Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Previous article
Next article
Previous article
Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Next article

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 6| June 2012| Page o1695
doi:10.1107/S1600536812020697

4-Cyano­pyridinium nitrate

Wen-Ni Zhenga*

aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: chenxinyuanseu@yahoo.com.cn

(Received 21 April 2012; accepted 8 May 2012; online 12 May 2012)

The title compound, C6H5N2+·NO3−, is a proton-transfer compound between 4-cyano­pyridine and nitric acid. In the asymmetric unit, the components are linked by a strong N—H⋯O hydrogen bond. In the crystal, mol­ecules are linked into a C(6) chain along [010] by C—H⋯O inter­actions.

Related literature

For the structures and ferroelectric properties of related compounds, see: Fu et al. (2011a[Fu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G. & Huang, S. P. D. (2011a). J. Am. Chem. Soc. 133, 12780-12786.],b[Fu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G., Huang, S. P. D. & Nakamura, T. (2011b). Angew. Chem. Int. Ed. 50, 11947-11951.],c[Fu, D.-W., Zhang, W., Cai, H.-L., Ge, J.-Z., Zhang, Y. & Xiong, R.-G. (2011c). Adv. Mater. 23, 5658-5662.]); Dai & Chen (2011[Dai, J. & Chen, X.-Y. (2011). Acta Cryst. E67, o287.]); Xu et al. (2011[Xu, R.-J., Fu, D.-W., Dai, J., Zhang, Y., Ge, J.-Z. & Ye, H.-Y. (2011). Inorg. Chem. Commun. 14, 1093-1096.]); Zheng (2011[Zheng, W.-N. (2011). Acta Cryst. E67, m344.]). For graph-set motif see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data

  • C6H5N2+·NO3−

  • Mr = 167.13

  • Monoclinic, P 21 /c

  • a = 6.3663 (2) Å

  • b = 13.2868 (9) Å

  • c = 9.1019 (2) Å

  • β = 103.755 (1)°

  • V = 747.83 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.12 mm−1

  • T = 298 K

  • 0.10 × 0.05 × 0.05 mm
Data collection

  • Rigaku Mercury2 diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.910, Tmax = 1.000

  • 5151 measured reflections

  • 1694 independent reflections

  • 1349 reflections with I > 2σ(I)

  • Rint = 0.031
Refinement

  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.146

  • S = 1.14

  • 1694 reflections

  • 109 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O3 0.90 1.75 2.6481 (18) 176
C4—H4A⋯O3i 0.93 2.29 3.220 (2) 179
Symmetry code: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812020697/bx2407sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020697/bx2407Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020697/bx2407Isup3.cml

checkCIF report


Comment top

Simple organic salts containing strong intermolecular H-bonds have attracted an attention as materials which display ferroelectric-paraelectric phase transitions (Fu et al., 2011a, 2011b, 2011c). With the purpose of obtaining phase transition crystals of organic salts, various organic molecules have been studied and a series of new materials have been prepared (Dai & Chen 2011; Xu, et al. 2011; Zheng 2011). We report here the crystal structure of the title compound. The title compound (C6H5N2)+.NO3- is a proton-transfer compound between 4-cyanopyridine and nitric acid. In the asymmetric unit the components are linked by one strong N—H···O hydrogen bond interaction, Fig 1. In the crystal the molecules are linked into C(6) chain by simple C—H···O interactions along [010] (Bernstein, et al., 1995), (Fig. 2, Table1).

Related literature top

For the structures and ferroelectric properties of related compounds, see: Fu et al. (2011a,b,c); Dai & Chen (2011); Xu et al. (2011); Zheng (2011). For graph-set motif see: Bernstein et al. (1995).

Experimental top

The HNO3 (5 mL), isonicotinonitrile (20 mmol) and ethanol (50 mL) were added into a 100mL flask. The mixture was stirred at 60oC for 2 h, and then the precipitate was filtrated out. Colourless crystals suitable for X-ray diffraction were obtained by slow evaporation of the solution.

Refinement top

All the H atoms attached to C atoms were situated into the idealized positions and treated as riding with C–H = 0.93 Å (aromatic) with Uiso(H)=1.2Ueq(C). The positional parameters of the H atom (N) was refined freely and in the last stage of the refinement, it was restrained with the N—H = 0.90Å, with Uiso(H)=1.2Ueq(N).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit with the atomic numbering scheme. The displacement ellipsoids were drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed along the a axis showing the N—H···O and C—H···O interactions (dotted line) in the title compound. : symmetry code (i): -x+1, y+1/2, -z+1/2.
4-Cyanopyridinium nitrate top
Crystal data top
C6H5N2+·NO3−F(000) = 344
Mr = 167.13Dx = 1.484 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1694 reflections
a = 6.3663 (2) Åθ = 2.8–27.5°
b = 13.2868 (9) ŵ = 0.12 mm−1
c = 9.1019 (2) ÅT = 298 K
β = 103.755 (1)°Block, colourless
V = 747.83 (6) Å30.10 × 0.05 × 0.05 mm
Z = 4
Data collection top
Rigaku Mercury2
diffractometer		1694 independent reflections
Radiation source: fine-focus sealed tube1349 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 2.8°
CCD profile fitting scansh = −8→7
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −17→15
Tmin = 0.910, Tmax = 1.000l = −11→11
5151 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0719P)2 + 0.0927P]
where P = (Fo2 + 2Fc2)/3
1694 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.23 e Å−3
1 restraintΔρmin = −0.19 e Å−3
Crystal data top
C6H5N2+·NO3−V = 747.83 (6) Å3
Mr = 167.13Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.3663 (2) ŵ = 0.12 mm−1
b = 13.2868 (9) ÅT = 298 K
c = 9.1019 (2) Å0.10 × 0.05 × 0.05 mm
β = 103.755 (1)°
Data collection top
Rigaku Mercury2
diffractometer		1694 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		1349 reflections with I > 2σ(I)
Tmin = 0.910, Tmax = 1.000Rint = 0.031
5151 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0501 restraint
wR(F2) = 0.146H-atom parameters constrained
S = 1.14Δρmax = 0.23 e Å−3
1694 reflectionsΔρmin = −0.19 e Å−3
109 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) top
xyzUiso*/Ueq
O30.7551 (2)0.46541 (8)0.20815 (14)0.0477 (4)
N30.7428 (2)0.42233 (11)0.08092 (16)0.0447 (4)
N10.7453 (2)0.66359 (10)0.17652 (16)0.0440 (4)
H10.74130.59620.18600.053*
C30.7627 (3)0.86509 (12)0.13720 (18)0.0400 (4)
N20.7637 (3)1.05763 (13)0.0946 (2)0.0648 (5)
C40.6008 (3)0.82380 (12)0.1963 (2)0.0456 (4)
H4A0.49740.86480.22300.055*
O20.7350 (2)0.32899 (10)0.07536 (16)0.0631 (4)
C20.9185 (3)0.80337 (13)0.0992 (2)0.0455 (4)
H2A1.02870.83040.06030.055*
C50.5955 (3)0.72140 (13)0.2149 (2)0.0466 (4)
H5A0.48770.69240.25430.056*
O10.7392 (3)0.47362 (11)−0.03265 (17)0.0684 (5)
C10.9049 (3)0.70149 (13)0.1208 (2)0.0474 (4)
H1A1.00730.65870.09660.057*
C60.7672 (3)0.97304 (14)0.1142 (2)0.0484 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O30.0566 (8)0.0384 (6)0.0478 (7)−0.0022 (5)0.0118 (6)−0.0026 (5)
N30.0376 (8)0.0469 (8)0.0511 (9)0.0017 (6)0.0136 (6)−0.0006 (6)
N10.0483 (8)0.0339 (7)0.0491 (8)−0.0012 (6)0.0102 (6)0.0000 (6)
C30.0417 (9)0.0359 (8)0.0399 (8)−0.0008 (6)0.0047 (6)0.0005 (6)
N20.0756 (13)0.0408 (9)0.0743 (12)−0.0017 (8)0.0107 (10)0.0084 (7)
C40.0448 (9)0.0431 (9)0.0513 (10)0.0059 (7)0.0165 (8)0.0003 (7)
O20.0760 (10)0.0423 (8)0.0727 (10)−0.0014 (6)0.0211 (8)−0.0115 (6)
C20.0419 (9)0.0464 (9)0.0506 (10)−0.0030 (7)0.0157 (7)0.0009 (7)
C50.0448 (10)0.0457 (10)0.0513 (10)−0.0031 (8)0.0153 (8)0.0032 (7)
O10.0877 (11)0.0705 (10)0.0542 (8)0.0080 (8)0.0313 (7)0.0124 (7)
C10.0466 (10)0.0447 (9)0.0527 (10)0.0046 (8)0.0155 (8)−0.0042 (7)
C60.0504 (11)0.0429 (10)0.0495 (9)−0.0015 (7)0.0071 (8)0.0018 (7)
Geometric parameters (Å, º) top
O3—N31.2774 (18)C3—C61.451 (2)
N3—O11.234 (2)N2—C61.137 (2)
N3—O21.2418 (19)C4—C51.373 (2)
N1—C51.334 (2)C4—H4A0.9300
N1—C11.337 (2)C2—C11.374 (2)
N1—H10.9005C2—H2A0.9300
C3—C41.385 (2)C5—H5A0.9300
C3—C21.392 (2)C1—H1A0.9300
O1—N3—O2121.67 (16)C3—C4—H4A120.6
O1—N3—O3119.80 (15)C1—C2—C3118.17 (15)
O2—N3—O3118.53 (14)C1—C2—H2A120.9
C5—N1—C1122.52 (15)C3—C2—H2A120.9
C5—N1—H1120.6N1—C5—C4119.88 (16)
C1—N1—H1116.9N1—C5—H5A120.1
C4—C3—C2120.22 (15)C4—C5—H5A120.1
C4—C3—C6119.33 (15)N1—C1—C2120.31 (16)
C2—C3—C6120.44 (15)N1—C1—H1A119.8
C5—C4—C3118.89 (15)C2—C1—H1A119.8
C5—C4—H4A120.6N2—C6—C3177.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O30.901.752.6481 (18)176
C4—H4A···O3i0.932.293.220 (2)179
Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formulaC6H5N2+·NO3−
Mr167.13
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)6.3663 (2), 13.2868 (9), 9.1019 (2)
β (°) 103.755 (1)
V (Å3)747.83 (6)
Z4
Radiation typeMo Kα
µ (mm−1)0.12
Crystal size (mm)0.10 × 0.05 × 0.05
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.910, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		5151, 1694, 1349
Rint0.031
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.146, 1.14
No. of reflections1694
No. of parameters109
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.23, −0.19

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O30.901.752.6481 (18)175.6
C4—H4A···O3i0.932.293.220 (2)179
Symmetry code: (i) −x+1, y+1/2, −z+1/2.
 

Acknowledgements

This work was supported by a start-up grant from Southeast University, China.

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
 First citationDai, J. & Chen, X.-Y. (2011). Acta Cryst. E67, o287.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationDolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationFu, D.-W., Zhang, W., Cai, H.-L., Ge, J.-Z., Zhang, Y. & Xiong, R.-G. (2011c). Adv. Mater. 23, 5658–5662.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationFu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G. & Huang, S. P. D. (2011a). J. Am. Chem. Soc. 133, 12780–12786.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationFu, D.-W., Zhang, W., Cai, H.-L., Zhang, Y., Ge, J.-Z., Xiong, R.-G., Huang, S. P. D. & Nakamura, T. (2011b). Angew. Chem. Int. Ed. 50, 11947–11951.  Web of Science CSD CrossRef CAS Google Scholar
 First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationXu, R.-J., Fu, D.-W., Dai, J., Zhang, Y., Ge, J.-Z. & Ye, H.-Y. (2011). Inorg. Chem. Commun. 14, 1093-1096.  Web of Science CSD CrossRef CAS Google Scholar
 First citationZheng, W.-N. (2011). Acta Cryst. E67, m344.  Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 6| June 2012| Page o1695
doi:10.1107/S1600536812020697
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS