2007). E63, o1792–o1794 Yathirajanet al. _C

19H25N2S+C6H2N3O7

o1793

The structure of the title compound, with the atom numbering. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2

Least-squares fit of the ethopropazinium cations in (I) (full bonds) and (Ia) (open bonds). H atoms have been omitted.

Figure 3

Bruno, I. J., Cole, J. C., Kessler, M., Luo, J., Motherwell, W. D. S., Purkis, L. H., Smith, B. R., Taylor, R., Cooper, R. I., Harris, S. E. & Orpen, A. G. (2004).J. Chem. Inf. Comput. Sci.44, 2133–2144.

Gowda, N. M. M., Zhang, L. & Barnes, C. L. (1994).J. Chem. Crystallogr.24, 89–93.

Klein, C. L., Lear, J., O’Rourke, S., Williams, S. & Liang, L. (1994).J. Pharm. Sci.83, 1253–1256.

Marsau, P. & Calas, M.-R. (1971).Acta Cryst.B27, 2058–2062.

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

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Stoe & Cie (2001).X-AREA. Stoe & Cie, Darmstadt, Germany.

organic papers

o1794

supporting information

sup-1

Acta Cryst. (2007). E63, o1792–o1794

supporting information

Acta Cryst. (2007). E63, o1792–o1794 [https://doi.org/10.1107/S1600536807011543]

Ethopropazinium picrate

H. S. Yathirajan, M. A. Ashok, B. Narayana Achar and Michael Bolte

10-[2-(diethylamino)propyl]phenothiazinium 2,4,6-trinitrophenolate

Crystal data

C19H25N2S+·C6H2N3O7− Mr = 541.58

Monoclinic, C2/c Hall symbol: -C 2yc a = 36.876 (3) Å b = 8.4622 (4) Å c = 16.5727 (11) Å β = 104.163 (6)° V = 5014.3 (6) Å3 Z = 8

F(000) = 2272 Dx = 1.435 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 17551 reflections θ = 1.7–24.9°

µ = 0.19 mm−1 T = 173 K Block, yellow

0.29 × 0.26 × 0.25 mm

Data collection

Stoe IPDS-II two-circle diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan

(MULABS; Spek, 2003; Blessing, 1995) Tmin = 0.938, Tmax = 0.945

22001 measured reflections 4421 independent reflections 3505 reflections with I > 2σ(I) Rint = 0.081

θmax = 25.0°, θmin = 2.5° h = −43→41

k = −10→10 l = −19→19

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.077} wR(F2_{) = 0.212} S = 1.06 4421 reflections 347 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) + (0.1318P)2 + 4.3473P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.003

Δρmax = 0.46 e Å−3

Δρmin = −0.55 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

supporting information

sup-2

Acta Cryst. (2007). E63, o1792–o1794

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.

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

x y z Uiso*/Ueq

supporting information

sup-3

Acta Cryst. (2007). E63, o1792–o1794

H23 0.6443 0.4650 0.1221 0.055* C24 0.68683 (10) 0.5534 (4) 0.0760 (2) 0.0525 (8) H24 0.6766 0.5208 0.0202 0.063* C25 0.72014 (11) 0.6338 (4) 0.0956 (2) 0.0593 (9) H25 0.7323 0.6616 0.0532 0.071* C26 0.73591 (10) 0.6742 (4) 0.1781 (2) 0.0568 (8) H26 0.7591 0.7292 0.1924 0.068* O31 0.58894 (6) 0.6879 (3) 0.58246 (13) 0.0500 (6) C31 0.56212 (9) 0.6614 (4) 0.52054 (18) 0.0479 (7) C32 0.53700 (10) 0.7777 (5) 0.4734 (2) 0.0581 (9) C33 0.50836 (10) 0.7423 (6) 0.4047 (2) 0.0682 (12) H33 0.4928 0.8240 0.3759 0.082* C34 0.50253 (10) 0.5873 (6) 0.3781 (2) 0.0654 (11) C35 0.52634 (10) 0.4675 (5) 0.41689 (19) 0.0601 (9) H35 0.5232 0.3620 0.3968 0.072* C36 0.55451 (9) 0.5054 (4) 0.48485 (18) 0.0501 (8) N32 0.54170 (9) 0.9432 (4) 0.4958 (2) 0.0689 (9) N34 0.47234 (10) 0.5499 (8) 0.3072 (2) 0.0889 (14) N36 0.57944 (8) 0.3774 (3) 0.52291 (16) 0.0521 (7) O321 0.55961 (9) 0.9794 (3) 0.5661 (2) 0.0787 (8) O322 0.52714 (8) 1.0442 (4) 0.4438 (2) 0.0908 (11) O341 0.45479 (9) 0.6596 (6) 0.26505 (18) 0.1063 (15) O342 0.46524 (9) 0.4110 (7) 0.2904 (2) 0.1079 (14) O361 0.59591 (8) 0.3034 (3) 0.47877 (16) 0.0707 (7) O362 0.58297 (7) 0.3499 (3) 0.59752 (14) 0.0557 (6)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-4

Acta Cryst. (2007). E63, o1792–o1794

C24 0.066 (2) 0.0523 (18) 0.0402 (16) 0.0018 (16) 0.0147 (15) −0.0022 (14) C25 0.069 (2) 0.066 (2) 0.0502 (18) −0.0036 (18) 0.0288 (17) −0.0046 (16) C26 0.0534 (19) 0.067 (2) 0.0535 (19) −0.0064 (16) 0.0204 (16) −0.0075 (16) O31 0.0513 (13) 0.0556 (13) 0.0393 (11) −0.0017 (10) 0.0039 (10) 0.0045 (9) C31 0.0445 (17) 0.062 (2) 0.0364 (15) −0.0057 (14) 0.0085 (13) 0.0118 (13) C32 0.0493 (19) 0.072 (2) 0.0513 (18) −0.0073 (16) 0.0099 (15) 0.0249 (17) C33 0.0452 (19) 0.111 (3) 0.0456 (19) −0.010 (2) 0.0058 (15) 0.032 (2) C34 0.0467 (19) 0.114 (3) 0.0335 (16) −0.015 (2) 0.0067 (14) 0.0107 (19) C35 0.0517 (19) 0.095 (3) 0.0344 (15) −0.0158 (19) 0.0131 (14) −0.0032 (16) C36 0.0489 (17) 0.066 (2) 0.0356 (15) −0.0079 (15) 0.0111 (13) 0.0048 (14) N32 0.0534 (17) 0.071 (2) 0.077 (2) −0.0043 (15) 0.0071 (16) 0.0368 (18) N34 0.0479 (19) 0.185 (5) 0.0326 (16) −0.015 (3) 0.0079 (14) 0.002 (2) N36 0.0546 (16) 0.0591 (17) 0.0417 (14) −0.0094 (13) 0.0101 (12) −0.0048 (12) O321 0.0767 (19) 0.0561 (16) 0.090 (2) 0.0013 (13) −0.0049 (16) 0.0175 (14) O322 0.0670 (18) 0.093 (2) 0.105 (2) −0.0008 (15) 0.0071 (16) 0.0649 (19) O341 0.0587 (17) 0.212 (5) 0.0421 (15) −0.009 (2) 0.0003 (13) 0.032 (2) O342 0.0620 (19) 0.194 (4) 0.0610 (19) −0.015 (2) 0.0019 (15) −0.038 (2) O361 0.0749 (17) 0.0812 (19) 0.0587 (15) 0.0031 (14) 0.0218 (13) −0.0149 (13) O362 0.0672 (15) 0.0579 (14) 0.0405 (12) −0.0047 (11) 0.0104 (10) 0.0035 (10)

Geometric parameters (Å, º)

supporting information

sup-5

Acta Cryst. (2007). E63, o1792–o1794

C7—H7A 0.9800 C36—N36 1.460 (5) C7—H7B 0.9800 N32—O321 1.228 (5) C7—H7C 0.9800 N32—O322 1.239 (4) C11—C16 1.391 (4) N34—O342 1.222 (6) C11—C12 1.400 (5) N34—O341 1.244 (6) C12—C13 1.397 (4) N36—O361 1.231 (4) C13—C14 1.398 (4) N36—O362 1.233 (3) C13—H13 0.9500

supporting information

sup-6

Acta Cryst. (2007). E63, o1792–o1794

H5B—C5—H5C 109.5 C33—C34—C35 120.8 (3) N2—C6—C7 113.3 (3) C33—C34—N34 119.8 (4) N2—C6—H6A 108.9 C35—C34—N34 119.4 (5) C7—C6—H6A 108.9 C36—C35—C34 118.4 (4) N2—C6—H6B 108.9 C36—C35—H35 120.8 C7—C6—H6B 108.9 C34—C35—H35 120.8 H6A—C6—H6B 107.7 C35—C36—C31 125.6 (3) C6—C7—H7A 109.5 C35—C36—N36 116.8 (3) C6—C7—H7B 109.5 C31—C36—N36 117.5 (3) H7A—C7—H7B 109.5 O321—N32—O322 121.9 (4) C6—C7—H7C 109.5 O321—N32—C32 119.2 (3) H7A—C7—H7C 109.5 O322—N32—C32 119.0 (4) H7B—C7—H7C 109.5 O342—N34—O341 122.5 (4) C16—C11—C12 121.0 (3) O342—N34—C34 118.5 (5) C16—C11—S1 119.1 (2) O341—N34—C34 119.1 (5) C12—C11—S1 119.8 (2) O361—N36—O362 123.6 (3) C13—C12—C11 118.2 (3) O361—N36—C36 118.1 (3) C13—C12—N1 122.3 (3) O362—N36—C36 118.3 (3) C11—C12—N1 119.4 (3)

supporting information

sup-7

Acta Cryst. (2007). E63, o1792–o1794

S1—C11—C16—C15 −175.4 (2) C31—C32—N32—O322 161.0 (3) C11—S1—C21—C26 143.3 (3) C33—C34—N34—O342 −172.3 (3) C11—S1—C21—C22 −40.7 (3) C35—C34—N34—O342 10.2 (5) C26—C21—C22—C23 5.7 (5) C33—C34—N34—O341 8.5 (5) S1—C21—C22—C23 −170.2 (2) C35—C34—N34—O341 −169.0 (3) C26—C21—C22—N1 −174.4 (3) C35—C36—N36—O361 56.4 (4) S1—C21—C22—N1 9.7 (4) C31—C36—N36—O361 −122.1 (3) C12—N1—C22—C23 −143.9 (3) C35—C36—N36—O362 −123.9 (3) C1—N1—C22—C23 14.7 (4) C31—C36—N36—O362 57.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N2—H2···O31i _{0.95 (5) 1.92 (5) 2.841 (4) 161 (4)}

C1—H1A···O31i _{0.99 2.45 3.234 (4) 136}

C23—H23···O31i _{0.95 2.37 3.316 (4) 175}