Benzyl­ammonium nitrate

organic papers

o1860

Structure Reports Online

ISSN 1600-5368

Benzylammonium nitrate

Melanie Rademeyer

School of Pure and Applied Chemistry, University of Natal, Durban 4041, South Africa

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 120 K

Mean(C±C) = 0.003 AÊ

Rfactor = 0.068

wRfactor = 0.172

Data-to-parameter ratio = 17.0

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

#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved

The crystal structure of benzylammonium nitrate, C7H10N+NO3ÿ, exhibits ionic layers separated by hydro-carbon layers. The hydrohydro-carbon layer contains the interdigi-tated benzyl groups, but no±interactions are observed. In the inorganic layer, the ammonium groups and nitrate ions interactviahydrogen-bonding.

Comment

As part of a study on the effect of anions on the crystal structures in organic±inorganic layered compounds, the crystal structure of benzylammonium nitrate, (I), has been deter-mined. Only one other structure containing a benzyl-ammonium cation and a polyatomic anion could be located in the literature, namely that of benzylammonium dihydrogen phosphate (Aakeroy et al., 1989). Even though a layered structure is formed for both compounds, the packing of the benzylammonium cations in the two structures differs.

The molecular structure of (I), and the atomic numbering used, is illustrated in Fig. 1. All bond distances and angles are within the ranges of accepted values.

A layered structure composed of alternating ionic and hydrocarbon layers is formed. The layers extend parallel to the ab plane. Fig. 2 illustrates the layered packing viewed down theaaxis. The organic layer is formed by interdigitated benzyl moieties. For this part of the cation, the atoms consti-tuting the aromatic ring and C7 are coplanar, with a standard uncertainty of 0.002 AÊ. The maximum absolute deviation from this plane is 0.015 (2) AÊ for atom C1. No intermolecular± interactions are observed in the organic layer, and the shortest centroid-to-centroid distance between aromatic rings is 4.978 (5) AÊ.

Received 16 October 2003 Accepted 22 October 2003 Online 31 October 2003

Figure 1

The ionic layer contains the ammonium groups and planar nitrate ions. In this layer, a complex hydrogen-bonding network is formed, where each ammonium N atom is hydrogen bonded to ®ve O atoms through one normal and four bifurcated hydrogen bonds. N O donor±acceptor distances range from 2.609 (2) to 3.286 (3) AÊ, and H O interactions range from 1.72 (3) to 2.46 (3) AÊ. Hydrogen-bonding parameters are listed in Table 1 and Fig. 3 shows these interactions in the inorganic layer.

In the nitrate ion, the NÐO bond distances differ signi®-cantly, with values of 1.181 (2) (N2ÐO2), 1.216 (2) (N2ÐO1) and 1.402 (3) AÊ (N2ÐO3). It is clear that the the NÐO bond for the O atom engaged in strong hydrogen bonding, O3 [H1C O3 hydrogen-bonding interaction of 1.72 (3) AÊ], is elongated.

Experimental

Benzylammonium nitrate was prepared by the dropwise addition of concentrated nitric acid (70%, Aldrich) to a solution of benzylamine

Crystal data

C7H10N+NO3ÿ

Mr= 170.17 Orthorhombic,Pbca a= 9.817 (2) AÊ

b= 11.043 (3) AÊ

c= 15.819 (4) AÊ

V= 1714.9 (7) AÊ3

Z= 8

Dx= 1.318 Mg mÿ3

MoKradiation Cell parameters from 944

re¯ections

= 2±32

= 0.10 mmÿ1

T= 120 (2) K Block, colourless 0.200.200.15 mm

Data collection

Oxford Excalibur2 diffractometer

!±2scans

Absorption correction: none 13 426 measured re¯ections 2060 independent re¯ections 1792 re¯ections withI> 2(I)

Rint= 0.037

max= 28.0

h=ÿ12!11

k=ÿ14!14

l=ÿ20!18

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.069}

wR(F2_{) = 0.172}

S= 1.29 2060 re¯ections 121 parameters

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

w= 1/[2_(F

o2) + (0.085P)2] whereP= (Fo2+ 2Fc2)/3 (/)max= 0.026

max= 0.29 e AÊÿ3 min=ÿ0.31 e AÊÿ3

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N1ÐH1B O2i _{0.99 (4) 2.15 (3) 3.071 (3) 154 (3)}

N1ÐH1C O3 0.89 (3) 1.72 (3) 2.609 (2) 178 (3) N1ÐH1A O2ii _{0.96 (3) 2.33 (3) 3.286 (3) 175 (2)}

N1ÐH1A O1ii _{0.96 (3) 2.46 (3) 3.221 (3) 136 (2)}

N1ÐH1B O3i _{0.99 (4) 2.08 (3) 2.772 (2) 126 (3)}

Symmetry codes: (i)1

2‡x;y;12ÿz; (ii)32ÿx;yÿ12;z.

H atoms bonded to C atoms were placed in calculated positions and re®ned using a riding model. For the ammonium group, H atoms were placed as observed in a Fourier map and re®ned. CÐC bond lengths in the phenyl ring were restrained to similar values.

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell re®nement: CrysAlis CCD; data reduction:CrysAlis RED (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) andMERCURY(Brunoet al., 2002); software used to prepare material for publication:WinGX(Farrugia, 1999).

The author acknowledges funding received for this work from the University of Natal Research Of®ce.

References

Aakeroy, C. B., Hitchcock, P. B., Moyle, B. D. & Seddon, K. R. (1989).J. Chem. Soc. Chem. Commun.23, 1856±1859.

Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M. K., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002).Acta Cryst.B58, 389±397.

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.

Figure 2

Packing diagram for (I), viewed down theaaxis, showing the layered packing and interdigitation (MERCURY; Brunoet al., 2002).

Figure 3

supporting information

sup-1 Acta Cryst. (2003). E59, o1860–o1861

supporting information

Acta Cryst. (2003). E59, o1860–o1861 [https://doi.org/10.1107/S1600536803024243]

Benzylammonium nitrate

Melanie Rademeyer

Benzylammonium nitrate

Crystal data

C7H10N+·NO3− Mr = 170.17

Orthorhombic, Pbca Hall symbol: -P 2ac 2ab a = 9.817 (2) Å

b = 11.043 (3) Å c = 15.819 (4) Å V = 1714.9 (7) Å3 Z = 8

F(000) = 720 Dx = 1.318 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 944 reflections θ = 2–32°

µ = 0.10 mm−1 T = 120 K Block, colourless 0.2 × 0.2 × 0.15 mm

Data collection

Oxford Excalibur2 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω–2θ scans

13426 measured reflections 2060 independent reflections

1792 reflections with I > 2σ(I) Rint = 0.037

θmax = 28.0°, θmin = 3.9° h = −12→11

k = −14→14 l = −20→18

Refinement

Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.069} wR(F2_{) = 0.172} S = 1.29 2060 reflections 121 parameters 15 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) + (0.085P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.026

Δρmax = 0.29 e Å−3 Δρmin = −0.31 e Å−3

Special details

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

O2 0.52714 (14) 1.08618 (16) 0.29904 (10) 0.0265 (4)

C1 0.89985 (19) 0.8805 (2) 0.46285 (13) 0.0185 (5)

C6 0.9542 (2) 0.7694 (2) 0.50094 (14) 0.0238 (5)

H6 1.0275 0.7330 0.4737 0.029*

C7 0.9544 (2) 0.9432 (2) 0.38432 (13) 0.0234 (5)

H7A 0.9225 1.0264 0.3830 0.028*

H7B 1.0532 0.9444 0.3860 0.028*

C2 0.79586 (19) 0.9372 (2) 0.49952 (13) 0.0205 (5)

H2 0.7582 1.0082 0.4782 0.025*

C3 0.7481 (2) 0.8806 (2) 0.57320 (13) 0.0253 (5)

H3 0.6755 0.9172 0.6010 0.030*

C5 0.9062 (2) 0.7130 (2) 0.57448 (15) 0.0263 (5)

H5 0.9441 0.6423 0.5961 0.032*

N1 0.90714 (18) 0.8778 (2) 0.30571 (11) 0.0189 (4)

O1 0.72202 (14) 1.10996 (16) 0.31419 (10) 0.0274 (4)

O3 0.64631 (15) 0.91142 (15) 0.28442 (11) 0.0264 (4)

N2 0.63336 (17) 1.03605 (19) 0.29935 (11) 0.0209 (4)

C4 0.8026 (2) 0.7688 (2) 0.61023 (14) 0.0267 (6)

H4 0.7638 0.7373 0.6592 0.032*

H1A 0.922 (2) 0.792 (3) 0.3060 (16) 0.026 (7)*

H1B 0.947 (3) 0.924 (3) 0.259 (2) 0.055 (9)*

H1C 0.819 (3) 0.889 (2) 0.2975 (16) 0.031 (7)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

O2 0.0087 (7) 0.0446 (11) 0.0263 (9) 0.0052 (6) −0.0016 (6) −0.0070 (7)

C1 0.0120 (9) 0.0293 (12) 0.0143 (10) −0.0061 (8) −0.0017 (7) −0.0033 (9)

C6 0.0138 (9) 0.0356 (14) 0.0221 (11) 0.0007 (9) −0.0006 (8) −0.0060 (10)

C7 0.0143 (9) 0.0405 (14) 0.0153 (10) −0.0081 (9) −0.0001 (7) −0.0045 (10)

C2 0.0142 (10) 0.0291 (13) 0.0183 (10) −0.0016 (8) −0.0021 (7) −0.0005 (9)

C3 0.0118 (9) 0.0449 (15) 0.0192 (11) −0.0047 (9) 0.0012 (8) −0.0059 (10)

C5 0.0234 (11) 0.0298 (13) 0.0257 (12) 0.0000 (9) −0.0073 (8) 0.0042 (10)

N1 0.0119 (9) 0.0303 (12) 0.0145 (9) −0.0038 (7) −0.0002 (6) −0.0006 (8)

O1 0.0118 (7) 0.0357 (10) 0.0346 (10) −0.0050 (6) −0.0067 (6) 0.0005 (7)

O3 0.0158 (7) 0.0300 (10) 0.0333 (10) −0.0003 (6) −0.0033 (6) −0.0022 (7)

N2 0.0137 (9) 0.0330 (11) 0.0161 (9) 0.0001 (7) −0.0017 (6) 0.0011 (8)

supporting information

sup-3 Acta Cryst. (2003). E59, o1860–o1861

Geometric parameters (Å, º)

O2—N2 1.181 (2) C3—C4 1.468 (3)

C1—C2 1.331 (3) C3—H3 0.9300

C1—C6 1.467 (3) C5—C4 1.317 (3)

C1—C7 1.520 (3) C5—H5 0.9300

C6—C5 1.402 (3) N1—H1A 0.96 (3)

C6—H6 0.9300 N1—H1B 0.99 (4)

C7—N1 1.511 (3) N1—H1C 0.89 (3)

C7—H7A 0.9700 O1—N2 1.216 (2)

C7—H7B 0.9700 O3—N2 1.402 (3)

C2—C3 1.403 (3) C4—H4 0.9300

C2—H2 0.9300

C2—C1—C6 119.6 (2) C4—C3—H3 117.1

C2—C1—C7 114.3 (2) C4—C5—C6 114.1 (2)

C6—C1—C7 126.06 (19) C4—C5—H5 123.0

C5—C6—C1 126.2 (2) C6—C5—H5 123.0

C5—C6—H6 116.9 C7—N1—H1A 115.0 (16)

C1—C6—H6 116.9 C7—N1—H1B 105 (2)

N1—C7—C1 110.24 (17) H1A—N1—H1B 117 (2)

N1—C7—H7A 109.6 C7—N1—H1C 111.0 (17)

C1—C7—H7A 109.6 H1A—N1—H1C 106 (2)

N1—C7—H7B 109.6 H1B—N1—H1C 102 (3)

C1—C7—H7B 109.6 O2—N2—O1 108.6 (2)

H7A—C7—H7B 108.1 O2—N2—O3 122.66 (18)

C1—C2—C3 114.1 (2) O1—N2—O3 128.78 (17)

C1—C2—H2 122.9 C5—C4—C3 120.3 (2)

C3—C2—H2 122.9 C5—C4—H4 119.9

C2—C3—C4 125.7 (2) C3—C4—H4 119.9

C2—C3—H3 117.1

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1B···O2i _{0.99 (4) 2.15 (3) 3.071 (3) 154 (3)}

N1—H1C···O3 0.89 (3) 1.72 (3) 2.609 (2) 178 (3)

N1—H1A···O2ii _{0.96 (3) 2.33 (3) 3.286 (3) 175 (2)}

N1—H1A···O1ii _{0.96 (3) 2.46 (3) 3.221 (3) 136 (2)}

N1—H1B···O3i _{0.99 (4) 2.08 (3) 2.772 (2) 126 (3)}