Piperazinium nitrate

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organic papers

Acta Cryst.(2005). E61, o2531–o2533 doi:10.1107/S1600536805021951 Perpe´tuo and Janczak _C

4H11N2+NO3

o2531

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Piperazinium nitrate

Genivaldo Julio Perpe´tuoaand

Jan Janczakb*

a

Departamento de Fisica, Instituto de Cieˆncias Exatas e Biolo´gicas, Universidade Federal de Ouro Preto, CEP 35.400-000 – Ouro Preto – MG, Brazil, andb_{Institute of Low Temperature}

and Structure Research, Polish Academy of Sciences, PO Box 1410, 50-950 Wrocław, Poland

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 295 K

Mean(C–C) = 0.002 A˚

Rfactor = 0.043

wRfactor = 0.108

Data-to-parameter ratio = 19.7

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

Crystals of the title compound, C4H11N2 +

NO3

, are built up from singly protonated piperazinium residues and nitrate anions. The components are linked by hydrogen bonds into a three-dimensional framework. The piperazinium residues are linked togetherviaN—H N hydrogen bonds into chains in the form of stacks along the [100] direction.

Comment

The present study is a continuation of the work on compounds that form non-covalent supramolecular framework structures in the solid-state viamultiple hydrogen bonds (Perpe´tuo & Janczak, 2004), in order to expand our understanding of the physical–organic chemistry of systems containing multiple N—H N and N—H O hydrogen bonds in the solid state. We present here the solid-state structure of piperazinium nitrate, (I). Selected geometric parameters are given in Table 1.

The singly protonated piperazinium ring in the crystal structure of (I) adopts the chair conformation (Fig. 1) predicted by molecular orbital calculations for the isolated ion (Frisch et al., 1998). As a result of protonation, the C—N bonds involving the protonated N atom are slightly longer than the C—N bonds containing the non-protonated N atom (Table 1). The correlation between the C—N bonds is similar to that found in the gas-phase structure obtained by DFT using the B3LYP method; the optimized C—N bond lengths involving the protonated N atom are 1.510 A˚ , while the C—N

[image:1.610.228.438.371.464.2] [image:1.610.206.460.626.723.2]

Received 16 June 2005 Accepted 8 July 2005 Online 16 July 2005

Figure 1

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bond lengths involving the non-protonated N atom are 1.445 A˚ .

The geometry of the nitrate anion in (I) shows a slight distortion fromD3hsymmetry obtained by molecular orbital

calculations [the three N—O bonds in the isolated NO

3 ion

[image:2.610.47.294.71.233.2]

are equivalent, with a length of 1.226 A˚ (Frisch et al., 1998)] due to the interaction with the piperazinium cation and the formation of hydrogen bonds. The N—O bond lengths in the nitrate anion are indicative of a bond order between 1 and 2, reflecting delocalization of two bonds over three N. . .O bonds. The O atom with the shortest N—O bond length (O3) does not form a hydrogen bond and the other two O atoms are involved in hydrogen bonds as acceptors, one in two hydrogen bonds (O1) and the other in one hydrogen bond (O2) (Table 2).

In the crystal structure, the piperazinium C4H11N

þ

2 cations

are linkedviaN—H N hydrogen bonds into chains, in the form of stacks parallel to the [100] direction (Fig. 2). These chains are interconnectedviaN—H O hydrogen bonds with the nitrate anions into a three-dimensional framework superstructure.

A survey of the Cambridge Structural Database (CSD; Version 5.26; Allen, 2002) for systems containing piperazinium cations yields over 300 structures with the doubly protonated piperazinium(2+) cation and a few structures with a singly protonated piperazinium(+) cation. The singly protonated piperazinium(+) cation mainly forms complexes with metals in which the non-protonated N atom of the piperazinium ring coordinates to the metal, as found in several open-framework structures (Neerajet al., 2001, 2002; Francis & Jacobson, 2001), or forms salts with large organic acids, as found in the struc-ture of piperazinium 5,7-dihydroxy-3-(4-hydroxyphenyl)-4H -1-benzopyran-4-one hydrate (Kozerski et al., 2003). In all structures containing the singly protonated piperazinium(+) cation, the ring, as observed for (I), adopts a chair confor-mation. The structures of piperazinium salts of basic organic

or inorganic acids contain doubly protonated

piper-azinium(2+) cations. Thus, (I) represents the first structurally characterized simple inorganic salt containing a singly protonated piperazinium cation.

Experimental

Piperazine (99%) purchased from Aldrich was dissolved in 10% nitric acid. After several days, colourless single crystals appeared.

Crystal data

C4H11N þ 2NO

3

Mr= 149.16

Monoclinic,P21=c

a= 4.4420 (9) A˚ b= 12.953 (3) A˚ c= 12.677 (3) A˚

= 95.62 (3)

V= 725.9 (3) A˚3

Z= 4

Dx= 1.365 Mg m 3

MoKradiation Cell parameters from 937

reflections

= 3.2–29.5

= 0.12 mm1

T= 295 (2) K

Parallelepiped, colourless 0.420.350.22 mm

Data collection

Kuma KM-4 CCD area-detector diffractometer

!scans

Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990) Tmin= 0.948,Tmax= 0.970

8599 measured reflections

1874 independent reflections 939 reflections withI> 2(I) Rint= 0.018

max= 29.5

h=5!5 k=17!16 l=16!17

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.043 wR(F2_{) = 0.108}

S= 1.05 1874 reflections 95 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2₍_F

o2) + (0.0421P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.003 max= 0.14 e A˚

3

min=0.14 e A˚ 3

[image:2.610.314.566.478.537.2]

Extinction correction:SHELXL97 Extinction coefficient: 0.012 (3)

Table 1

Selected geometric parameters (A˚ ,_).

N2—O3 1.2114 (15) N2—O2 1.2340 (14) N2—O1 1.2388 (15) N1—C2 1.4445 (18)

N1—C6 1.4592 (19) C3—N4 1.4841 (18) N4—C5 1.4669 (18)

O3—N2—O2 124.63 (14) O3—N2—O1 119.14 (14)

[image:2.610.314.565.598.654.2]

O2—N2—O1 116.22 (12)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N4—H41 O1 0.90 2.07 2.9222 (14) 158 N4—H41 O2 0.90 2.32 3.0849 (15) 142 N4—H42 N1i

0.90 1.92 2.8219 (16) 178 N1—H1 O1ii

0.85 (2) 2.27 (2) 3.0486 (15) 153 (1)

Symmetry codes: (i)xþ1;y;z; (ii)x1;yþ1 2;zþ

1 2.

The H atoms bonded to C atoms and N4 were placed in idealized positions and refined as riding atoms, with C—H and N—H distances constrained to 0.97 and 0.90 A˚ , respectively, and Uiso(H) =

1.5Ueq(parent atom). The H atom bonded to N1 was located in a

difference Fourier map and restrained with N—H = 0.85 (1) A˚ and

Uiso(H) = 1.5Ueq(N1).

organic papers

o2532

Perpe´tuo and Janczak _C

4H11N+2NO3 Acta Cryst.(2005). E61, o2531–o2533

Figure 2

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Data collection:KM-4 CCD Software (Kuma, 2001); cell refine-ment: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:SHELXTL (Sheldrick, 1990); software used to prepare material for publication:SHELXL97.

GJP thanks the CNPq foundation (Brazil) for financial support.

References

Allen, F. H. (2002).Acta Cryst.B58, 380–388.

Francis, R. J. & Jacobson, A. J. (2001).Angew. Chem. Int. Ed.40, 2879–2881.

Frisch, J. M., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Zakrzewski, V. G., Montgomery Jr, J. A., Stratmann, R. E., Burant, J. C.et al.(1998).GAUSSIAN98. Revision A3. Gaussian Inc., Pittsburgh, PA, USA.

Kozerski, L., Kamien´ski, B., Kawe´cki, R., Urbanczyk-Lipkowska, Z., Bocian, W., Bednarek, E., Sitkowski, J., Zakrzewska, K., Nielsen, K. T. & Hansen, P. E. (2003).Org. Biomol. Chem.1, 3578–3585.

Kuma (2001). KM-4 CCD Software. Version 171.1. Kuma Diffraction, Wrocław, Poland.

Neeraj, S., Forster, P. M., Rao, C. N. R. & Cheetham, A. K. (2001).Chem. Commun.pp. 2716–2717.

Neeraj, S., Noy, M. L., Rao, C. N. R. & Cheetham, A. N. (2002).J. Solid State Chem.167, 344–353.

Perpe´tuo, G. J. & Janczak, J. (2004).Acta Cryst.C60, o768–o770.

Sheldrick, G. M. (1990).SHELXTL.Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997).SHELXS97andSHELXL97. University of Go¨tingen, Germany.

organic papers

Acta Cryst.(2005). E61, o2531–o2533 Perpe´tuo and Janczak _C

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supporting information

sup-1 Acta Cryst. (2005). E61, o2531–o2533

supporting information

Acta Cryst. (2005). E61, o2531–o2533 [https://doi.org/10.1107/S1600536805021951]

Piperazinium nitrate

Genivaldo Julio Perp

é

tuo and Jan Janczak

(I)

Crystal data

C4H11N2+·NO3− Mr = 149.16

Monoclinic, P21/c Hall symbol: -P 2ybc a = 4.4420 (9) Å b = 12.953 (3) Å c = 12.677 (3) Å β = 95.62 (3)° V = 725.9 (3) Å3 Z = 4

F(000) = 320

Dx = 1.365 Mg m−3 Dm = 1.36 Mg m−3 Dm measured by flotation Mo Kα radiation, λ = 0.71073 Å Cell parameters from 937 reflections θ = 3.2–29.5°

µ = 0.12 mm−1 T = 295 K

Parallelepiped, colourless 0.42 × 0.35 × 0.22 mm

Data collection

Kuma KM-4 with CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1

ω scans

Absorption correction: analytical

face-indexed (SHELXTL; Sheldrick, 1990)

Tmin = 0.948, Tmax = 0.970 8599 measured reflections 1874 independent reflections 939 reflections with I > 2σ(I) Rint = 0.018

θmax = 29.5°, θmin = 3.2° h = −5→5

k = −17→16 l = −16→17

Refinement

Refinement on F2 Least-squares matrix: full R[F2_{> 2σ(F}2_{)] = 0.043} wR(F2_{) = 0.108} S = 1.05 1874 reflections 95 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) + (0.0421P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.003

Δρmax = 0.14 e Å−3 Δρmin = −0.14 e Å−3

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supporting information

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 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

N2 0.9850 (2) 0.04477 (10) 0.26449 (9) 0.0658 (4) O1 0.9832 (2) 0.14018 (8) 0.25769 (7) 0.0678 (4) O2 0.9157 (3) 0.00830 (8) 0.34873 (10) 0.0794 (5) O3 1.0575 (3) −0.00589 (10) 0.19074 (12) 0.0913 (5) N1 0.2485 (2) 0.29227 (10) 0.55572 (9) 0.0551 (4) H1 0.201 (3) 0.3301 (11) 0.6059 (12) 0.083* C2 0.4173 (3) 0.35955 (10) 0.49228 (12) 0.0605 (4) H21 0.5880 0.3887 0.5358 0.091* H22 0.2891 0.4159 0.4645 0.091* C3 0.5269 (3) 0.30026 (12) 0.40327 (10) 0.0612 (4) H31 0.3558 0.2746 0.3573 0.092* H32 0.6452 0.3449 0.3618 0.092* N4 0.7157 (2) 0.21240 (9) 0.44595 (9) 0.0595 (4) H41 0.7705 0.1741 0.3917 0.089* H42 0.8851 0.2369 0.4821 0.089* C5 0.5545 (3) 0.14682 (10) 0.51619 (12) 0.0634 (4) H51 0.6891 0.0934 0.5468 0.095* H52 0.3847 0.1136 0.4758 0.095* C6 0.4442 (3) 0.21019 (12) 0.60193 (10) 0.0611 (4) H61 0.3326 0.1670 0.6470 0.092* H62 0.6147 0.2400 0.6451 0.092*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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supporting information

Geometric parameters (Å, º)

N2—O3 1.2114 (15) C3—H31 0.9700 N2—O2 1.2340 (14) C3—H32 0.9700 N2—O1 1.2388 (15) N4—C5 1.4669 (18) N1—C2 1.4445 (18) N4—H41 0.9000 N1—C6 1.4592 (19) N4—H42 0.9000 N1—H1 0.846 (15) C5—C6 1.483 (2) C2—C3 1.486 (2) C5—H51 0.9700 C2—H21 0.9700 C5—H52 0.9700 C2—H22 0.9700 C6—H61 0.9700 C3—N4 1.4841 (18) C6—H62 0.9700

O3—N2—O2 124.63 (14) C5—N4—C3 111.92 (10) O3—N2—O1 119.14 (14) C5—N4—H41 109.2 O2—N2—O1 116.22 (12) C3—N4—H41 109.2 C2—N1—C6 109.99 (10) C5—N4—H42 109.2 C2—N1—H1 104.5 (10) C3—N4—H42 109.2 C6—N1—H1 107.6 (10) H41—N4—H42 107.9 N1—C2—C3 109.72 (12) N4—C5—C6 109.90 (11) N1—C2—H21 109.7 N4—C5—H51 109.7 C3—C2—H21 109.7 C6—C5—H51 109.7 N1—C2—H22 109.7 N4—C5—H52 109.7 C3—C2—H22 109.7 C6—C5—H52 109.7 H21—C2—H22 108.2 H51—C5—H52 108.2 N4—C3—C2 109.57 (11) N1—C6—C5 109.61 (11) N4—C3—H31 109.8 N1—C6—H61 109.7 C2—C3—H31 109.8 C5—C6—H61 109.7 N4—C3—H32 109.8 N1—C6—H62 109.7 C2—C3—H32 109.8 C5—C6—H62 109.7 H31—C3—H32 108.2 H61—C6—H62 108.2

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N4—H41···O1 0.90 2.07 2.9222 (14) 158 N4—H41···O2 0.90 2.32 3.0849 (15) 142 N4—H42···N1i _0.90 _1.92 _{2.8219 (16)} ₁₇₈ N1—H1···O1ii _{0.846 (15)} _{2.270 (15)} _{3.0486 (15)} _{153.2 (12)}