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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 12| December 2010| Page o3295
https://doi.org/10.1107/S1600536810048294

3-Cyano­anilinium iodide monohydrate

Jing Daia* and Xin-Yuan Chena

aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 13 November 2010; accepted 19 November 2010; online 24 November 2010)

In the crystal structure of the title compound, C7H7N2+·I−·H2O, [C7H7N2+]n chains extending along the a-axis direction are linked via N—H⋯N hydrogen bonds. The cations are further connected to the anions by N—H⋯I, N—H⋯O and O—H⋯I hydrogen bonds, leading to the formation of a sheet parallel to the ac plane. π–π inter­actions [centroid–centroid distance = 3.8378 (7) Å] link the sheets into a three-dimensional network.

Related literature

For related structures, see: Oueslati et al. (2005[Oueslati, A., Kefi, R., Akriche, S. & Nasr, C. B. (2005). Z. Kristallogr. New Cryst. Struct. 220, 365-366.]); Messai et al. (2009[Messai, A., Direm, A., Benali-Cherif, N., Luneau, D. & Jeanneau, E. (2009). Acta Cryst. E65, o460.]). For applications of salts of amides as phase-transition dielectric materials, see: Fu et al. (2007[Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S.-P.-D. (2007). J. Am. Chem. Soc. 129, 5346-5347.], 2008[Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461-3464.], 2009[Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994-997.]); Fu & Xiong (2008[Fu, D.-W. & Xiong, R.-G. (2008). Dalton Trans. pp. 3946-3948.]).

[Scheme 1]

Experimental

Crystal data

  • C7H7N2+·I−·H2O

  • Mr = 264.06

  • Monoclinic, P 21 /c

  • a = 8.0436 (16) Å

  • b = 16.603 (3) Å

  • c = 7.6746 (15) Å

  • β = 115.39 (3)°

  • V = 925.9 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.41 mm−1

  • T = 298 K

  • 0.10 × 0.03 × 0.03 mm
Data collection

  • Rigaku Mercury2 diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Version 1.4.0. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.910, Tmax = 1.000

  • 9455 measured reflections

  • 2117 independent reflections

  • 1978 reflections with I > 2σ(I)

  • Rint = 0.041
Refinement

  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.061

  • S = 1.21

  • 2117 reflections

  • 102 parameters

  • H-atom parameters constrained

  • Δρmax = 0.72 e Å−3

  • Δρmin = −0.89 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1C⋯N2i 0.89 2.11 2.991 (4) 169
N1—H1A⋯O1Wii 0.89 1.98 2.850 (4) 164
N1—H1B⋯I1iii 0.89 2.60 3.487 (3) 171
O1W—H1WB⋯I1ii 0.93 2.75 3.635 (3) 159
O1W—H1WA⋯I1 0.96 2.65 3.576 (3) 162
Symmetry codes: (i) x+1, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) x+1, y, z.

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Version 1.4.0. 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810048294/vm2061sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048294/vm2061Isup2.hkl

checkCIF report


Comment top

Salts of amides attracted much attention as phase transition dielectric materials for applications in micro-electronics and memory storage (Fu et al. 2007; Fu & Xiong 2008; Fu et al. 2008; Fu et al. 2009). With the purpose of obtaining phase transition crystals of 3-aminobenzonitrile salts, its interaction with various acids has been studied and we have elaborated a series of new materials with this organic molecule. In this paper, we describe the crystal structure of the title compound, 3-cyanoanilinium iodine monohydrate.

The asymmetric unit is composed of a iodine anion, a 3-cyanoanilinium cation and a water molecule (Fig.1). The geometric parameters of the title compound agree well with reported similar structures (Oueslati et al., 2005; Messai et al., 2009). The cation is almost planar (r.m.s. deviation 0.0097 Å for best plane through all non-H atoms of cation). Moreover, the C—NH3 (1.459 (2)Å) and C≡N (1.132 (3) Å) distances in the 3-cyanoanilinium cation are almost equal with respect to the C—NH3 (1.457 (4) Å) and C≡ N (1.137 (4) Å) observed in the crystal structure of 2-cyanoanilinium chloride (Oueslati et al., 2005).

The cations are surrounded by the anions and water molecules via hydrogen bonds which play an important role in stabilizing the crystal structure. In the crystal structure, all the amine group H atoms are involved in N—H···I, N—H···O and N—H···N hydrogen bonds with N···I, N···O and N···N distances of 3.487 (3) Å, 2.850 (4)Å and 2.991 (4) Å. These hydrogen bonds link the ionic units into a two-dimensional graph-set motif parallel to the ac plane (Table 1, Fig. 2). Furthermore, π–π interactions [Cg(1)···Cg(1)i = 3.8378 (7) Å; Cg(1) is centroid of ring C2 - C7; symmetry operation: (i) x, 1/2 - y, 1/2 + z ] link the sheets into a three-dimensional network (Fig.3).

Related literature top

For related structures, see: Oueslati et al. (2005); Messai et al. (2009). For applications of salts of amides as phase-transition dielectric materials, see: Fu et al. (2007, 2008, 2009); Fu & Xiong (2008).

Experimental top

The commercial available 3-aminobenzonitrile (3 mmol, 324 mg) was dissolved in water/HI (50:1 v/v) solution. The solvent was slowly evaporated in air affording colourless block-shaped crystals of the title compound suitable for X-ray analysis.

While permittivity measurements show that there is no phase transition within the temperature range (from 100 K to 400 K), the permittivity is 6.8 at 1 MHz at room temperature.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with C–H = 0.93 Å, with Uiso(H) = 1.2Ueq(C). The NH3+ H atoms were calculated geometrically and were refined using a riding model with N—H = 0.89 Å, with Uiso(H) = 1.5Ueq(N). A rotating-group model was used for the –NH3 group. H atoms of water molecule were located in difference Fourier maps and freely refined. In the last stage of refinement they were treated as riding on the O atom, with Uiso(H) = 1.5Ueq(O).

Structure description top

Salts of amides attracted much attention as phase transition dielectric materials for applications in micro-electronics and memory storage (Fu et al. 2007; Fu & Xiong 2008; Fu et al. 2008; Fu et al. 2009). With the purpose of obtaining phase transition crystals of 3-aminobenzonitrile salts, its interaction with various acids has been studied and we have elaborated a series of new materials with this organic molecule. In this paper, we describe the crystal structure of the title compound, 3-cyanoanilinium iodine monohydrate.

The asymmetric unit is composed of a iodine anion, a 3-cyanoanilinium cation and a water molecule (Fig.1). The geometric parameters of the title compound agree well with reported similar structures (Oueslati et al., 2005; Messai et al., 2009). The cation is almost planar (r.m.s. deviation 0.0097 Å for best plane through all non-H atoms of cation). Moreover, the C—NH3 (1.459 (2)Å) and C≡N (1.132 (3) Å) distances in the 3-cyanoanilinium cation are almost equal with respect to the C—NH3 (1.457 (4) Å) and C≡ N (1.137 (4) Å) observed in the crystal structure of 2-cyanoanilinium chloride (Oueslati et al., 2005).

The cations are surrounded by the anions and water molecules via hydrogen bonds which play an important role in stabilizing the crystal structure. In the crystal structure, all the amine group H atoms are involved in N—H···I, N—H···O and N—H···N hydrogen bonds with N···I, N···O and N···N distances of 3.487 (3) Å, 2.850 (4)Å and 2.991 (4) Å. These hydrogen bonds link the ionic units into a two-dimensional graph-set motif parallel to the ac plane (Table 1, Fig. 2). Furthermore, π–π interactions [Cg(1)···Cg(1)i = 3.8378 (7) Å; Cg(1) is centroid of ring C2 - C7; symmetry operation: (i) x, 1/2 - y, 1/2 + z ] link the sheets into a three-dimensional network (Fig.3).

For related structures, see: Oueslati et al. (2005); Messai et al. (2009). For applications of salts of amides as phase-transition dielectric materials, see: Fu et al. (2007, 2008, 2009); Fu & Xiong (2008).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound, showing the two-dimensional hydrogen-bonded network parallel to the ac plane. H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.
[Figure 3] Fig. 3. The crystal packing of the title compound showing the π-π interactions linking the hydrogen-bonded network into a three-dimensional network.
3-Cyanoanilinium iodide monohydrate top
Crystal data top
C7H7N2+·I−·H2OF(000) = 504
Mr = 264.06Dx = 1.894 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2117 reflections
a = 8.0436 (16) Åθ = 3.1–27.5°
b = 16.603 (3) ŵ = 3.41 mm−1
c = 7.6746 (15) ÅT = 298 K
β = 115.39 (3)°Block, colorless
V = 925.9 (3) Å30.10 × 0.03 × 0.03 mm
Z = 4
Data collection top
Rigaku Mercury2
diffractometer		2117 independent reflections
Radiation source: fine-focus sealed tube1978 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
CCD profile fitting scansh = −10→10
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −21→21
Tmin = 0.910, Tmax = 1.000l = −9→9
9455 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.061 w = 1/[σ2(Fo2) + (0.0103P)2 + 0.9565P]
where P = (Fo2 + 2Fc2)/3
S = 1.21(Δ/σ)max < 0.001
2117 reflectionsΔρmax = 0.72 e Å−3
102 parametersΔρmin = −0.89 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0824 (16)
Crystal data top
C7H7N2+·I−·H2OV = 925.9 (3) Å3
Mr = 264.06Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.0436 (16) ŵ = 3.41 mm−1
b = 16.603 (3) ÅT = 298 K
c = 7.6746 (15) Å0.10 × 0.03 × 0.03 mm
β = 115.39 (3)°
Data collection top
Rigaku Mercury2
diffractometer		2117 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		1978 reflections with I > 2σ(I)
Tmin = 0.910, Tmax = 1.000Rint = 0.041
9455 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.21Δρmax = 0.72 e Å−3
2117 reflectionsΔρmin = −0.89 e Å−3
102 parameters
Special details top

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) top
xyzUiso*/Ueq
N11.0275 (3)0.37559 (16)0.8592 (4)0.0332 (6)
H1A0.96060.41460.87750.050*
H1B1.08610.39490.79270.050*
H1C1.10930.35750.97300.050*
N20.3209 (4)0.3013 (2)0.2122 (4)0.0483 (8)
C10.4542 (4)0.2842 (2)0.3388 (4)0.0350 (7)
C20.6270 (4)0.26503 (19)0.4998 (4)0.0288 (6)
C30.6773 (4)0.18539 (19)0.5508 (5)0.0343 (7)
H30.59950.14360.48290.041*
C40.8443 (4)0.1692 (2)0.7037 (5)0.0365 (7)
H40.87880.11610.73940.044*
C50.9614 (4)0.23118 (18)0.8048 (4)0.0306 (6)
H51.07470.22000.90650.037*
C60.9070 (4)0.30971 (17)0.7520 (4)0.0257 (6)
C70.7422 (4)0.32826 (19)0.6002 (4)0.0294 (6)
H70.70850.38150.56530.035*
O1W0.2139 (3)0.49557 (16)0.1596 (4)0.0488 (6)
H1WA0.23480.47070.28060.073*
H1WB0.33250.50710.17420.073*
I10.30166 (3)0.451061 (14)0.64728 (3)0.04440 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0275 (13)0.0362 (14)0.0302 (13)−0.0081 (10)0.0067 (10)−0.0028 (11)
N20.0317 (15)0.060 (2)0.0379 (15)0.0013 (13)0.0001 (13)−0.0064 (14)
C10.0271 (15)0.0425 (18)0.0300 (16)−0.0034 (13)0.0073 (13)−0.0073 (13)
C20.0214 (13)0.0374 (16)0.0244 (14)−0.0004 (12)0.0068 (11)−0.0034 (12)
C30.0298 (15)0.0344 (16)0.0380 (16)−0.0077 (12)0.0139 (13)−0.0100 (13)
C40.0361 (16)0.0293 (16)0.0391 (17)0.0031 (13)0.0116 (14)0.0000 (13)
C50.0244 (14)0.0367 (16)0.0277 (14)0.0035 (12)0.0083 (12)0.0028 (12)
C60.0217 (13)0.0311 (15)0.0231 (13)−0.0054 (11)0.0086 (11)−0.0033 (11)
C70.0258 (14)0.0307 (15)0.0278 (14)0.0013 (11)0.0079 (11)0.0014 (11)
O1W0.0377 (13)0.0442 (14)0.0516 (15)−0.0006 (11)0.0070 (11)−0.0055 (11)
I10.03749 (16)0.04184 (17)0.05167 (18)0.00206 (9)0.01702 (12)0.01218 (10)
Geometric parameters (Å, º) top
N1—C61.459 (4)C3—H30.9300
N1—H1A0.8900C4—C51.386 (4)
N1—H1B0.8900C4—H40.9300
N1—H1C0.8900C5—C61.380 (4)
N2—C11.132 (4)C5—H50.9300
C1—C21.444 (4)C6—C71.373 (4)
C2—C31.389 (4)C7—H70.9300
C2—C71.394 (4)O1W—H1WA0.9626
C3—C41.380 (4)O1W—H1WB0.9316
C6—N1—H1A109.5C3—C4—C5120.8 (3)
C6—N1—H1B109.5C3—C4—H4119.6
H1A—N1—H1B109.5C5—C4—H4119.6
C6—N1—H1C109.5C6—C5—C4118.9 (3)
H1A—N1—H1C109.5C6—C5—H5120.5
H1B—N1—H1C109.5C4—C5—H5120.5
N2—C1—C2178.0 (4)C7—C6—C5122.0 (3)
C3—C2—C7121.1 (3)C7—C6—N1118.5 (3)
C3—C2—C1120.5 (3)C5—C6—N1119.5 (3)
C7—C2—C1118.3 (3)C6—C7—C2118.1 (3)
C4—C3—C2119.0 (3)C6—C7—H7120.9
C4—C3—H3120.5C2—C7—H7120.9
C2—C3—H3120.5H1WA—O1W—H1WB103.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···N2i0.892.112.991 (4)169
N1—H1A···O1Wii0.891.982.850 (4)164
N1—H1B···I1iii0.892.603.487 (3)171
O1W—H1WB···I1ii0.932.753.635 (3)159
O1W—H1WA···I10.962.653.576 (3)162
Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC7H7N2+·I−·H2O
Mr264.06
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)8.0436 (16), 16.603 (3), 7.6746 (15)
β (°) 115.39 (3)
V (Å3)925.9 (3)
Z4
Radiation typeMo Kα
µ (mm−1)3.41
Crystal size (mm)0.10 × 0.03 × 0.03
Data collection
DiffractometerRigaku Mercury2
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.910, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		9455, 2117, 1978
Rint0.041
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.061, 1.21
No. of reflections2117
No. of parameters102
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.72, −0.89

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···N2i0.892.112.991 (4)169.4
N1—H1A···O1Wii0.891.982.850 (4)164.2
N1—H1B···I1iii0.892.603.487 (3)171.4
O1W—H1WB···I1ii0.932.753.635 (3)159.1
O1W—H1WA···I10.962.653.576 (3)161.7
Symmetry codes: (i) x+1, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z.
 

Acknowledgements

This work was supported by a start-up grant from where?.

References

First citationFu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997.  Web of Science CSD CrossRef CAS Google Scholar
 First citationFu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S.-P.-D. (2007). J. Am. Chem. Soc. 129, 5346–5347.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationFu, D.-W. & Xiong, R.-G. (2008). Dalton Trans. pp. 3946–3948.  Web of Science CSD CrossRef Google Scholar
 First citationFu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461–3464.  Web of Science CSD CrossRef CAS Google Scholar
 First citationMessai, A., Direm, A., Benali-Cherif, N., Luneau, D. & Jeanneau, E. (2009). Acta Cryst. E65, o460.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationOueslati, A., Kefi, R., Akriche, S. & Nasr, C. B. (2005). Z. Kristallogr. New Cryst. Struct. 220, 365–366.  CAS Google Scholar
 First citationRigaku (2005). CrystalClear. Version 1.4.0. 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

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 12| December 2010| Page o3295
https://doi.org/10.1107/S1600536810048294
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