Anilinium nitrate

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organic papers

o958

Melanie Rademeyer C₆H₈N+NO₃ÿ DOI: 10.1107/S1600536804010827 Acta Cryst.(2004). E60, o958±o960 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Anilinium nitrate

Melanie Rademeyer

School of Pure and Applied Chemistry, University of KwaZulu-Natal, Howard College Campus, Durban 4041, South Africa

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.003 AÊ

Rfactor = 0.055

wRfactor = 0.172

Data-to-parameter ratio = 22.2

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

The crystal structure of anilinium nitrate, C6H8N+NO3ÿ, consists of alternating organic and inorganic layers. The organic layer contains the aromatic groups, and the inorganic layer is comprised of the ammonium groups and nitrate ions. A hydrogen-bonding network of NÐH O interactions is established in the inorganic layer.

Comment

The crystal structure of anilinium nitrate, (I), was determined as part of an ongoing study of the structural characteristics of organic±inorganic layered compounds. A related structure, that of benzylammonium nitrate (C7H10N+NO3ÿ), has been reported previously (Rademeyer, 2003).

One anilinium cation and one nitrate anion comprise the asymmetric unit of the title compound. The molecular struc-ture of (I) and the atomic numbering used are shown in Fig. 1. As illustrated in Fig. 2, the crystal structure is comprised of alternating organic and inorganic layers, with the aromatic groups packing in the organic layer, and the ammonium groups and nitrate anions constituting the inorganic layer.

In the organic layer, aromatic groups are interdigitated and close to perpendicular to the layer plane, with the plane through the aromatic group (r.m.s. deviation 0.0035 AÊ) forming an angle of 88.31 (11) _{with the layer plane. In the}

case of benzylammonium nitrate, the cations are tilted relative to the ionic layer. In (I), neighbouring pairs of anilinium cations pack in alternating opposite directions when viewed down thebaxis (Fig. 2). No intermolecular±interactions are evident in the organic layer, and the shortest centroid-to-centroid distance between aromatic rings is 4.024 (2) AÊ. This

Received 28 April 2004 Accepted 4 May 2004 Online 8 May 2004

Figure 1

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distance is shorter than the value of 4.978 (5) AÊ found for benzylammonium nitrate.

In the inorganic layer, trigonal planar nitrate anions are tilted by 44.48 (6) _{relative to the layer plane. A}

hydrogen-bonding network of NÐH O hydrogen bonds is established between ammonium groups and nitrate anions. This network extends in two dimensions in the inorganic layer, parallel to theabplane. Atom N1 is hydrogen bonded to ®ve O atoms in three different nitrate ions through one normal and four bifurcated hydrogen bonds. In the nitrate ion, NÐO bond lengths differ signi®cantly, with values of 1.232 (2) (N2ÐO2), 1.238 (2) (N2ÐO1) and 1.348 (2) AÊ (N2ÐO3). The N2ÐO3 bond, which is engaged in strong hydrogen bonding [H1C O3 interaction of 1.81 (2) AÊ], is elongated. Hydrogen-bonding parameters are listed in Table 1, and the interactions are illustrated in Fig. 3. The same number and type of hydrogen-bonding interactions were observed in the benzyl-ammonium structure.

Experimental

Anilinium nitrate was prepared by the dropwise addition of concentrated nitric acid (70%, Aldrich) to a solution of aniline (99%, Aldrich) in chloroform. The resulting precipitate was ®ltered. Good-quality single crystals were obtained by recrystallization from water at room temperature.

Crystal data C6H8N+NO3ÿ

Mr= 156.14

Orthorhombic,Pbca a= 9.255 (4) AÊ b= 10.161 (4) AÊ c= 16.188 (5) AÊ V= 1522.4 (10) AÊ3

Z= 8

Dx= 1.369 Mg mÿ3

MoKradiation Cell parameters from 833

re¯ections

= 2±31

= 0.11 mmÿ1

T= 293 (2) K Block, light brown 0.400.200.20 mm

Data collection

Oxford Diffraction Excalibur2 diffractometer

!±2scans

13 740 measured re¯ections 2485 independent re¯ections 1306 re¯ections withI> 2(I)

Rint= 0.042 max= 34.4 h=ÿ13!14 k=ÿ13!12 l=ÿ23!23

Re®nement Re®nement onF2

R[F2_{> 2}₍_F2_{)] = 0.055}

wR(F2_{) = 0.172}

S= 1.06 2485 re¯ections 112 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2₍_F

o2) + (0.0769P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.002 max= 0.17 e AÊÿ3 min=ÿ0.19 e AÊÿ3

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N1ÐH1A O1i _{0.92 (2)} _{2.13 (2)} _{3.046 (2)} _{179 (2)}

N1ÐH1A O2i _{0.92 (2)} _{2.59 (2)} _{3.272 (2)} _{131 (2)}

N1ÐH1C O3ii _{0.88 (2)} _{1.81 (2)} _{2.689 (2)} _{177 (2)}

N1ÐH1B O1iii _{0.91 (2)} _{1.99 (2)} _{2.880 (2)} _{167 (2)}

N1ÐH1B O3iii _{0.91 (2)} _{2.50 (2)} _{3.036 (2)} _{118 (2)} Symmetry codes: (i) 1ÿx;ÿy;2ÿz; (ii)xÿ1;1

2ÿy;12z; (iii)xÿ12;12ÿy;2ÿz.

H atoms bonded to C atoms were placed in calculated positions (CÐH = 0.93 AÊ) and were re®ned using a riding model withUiso(H) =

1.2Ueq(parent atom). For the ammonium group, H atoms were placed

as observed in a Fourier map and re®ned. The NÐH bond lengths lie in the range 0.88 (2)±0.92 (2) AÊ.

Data collection: CrysAlisCCD (Oxford Diffraction, 2003); cell re®nement: CrysAlisCCD; data reduction: CrysAlisRED (Oxford Diffraction, 2003); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON(Spek, 2003) andWinGX(Farrugia, 1999).

The author acknowledges funding received for this work from the University of KwaZulu-Natal Research Of®ce, and the National Research Foundation (GUN:2054350).

Acta Cryst.(2004). E60, o958±o960 Melanie Rademeyer C₆H₈N+NO₃ÿ

o959

organic papers

Figure 2

Packing diagram (ORTEP-3; Farrugia, 1997) for (I), viewed along theb

axis. H atoms have been omitted for clarity.

Figure 3

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organic papers

o960

Melanie Rademeyer C₆H₈N+NO₃ÿ Acta Cryst.(2004). E60, o958±o960

References

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838.

Oxford Diffraction (2003).CrysAlis CCDandCrysAlis RED. Version 1.170. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Rademeyer, M. (2003).Acta Cryst.E59, o1860±o1861.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.

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supporting information

sup-1 Acta Cryst. (2004). E60, o958–o960

supporting information

Acta Cryst. (2004). E60, o958–o960 [https://doi.org/10.1107/S1600536804010827]

Anilinium nitrate

Melanie Rademeyer

Anilinium nitrate

Crystal data

C6H8N+·NO3−

Mr = 156.14

Orthorhombic, Pbca

Hall symbol: -P 2ac 2ab

a = 9.255 (4) Å

b = 10.161 (4) Å

c = 16.188 (5) Å

V = 1522.4 (10) Å3

Z = 8

F(000) = 656

Dx = 1.369 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 833 reflections

θ = 2–31°

µ = 0.11 mm−1

T = 293 K

Block, light brown 0.40 × 0.20 × 0.20 mm

Data collection

Oxford Excalibur2 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω–2θ scans

13740 measured reflections 2485 independent reflections

1306 reflections with I > 2σ(I)

Rint = 0.042

θmax = 34.4°, θmin = 4.8°

h = −13→14

k = −13→12

l = −23→23

Refinement

Refinement on F2 Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.055}

wR(F2_{) = 0.172}

S = 1.06 2485 reflections 112 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) + (0.0769P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.002

Δρmax = 0.17 e Å−3 Δρmin = −0.19 e Å−3

Special details

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supporting information

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

N1 0.11480 (17) 0.14873 (18) 1.15203 (9) 0.0464 (4)

H1A 0.145 (2) 0.066 (2) 1.1676 (12) 0.055 (5)*

H1B 0.156 (2) 0.223 (2) 1.1730 (13) 0.070 (7)*

H1C 0.031 (2) 0.164 (2) 1.1759 (12) 0.064 (6)*

N2 0.86466 (13) 0.17165 (16) 0.74697 (9) 0.0490 (4)

C1 0.11168 (15) 0.15727 (17) 1.06176 (10) 0.0444 (4)

O1 0.78123 (13) 0.12482 (13) 0.79900 (8) 0.0602 (4)

O2 0.94309 (13) 0.08799 (15) 0.71502 (8) 0.0656 (4)

O3 0.86432 (12) 0.30163 (14) 0.73030 (10) 0.0668 (4)

C6 0.17875 (19) 0.0579 (2) 1.01585 (11) 0.0589 (5)

H6 0.2235 −0.0129 1.0417 0.071*

C4 0.1083 (2) 0.1778 (3) 0.89290 (13) 0.0820 (8)

H4 0.1087 0.1847 0.8356 0.098*

C2 0.0417 (2) 0.2668 (2) 1.02483 (12) 0.0616 (5)

H2 −0.0024 0.3310 1.0570 0.074*

C5 0.1763 (2) 0.0684 (3) 0.93062 (13) 0.0777 (7)

H5 0.2192 0.0038 0.8982 0.093*

C3 0.0410 (2) 0.2752 (3) 0.93939 (14) 0.0805 (7)

H3 −0.0042 0.3456 0.9133 0.097*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

N1 0.0420 (7) 0.0568 (10) 0.0402 (8) 0.0002 (7) 0.0023 (6) 0.0003 (7)

N2 0.0362 (6) 0.0688 (11) 0.0419 (8) −0.0006 (7) −0.0027 (6) 0.0053 (7)

C1 0.0343 (7) 0.0595 (11) 0.0394 (9) −0.0112 (7) 0.0011 (6) 0.0007 (8)

O1 0.0464 (7) 0.0741 (10) 0.0601 (8) 0.0031 (6) 0.0144 (5) 0.0137 (6)

O2 0.0482 (7) 0.0854 (10) 0.0632 (9) 0.0146 (6) 0.0124 (6) −0.0003 (7)

O3 0.0527 (7) 0.0661 (10) 0.0815 (10) 0.0024 (6) 0.0114 (6) 0.0159 (7)

C6 0.0425 (9) 0.0807 (13) 0.0534 (11) 0.0016 (9) 0.0049 (8) −0.0044 (9)

C4 0.0484 (11) 0.155 (2) 0.0425 (11) −0.0250 (13) 0.0019 (8) 0.0016 (13)

C2 0.0558 (10) 0.0761 (14) 0.0529 (11) 0.0060 (9) −0.0019 (9) 0.0040 (10)

C5 0.0497 (10) 0.129 (2) 0.0541 (12) −0.0087 (12) 0.0134 (9) −0.0235 (12)

C3 0.0618 (12) 0.120 (2) 0.0592 (14) −0.0012 (13) −0.0112 (10) 0.0244 (13)

Geometric parameters (Å, º)

N1—C1 1.464 (2) C6—C5 1.384 (3)

N1—H1A 0.92 (2) C6—H6 0.93

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supporting information

N1—H1C 0.88 (2) C4—C5 1.416 (4)

N2—O2 1.2318 (19) C4—H4 0.93

N2—O1 1.2377 (17) C2—C3 1.386 (3)

N2—O3 1.348 (2) C2—H2 0.93

C1—C6 1.399 (2) C5—H5 0.93

C1—C2 1.419 (3) C3—H3 0.93

C1—N1—H1A 109.5 (12) C1—C6—H6 121.1

C1—N1—H1B 109.4 (13) C3—C4—C5 121.6 (2)

H1A—N1—H1B 121.9 (19) C3—C4—H4 119.2

C1—N1—H1C 114.2 (13) C5—C4—H4 119.2

H1A—N1—H1C 107.8 (18) C3—C2—C1 118.08 (19)

H1B—N1—H1C 93.4 (18) C3—C2—H2 121.0

O2—N2—O1 112.84 (15) C1—C2—H2 121.0

O2—N2—O3 126.40 (14) C6—C5—C4 119.9 (2)

O1—N2—O3 120.76 (14) C6—C5—H5 120.1

C6—C1—C2 122.99 (16) C4—C5—H5 120.1

C6—C1—N1 118.60 (16) C2—C3—C4 119.6 (2)

C2—C1—N1 118.41 (16) C2—C3—H3 120.2

C5—C6—C1 117.80 (19) C4—C3—H3 120.2

C5—C6—H6 121.1

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1A···O1i _{0.92 (2)} _{2.13 (2)} _{3.046 (2)} _{179 (2)}

N1—H1A···O2i _{0.92 (2)} _{2.59 (2)} _{3.272 (2)} _{131 (2)}

N1—H1C···O3ii _{0.88 (2)} _{1.81 (2)} _{2.689 (2)} _{177 (2)}

N1—H1B···O1iii _{0.91 (2)} _{1.99 (2)} _{2.880 (2)} _{167 (2)}

N1—H1B···O3iii _{0.91 (2)} _{2.50 (2)} _{3.036 (2)} _{118 (2)}