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The title compound, C7H7N2+·ClO4, comprises discrete ions which are inter­connected by N—H...O hydrogen bonds, leading to a neutral one-dimensional network along the [100] direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808030687/bx2181sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536808030687/bx2181Isup2.hkl
Contains datablock I

CCDC reference: 706139

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.036
  • wR factor = 0.097
  • Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT220_ALERT_2_C Large Non-Solvent N Ueq(max)/Ueq(min) ... 2.65 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cl1 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C1 - C2 ... 1.45 Ang. PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.94 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 3000 Deg.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.942 Tmax scaled 0.942 Tmin scaled 0.886
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Nitrile derivatives have found wide range of applications in industry and coordination chemistry as ligands. For example, phthalonitriles have been used as starting materials for phthalocyanines (Jin et al., 1994), which are important components for dyes, pigments, gas sensors, optical limiters and liquid crystals, and which are also used in medicine, as singlet oxygen photosensitisers for photodynamic therapy (Brewis et al., 2003). And nitrile compounds are the precursor of tetrazole complexes (Duncia et al., 1991; Xiong et al., 2002; Fu et al., 2008). Recently, a series of benzonitrile compounds have been reported (Fu & Zhao, 2007; Dai & Fu, 2008; Smith et al., 2000). As an extension of these work on the structural characterization, we report here the crystal structure of the title compound p-cyanoanilinium perchloride. The crystal data show that in the title compound, the N1 atom of the amine group is protonated. The nitrile group and the benzene ring are essentially coplanar. The C1N2 bond length of 1.135 (3) Å is within the normal range (Fig. 1).The crystal packing is stablized by cation–anion N—H···O hydrogen bonds, building an infinite one-dimensional chain parallel to the a axis. (Table 1, Fig. 2).

Related literature top

For the chemistry of nitrile derivatives, see: Xiong et al. (2002); Jin et al. (1994); Brewis et al. (2003); Fu et al. (2008); Duncia et al. (1991); Fu & Zhao (2007); Dai & Fu (2008); Smith et al. (2000).

Experimental top

p-cyanoaniline (3 mmol, 354 mg) was dissolved in the solution of distilled water (10 ml) and perchloride acid (0.5 ml), and evaporated in the air affording colorless block crystals of this compound suitable for X-ray analysis were obtained.

Refinement top

All H atoms attached to C and N atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) and N—H = 0.89 Å with Uiso(H) = 1.2Ueq(C or 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: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003); 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 viewed along the b axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.
4-Cyanoanilinium perchlorate top
Crystal data top
C7H7N2+·ClO4Z = 2
Mr = 218.60F(000) = 224
Triclinic, P1Dx = 1.559 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.9905 (10) ÅCell parameters from 1806 reflections
b = 6.9465 (14) Åθ = 3.0–27.5°
c = 13.998 (3) ŵ = 0.40 mm1
α = 94.87 (3)°T = 298 K
β = 95.68 (3)°Block, colourless
γ = 103.99 (3)°0.25 × 0.15 × 0.15 mm
V = 465.57 (17) Å3
Data collection top
Rigaku Mercury2
diffractometer
2126 independent reflections
Radiation source: fine-focus sealed tube1851 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = 66
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 88
Tmin = 0.941, Tmax = 1.000l = 1818
4861 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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0483P)2 + 0.1253P]
where P = (Fo2 + 2Fc2)/3
2126 reflections(Δ/σ)max < 0.001
128 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C7H7N2+·ClO4γ = 103.99 (3)°
Mr = 218.60V = 465.57 (17) Å3
Triclinic, P1Z = 2
a = 4.9905 (10) ÅMo Kα radiation
b = 6.9465 (14) ŵ = 0.40 mm1
c = 13.998 (3) ÅT = 298 K
α = 94.87 (3)°0.25 × 0.15 × 0.15 mm
β = 95.68 (3)°
Data collection top
Rigaku Mercury2
diffractometer
2126 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
1851 reflections with I > 2σ(I)
Tmin = 0.941, Tmax = 1.000Rint = 0.023
4861 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.05Δρmax = 0.25 e Å3
2126 reflectionsΔρmin = 0.34 e Å3
128 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
N10.6157 (3)0.2508 (2)0.12597 (11)0.0399 (4)
H1A0.47710.24050.07910.048*
H1B0.68760.14600.11800.048*
H1C0.74680.36230.12380.048*
N20.0727 (7)0.2647 (4)0.5503 (2)0.1058 (10)
C10.1672 (6)0.2642 (4)0.47983 (19)0.0743 (8)
C20.2877 (5)0.2620 (3)0.38998 (16)0.0549 (5)
C30.2722 (5)0.4100 (3)0.33016 (17)0.0557 (5)
H30.18600.51010.34780.067*
C40.3859 (4)0.4064 (3)0.24466 (15)0.0458 (4)
H40.37890.50490.20410.055*
C50.5097 (3)0.2566 (3)0.21961 (13)0.0362 (4)
C60.5293 (4)0.1094 (3)0.27829 (14)0.0464 (5)
H60.61690.01040.26040.056*
C70.4158 (5)0.1127 (4)0.36408 (16)0.0574 (6)
H70.42520.01450.40460.069*
Cl10.00044 (8)0.22266 (6)0.91125 (3)0.03315 (14)
O10.2849 (3)0.1812 (2)0.92711 (11)0.0552 (4)
O20.1712 (3)0.3237 (2)0.99794 (12)0.0598 (4)
O30.0665 (3)0.0398 (2)0.88369 (13)0.0593 (4)
O40.0420 (4)0.3478 (2)0.83610 (12)0.0668 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0442 (8)0.0392 (8)0.0403 (9)0.0162 (7)0.0100 (6)0.0048 (6)
N20.141 (3)0.0996 (19)0.0746 (17)0.0122 (17)0.0625 (17)0.0038 (14)
C10.0839 (18)0.0741 (17)0.0597 (16)0.0059 (14)0.0296 (13)0.0047 (13)
C20.0545 (12)0.0599 (13)0.0450 (12)0.0039 (10)0.0167 (9)0.0053 (10)
C30.0560 (13)0.0514 (12)0.0617 (14)0.0159 (10)0.0210 (10)0.0056 (10)
C40.0485 (11)0.0424 (10)0.0506 (12)0.0168 (8)0.0126 (9)0.0046 (8)
C50.0328 (8)0.0375 (9)0.0366 (9)0.0068 (7)0.0046 (7)0.0004 (7)
C60.0547 (11)0.0455 (10)0.0441 (11)0.0205 (9)0.0097 (9)0.0072 (8)
C70.0714 (15)0.0609 (13)0.0425 (12)0.0163 (11)0.0126 (10)0.0140 (10)
Cl10.0306 (2)0.0284 (2)0.0426 (3)0.00948 (15)0.00733 (15)0.00697 (15)
O10.0333 (7)0.0667 (9)0.0627 (10)0.0079 (6)0.0146 (6)0.0046 (7)
O20.0531 (9)0.0534 (9)0.0661 (10)0.0147 (7)0.0150 (7)0.0090 (7)
O30.0595 (9)0.0396 (7)0.0839 (12)0.0271 (7)0.0058 (8)0.0036 (7)
O40.0880 (12)0.0539 (9)0.0623 (11)0.0127 (8)0.0217 (9)0.0293 (8)
Geometric parameters (Å, º) top
N1—C51.462 (2)C4—C51.371 (3)
N1—H1A0.8900C4—H40.9300
N1—H1B0.8900C5—C61.380 (3)
N1—H1C0.8900C6—C71.378 (3)
N2—C11.135 (3)C6—H60.9300
C1—C21.447 (3)C7—H70.9300
C2—C71.385 (3)Cl1—O41.4202 (15)
C2—C31.392 (3)Cl1—O31.4215 (14)
C3—C41.375 (3)Cl1—O11.4222 (14)
C3—H30.9300Cl1—O21.4346 (16)
C5—N1—H1A109.5C4—C5—C6122.22 (18)
C5—N1—H1B109.5C4—C5—N1118.25 (16)
H1A—N1—H1B109.5C6—C5—N1119.50 (16)
C5—N1—H1C109.5C7—C6—C5118.39 (19)
H1A—N1—H1C109.5C7—C6—H6120.8
H1B—N1—H1C109.5C5—C6—H6120.8
N2—C1—C2179.6 (3)C6—C7—C2120.1 (2)
C7—C2—C3120.66 (19)C6—C7—H7120.0
C7—C2—C1119.9 (2)C2—C7—H7120.0
C3—C2—C1119.4 (2)O4—Cl1—O3109.51 (11)
C4—C3—C2119.1 (2)O4—Cl1—O1109.25 (11)
C4—C3—H3120.4O3—Cl1—O1108.89 (10)
C2—C3—H3120.4O4—Cl1—O2109.01 (11)
C5—C4—C3119.54 (19)O3—Cl1—O2110.69 (10)
C5—C4—H4120.2O1—Cl1—O2109.47 (10)
C3—C4—H4120.2
C7—C2—C3—C40.0 (3)C4—C5—C6—C71.1 (3)
C1—C2—C3—C4179.7 (2)N1—C5—C6—C7176.89 (19)
C2—C3—C4—C50.6 (3)C5—C6—C7—C20.4 (3)
C3—C4—C5—C61.2 (3)C3—C2—C7—C60.1 (4)
C3—C4—C5—N1176.83 (18)C1—C2—C7—C6179.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.892.042.881 (2)158
N1—H1B···O3ii0.891.982.855 (2)166
N1—H1C···O4iii0.892.042.871 (2)156
Symmetry codes: (i) x, y, z1; (ii) x+1, y, z+1; (iii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC7H7N2+·ClO4
Mr218.60
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)4.9905 (10), 6.9465 (14), 13.998 (3)
α, β, γ (°)94.87 (3), 95.68 (3), 103.99 (3)
V3)465.57 (17)
Z2
Radiation typeMo Kα
µ (mm1)0.40
Crystal size (mm)0.25 × 0.15 × 0.15
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.941, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
4861, 2126, 1851
Rint0.023
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.097, 1.05
No. of reflections2126
No. of parameters128
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.34

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.892.042.881 (2)157.8
N1—H1B···O3ii0.891.982.855 (2)165.7
N1—H1C···O4iii0.892.042.871 (2)155.8
Symmetry codes: (i) x, y, z1; (ii) x+1, y, z+1; (iii) x+1, y+1, z+1.
 

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