A co crystal of ethylenediammonium bis(3,5 dinitrobenzoate) and 3,5 dinitrobenzoic acid

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organic papers

Acta Cryst.(2005). E61, o1823–o1825 doi:10.1107/S1600536805015333 Joneset al. _C

2H10N22+2C7H3N2O62C7H4N2O6

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Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

A co-crystal of ethylenediammonium

bis(3,5-dinitrobenzoate) and 3,5-dinitrobenzoic acid

Helen P. Jones, Amy L. Gillon‡ and Roger J. Davey*

Colloids, Crystals and Interfaces Group, School of Chemical Engineering and Analytical Sciences, The University of Manchester, PO Box 88, Manchester M60 1QD, England

‡ Current address: Pharmaceutical R&D, Pfizer Global R&D (IPC 435), Ramsgate Road, Sand-wich, Kent CT13 9NJ, England.

Correspondence e-mail:

h.jones-2@postgrad.manchester.ac.uk

Key indicators Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.046

wRfactor = 0.135

Data-to-parameter ratio = 11.0

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

The co-crystal of ethylenediammonium bis(3,5-dinitro-benzoate) and 3,5-dinitrobenzoic acid, namely ethyl-enediaminium–3,5-dinitrobenzoate–3,5-dinitrobenzoic acid (1/2/2), C2H10N2

2+

2C7H3N2O6

2C7H4N2O6, has as the

asym-metric unit one dinitrobenzoic acid molecule, one 3,5-dinitrobenzoate ion and one-half of the ethylenediammonium ion, as this cation lies on an inversion centre. Each ethylenediammonium ion is hydrogen bonded to four benzoate ions and two benzoic acid molecules.

Comment

During experiments to measure the solubility of the mono-clinic form of ethylenediammonium bis(3,5-dinitrobenzoate), cocrystals, (I), of this salt with 3,5-dinitrobenzoic acid were obtained.

To measure the solubility of ethylenediammonium bis(3,5-dinitrobenzoate) as a function of pH at 323 K, a suspension of the salt in water was prepared and allowed to equilibrate (Joneset al., 2005). In one experiment, the pH was found to be unusually low for a slurry of this salt and the experiment was stopped, but the sample continued to be held at 323 K. The cocrystals grew as pale-yellow prisms and were recovered on filtration of the slurry. Formation of these cocrystals was not observed in other solubility measurements at higher pH. Protonated 3,5-dinitrobenzoic acid is only expected to be present below pH 5 at 323 K (de Levieet al., 1999).

In the crystal structure, both a protonated and a deprotonated 3,5-dinitrobenzoic acid molecule are present in the asymmetric unit. The ethylenediammonium ion lies on an inversion centre so that only one-half of the ion is in the asymmetric unit. Fig. 1 shows the structure and atom labelling. Each ethylenediammonium ion is hydrogen bonded to four benzoate ions and two benzoic acid molecules (Fig. 2). The crystal structure contains hydrogen-bonded chains of ethyl-enediammonium and benzoate ions along the a axis in the motifC2

2(6) (Fig. 3), hydrogen-bonded dimers of benzoate ions

with benzoic acid molecules with an O—H O hydrogen bond through atom H7 in the motif D1

1(2), and dimers of

ethylenediammonium ions hydrogen bonded to the carbonyl group of a benzoic acid molecule in the motif D1

1(2). The

benzoate ions in this structure all lie in one plane and the benzoic acid molecules all lie in another orientation.

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Experimental

Monoclinic ethylenediaminium bis(3,5-dinitrobenzoate) was prepared by precipitation from a mixture of solutions of ethyl-enediamine (0.0145 mol) and 3,5-dinitrobenzoic acid (0.029 mol; supplied by Sigma–Aldrich, 99%) in ethanol (50 ml). An excess of monoclinic ethylenediammonium bis(3,5-dinitrobenzoate) (0.0145 mol) was suspended in water (40 ml) at 323 K with stirring. The solution pH was recorded as 3.79. After 20 h, stirring was stopped and the suspension was held at 323 K for 5 d. The suspension was filtered and pale-yellow prisms were observed in the powder of the monoclinic ethylenediammonium bis(3,5-dinitrobenzoate).

Crystal data

C2H10N22 þ_2C

7H3N2O6

-2C7H4N2O6

Mr= 908.6

Triclinic,P1

a= 7.0452 (3) A˚

b= 11.2345 (4) A˚

c= 11.7627 (5) A˚

= 91.838 (2)

= 96.230 (2)

= 98.710 (1) V= 913.72 (6) A˚3

Z= 1

Dx= 1.651 Mg m

3

MoKradiation Cell parameters from 5294

reflections

= 1.0–25.0

= 0.15 mm1 T= 293 (2) K Prism, pale yellow 0.30.20.1 mm

Data collection

Nonius KappaCCD diffractometer Thick-slice’and!scans to fill

asymmetric unit

Absorption correction: multi-scan (Blessing, 1995)

Tmin= 0.916,Tmax= 0.986

8852 measured reflections

3241 independent reflections 2256 reflections withI> 2(I)

Rint= 0.046

max= 25.2

h=8!8

k=13!13

l=14!12

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.046

wR(F2_{) = 0.136} S= 1.01 3241 reflections 294 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2₍_F

o2) + (0.0776P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.20 e A˚ 3

min=0.21 e A˚ 3

Extinction correction:SHELXL97

Extinction coefficient: 0.016 (4)

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O7—H7 O1 0.83 (1) 1.68 (1) 2.507 (2) 173 (4) N5—H5A O2 0.89 1.88 2.732 (3) 161 N5—H5B O8ii

0.89 2.17 2.820 (3) 129 N5—H5C O1ii

0.89 2.02 2.899 (3) 170

Symmetry code: (ii)xþ1;y;z.

organic papers

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Joneset al. _C

2H10N22+2C7H3N2O62C7H4N2O6 Acta Cryst.(2005). E61, o1823--o1825

Figure 2

Hydrogen bonding (dashed lines) between the ethylenediaminium and 3,5-dinitrobenzoate ions and the 3,5-dinitrobenzoic acid molecules. Figure 1

View of the asymmetric unit of (I), including the whole ethyl-enediaminium ion, which is on an inversion centre. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i)

x,y,z.]

Figure 3

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All H atoms attached to C and N atoms were fixed using a riding model, with C—H distances 0.93 A˚ (CArH) and 0.97 A˚ (CH2), and

N—H distances 0.89 A˚ . TheUiso(H) values were set equal to 1.2Ueq

of the carrier atom for these H atoms. The hydroxy H atom was located in a Fourier difference map and the coordinates were refined with the O—H bond distance restrained to 0.82 (1) A˚ .

Data collection:COLLECT(Nonius, 2000); cell refinement:HKL SCALEPACK(Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); soft-ware used to prepare material for publication: WinGX (Farrugia, 1999).

The authors thank Sanofi–Aventis Ltd for funding.

References

Blessing, R. H. (1995).Acta Cryst.A51, 33–38. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.

Jones, H. P., Davey, R. J. & Cox, B. G. (2005).J. Phys. Chem. B,109, 5273–5278. Levie, R. de (1999).Aqueous Acid–Base Equilibria and Titrations. New York:

Oxford University Press.

Nonius (2000).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 & R. M. Sweet, pp. 307–326. New York: Academic Press.

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

organic papers

Acta Cryst.(2005). E61, o1823–o1825 Joneset al. _C

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Acta Cryst. (2005). E61, o1823–o1825

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Acta Cryst. (2005). E61, o1823–o1825 [https://doi.org/10.1107/S1600536805015333]

A co-crystal of ethylenediammonium bis(3,5-dinitrobenzoate) and

3,5-dinitro-benzoic acid

Helen P. Jones, Amy L. Gillon and Roger J. Davey

ethylenediaminium–3,5-dinitrobenzoate–3,5-dinitrobenzoic acid (1/2/2), C2H10N22+·2C7H3N2O6-·2C7H4N2O6

Crystal data

0.5C2H10N22+·C7H3N2O6−·C7H4N2O6 Mr = 454.3

Triclinic, P1 Hall symbol: -P 1

a = 7.0452 (3) Å

b = 11.2345 (4) Å

c = 11.7627 (5) Å

α = 91.838 (2)°

β = 96.230 (2)°

γ = 98.710 (1)°

V = 913.72 (6) Å3

Z = 2

F(000) = 466

Dx = 1.651 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 5294 reflections

θ = 1.0–25.0°

µ = 0.15 mm−1 T = 293 K

Prism, pale yellow 0.3 × 0.2 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer

Radiation source: Enraf–Nonius FR590 Graphite monochromator

φ or ω scans?

Absorption correction: multi-scan (Blessing, 1995)

Tmin = 0.916, Tmax = 0.986

8852 measured reflections 3241 independent reflections 2256 reflections with I > 2σ(I)

Rint = 0.046

θmax = 25.2°, θmin = 2.5° h = −8→8

k = −13→13

l = −14→12

Refinement

Refinement on F2

Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.046} wR(F2_{) = 0.136} S = 1.01 3241 reflections 294 parameters 1 restraint

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) + (0.0776P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.20 e Å−3

Δρmin = −0.21 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2_θ_)]-1/4

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Special details

Experimental. Solution pH was measured using an Accumet Basic AB15 pH meter with an Accumet glass calomel pH electrode and an ATC probe to compensate for temperature changes.

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

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C10 0.4134 (3) 0.63433 (18) 0.60626 (17) 0.0404 (5) C11 0.5990 (3) 0.68435 (18) 0.64562 (17) 0.0400 (5) H11 0.6405 0.7669 0.6452 0.048* C12 0.7218 (3) 0.60689 (18) 0.68589 (17) 0.0375 (5) C13 0.6631 (3) 0.48361 (18) 0.68852 (17) 0.0382 (5) H13 0.7496 0.4332 0.7152 0.046* C14 0.3964 (4) 0.30531 (19) 0.65396 (18) 0.0432 (6) C15 0.9287 (3) −0.01948 (18) 0.54167 (18) 0.0421 (5) H15A 0.8006 −0.007 0.5102 0.051* H15B 0.9249 −0.1048 0.5538 0.051* H7 0.469 (5) 0.1743 (18) 0.709 (3) 0.123 (14)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Geometric parameters (Å, º)

O1—C7 1.271 (3) C1—C2 1.388 (3) O2—C7 1.229 (3) C1—C7 1.516 (3) O3—N1 1.226 (2) C2—C3 1.379 (3) O4—N1 1.224 (2) C2—H2 0.93 O5—N2 1.223 (3) C3—C4 1.371 (3) O6—N2 1.215 (3) C4—C5 1.376 (3) O7—C14 1.292 (3) C4—H4 0.93 O7—H7 0.833 (10) C5—C6 1.390 (3) O8—C14 1.205 (3) C6—H6 0.93 O9—N3 1.204 (3) C8—C9 1.384 (3) O10—N3 1.219 (3) C8—C13 1.386 (3) O11—N4 1.232 (2) C8—C14 1.502 (3) O12—N4 1.213 (2) C9—C10 1.379 (3) N1—C3 1.468 (3) C9—H9 0.93 N2—C5 1.469 (3) C10—C11 1.367 (3) N3—C10 1.477 (3) C11—C12 1.377 (3) N4—C12 1.468 (3) C11—H11 0.93 N5—C15 1.483 (3) C12—C13 1.386 (3) N5—H5A 0.89 C13—H13 0.93 N5—H5B 0.89 C15—C15i _{1.506 (4)}

N5—H5C 0.89 C15—H15A 0.97 C1—C6 1.377 (3) C15—H15B 0.97

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C3—C2—H2 120.3 C12—C13—H13 120.8 C1—C2—H2 120.3 O8—C14—O7 125.3 (2) C4—C3—C2 122.5 (2) O8—C14—C8 120.6 (2) C4—C3—N1 118.23 (19) O7—C14—C8 114.1 (2) C2—C3—N1 119.3 (2) N5—C15—C15i _{110.4 (2)}

C3—C4—C5 116.8 (2) N5—C15—H15A 109.6 C3—C4—H4 121.6 C15i_{—C15—H15A} _109.6

C5—C4—H4 121.6 N5—C15—H15B 109.6 C4—C5—C6 122.9 (2) C15i_{—C15—H15B} _109.6

C4—C5—N2 118.01 (19) H15A—C15—H15B 108.1 C6—C5—N2 119.0 (2)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O7—H7···O1 0.83 (1) 1.68 (1) 2.507 (2) 173 (4) N5—H5A···O2 0.89 1.88 2.732 (3) 161 N5—H5B···O8ii _0.89 _2.17 _{2.820 (3)} ₁₂₉

N5—H5C···O1ii _0.89 _2.02 _{2.899 (3)} ₁₇₀