Acta Cryst.(2004). E60, o911±o912 DOI: 10.1107/S1600536804010013 Duncan M. Tookeet al. C6H9N2+NO3ÿ
o911
organic papers
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
(2-Pyridylmethyl)ammonium nitrate
Duncan M. Tooke,a*
Anthony L. Spek,aJan Reedijkb
and Ramu Kannappanb
aBijvoet Center for Biomolecular Research,
Department of Crystal and Structural Chemistry, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands, andbLeiden Institute
of Chemistry, Einsteinweg 55, Leiden 2333 AC, The Netherlands
Correspondence e-mail: [email protected]
Key indicators Single-crystal X-ray study
T= 150 K
Mean(C±C) = 0.002 AÊ
Rfactor = 0.043
wRfactor = 0.097
Data-to-parameter ratio = 15.0
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The single-crystal structure of (2-pyridylmethyl)ammonium nitrate, C6H9N2+NO3ÿ, is presented, in what is only the third reported structure containing this cation. The structure contains extensively hydrogen-bonded layers.
Comment
During research into novel chelating ligands, the crystal structure of the title compound, (I), was determined (Fig. 1). The structure of the (2-pyridylmethyl)ammonium cation has only been determined twice previously, once in a silver nitrate complex (Sailaja et al., 2001) and once as the pyridine-2-carboxylate salt (Dùssinget al., 2001). In both of these struc-tures, four hydrogen bonds were formed from the ammonium group.
In (I), ®ve hydrogen bonds are formed between the ammonium group and nitrate O atoms. These bonds, withDÐ H A distances of between 2.8237 (19) and 3.110 (2) AÊ, are comparable with the bonds reported in the AgNO3complex, and cause the formation of a two-dimensional network with thebandcaxes as the base vectors (Fig. 2).
Experimental
2-(Aminomethyl)pyridine (2.16 g, 0.02 mol) was dissolved in ethanol (5 ml) and added to a stirred ethanol solution ofo-vanillin (3.04 g, 0.02 mol). The reaction mixture was stirred overnight. The solvent was removed using a rotary evaporator to give a red residue, which was recrystallized from the minimum amount of hot methanol, yielding good quality single crystals.
Received 21 April 2004 Accepted 26 April 2004 Online 30 April 2004
Figure 1
Crystal data
C6H9N2+NO3ÿ Mr= 171.16
Monoclinic, P21=c a= 8.2492 (4) AÊ
b= 10.4014 (5) AÊ
c= 9.3850 (5) AÊ
= 105.171 (4) V= 777.20 (7) AÊ3 Z= 4
Dx= 1.463 Mg mÿ3
MoKradiation Cell parameters from 59
re¯ections, based on ±scan (Duisenberget al., 2000)
= 5.5±20.8
= 0.12 mmÿ1 T= 150 (2) K Block, colourless 0.20.10.1 mm
Data collection
Nonius KappaCCD diffractometer
'and!scans
Absorption correction: none 18 148 measured re¯ections 1774 independent re¯ections 1228 re¯ections withI> 2(I)
Rint= 0.057
max= 27.4 h=ÿ10!10
k=ÿ13!13
l=ÿ12!12
Re®nement
Re®nement onF2 R[F2> 2(F2)] = 0.043 wR(F2) = 0.097 S= 1.05 1774 re¯ections 118 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.0364P)2
+ 0.3509P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.19 e AÊÿ3
min=ÿ0.23 e AÊÿ3
Table 1
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N2ÐH2A O2i 0.958 (19) 2.155 (18) 2.8817 (19) 131.7 (15)
N2ÐH2A N1i 0.958 (19) 2.345 (18) 3.037 (2) 128.7 (13)
N2ÐH2B O1ii 0.925 (18) 1.931 (18) 2.8237 (19) 161.4 (16)
N2ÐH2B O3ii 0.925 (18) 2.440 (19) 3.110 (2) 129.3 (15)
N2ÐH2C O1 0.942 (18) 1.923 (18) 2.8412 (18) 164.3 (16)
Symmetry codes: (i) 1ÿx;1ÿy;ÿz; (ii)x;1 2ÿy;zÿ12.
The aromatic H atoms were placed in geometrically idealized positions (CÐH = 0.95 AÊ) and constrained to ride on their parent atoms withUiso(H) = 1.2Ueq(C). The H atoms on the N atom were found in a difference electron-density map and re®ned withUiso= 1.5Ueq(N).
Data collection: COLLECT (Nonius, 1998); cell re®nement:
DIRAX(Duisenberg, 1992); data reduction:EvalCCD(Duisenberg
et al., 2003); program(s) used to solve structure:SHELXS86
(Shel-drick, 1985); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:PLATON(Spek, 2003); soft-ware used to prepare material for publication:PLATON.
This work was supported in part (ALS) by the Council for the Chemical Sciences of the Netherlands Organization for Scienti®c Research (CW±NWO).
References
Dùssing, A., Skands, M. C. & Madsen, A. é. (2001).Acta Cryst.C57, 1460± 1461.
Duisenberg, A. J. M. (1992).J. Appl. Cryst.25, 92±96.
Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000).
J. Appl. Cryst.33, 893±898.
Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).
J. Appl. Cryst.36, 220±229.
Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands.
Sailaja, S., Swarnabala, G. & Rajasekharan, M. V. (2001).Acta Cryst.C57, 1162±1165.
Sheldrick, G. M. (1985).SHELXS86. University of GoÈttingen, Germany. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Spek, A. L. (2003).J. Appl. Cryst.36, 7±13.
Figure 2
supporting information
sup-1
Acta Cryst. (2004). E60, o911–o912
supporting information
Acta Cryst. (2004). E60, o911–o912 [https://doi.org/10.1107/S1600536804010013]
(2-Pyridylmethyl)ammonium nitrate
Duncan M. Tooke, Anthony L. Spek, Jan Reedijk and Ramu Kannappan
(I)
Crystal data
C6H9N2+·NO3− Mr = 171.16 Monoclinic, P21/c Hall symbol: -P 2ybc a = 8.2492 (4) Å b = 10.4014 (5) Å c = 9.3850 (5) Å β = 105.171 (4)° V = 777.20 (7) Å3 Z = 4
F(000) = 360 Dx = 1.463 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 59 reflections θ = 5.5–20.8°
µ = 0.12 mm−1 T = 150 K Block, colourless 0.2 × 0.1 × 0.1 mm
Data collection
Nonius KappaCCD diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
18148 measured reflections 1774 independent reflections
1228 reflections with I > 2σ(I) Rint = 0.057
θmax = 27.4°, θmin = 2.6° h = −10→10
k = −13→13 l = −12→12
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.043 wR(F2) = 0.097 S = 1.05 1774 reflections 118 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: mixed
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.0364P)2 + 0.3509P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.19 e Å−3 Δρmin = −0.23 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 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 0.30006 (17) 0.43664 (13) 0.09967 (14) 0.0227 (3)
N2 0.52094 (18) 0.32680 (14) −0.02714 (16) 0.0212 (3)
H2A 0.502 (2) 0.4097 (19) −0.073 (2) 0.032*
H2B 0.590 (2) 0.2819 (18) −0.073 (2) 0.032*
H2C 0.578 (2) 0.3381 (17) 0.073 (2) 0.032*
C1 0.2010 (2) 0.49371 (18) 0.17383 (18) 0.0270 (4)
H1 0.2345 0.5751 0.2176 0.032*
C2 0.0542 (2) 0.44125 (18) 0.19013 (19) 0.0295 (4)
H2 −0.0119 0.4854 0.2435 0.035*
C3 0.0050 (2) 0.32320 (19) 0.12727 (19) 0.0314 (4)
H3 −0.0961 0.2844 0.1363 0.038*
C4 0.1047 (2) 0.26232 (18) 0.05104 (18) 0.0272 (4)
H4 0.0739 0.1807 0.0069 0.033*
C5 0.2507 (2) 0.32224 (16) 0.03990 (17) 0.0210 (4)
C6 0.3627 (2) 0.25603 (16) −0.04054 (18) 0.0248 (4)
H6A 0.3888 0.1683 0.0000 0.030*
H6B 0.3025 0.2479 −0.1462 0.030*
O1 0.66629 (15) 0.31660 (11) 0.28255 (12) 0.0263 (3)
O2 0.68263 (16) 0.52342 (12) 0.26607 (14) 0.0349 (3)
O3 0.7063 (2) 0.43410 (13) 0.47739 (14) 0.0455 (4)
N3 0.68525 (17) 0.42684 (14) 0.34289 (15) 0.0249 (3)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
N1 0.0275 (8) 0.0202 (7) 0.0217 (7) 0.0009 (6) 0.0089 (6) 0.0011 (6)
N2 0.0266 (8) 0.0185 (8) 0.0211 (8) 0.0002 (6) 0.0105 (6) −0.0023 (6)
C1 0.0340 (10) 0.0246 (9) 0.0245 (9) 0.0058 (8) 0.0116 (7) 0.0019 (7)
C2 0.0279 (10) 0.0372 (11) 0.0264 (9) 0.0110 (8) 0.0124 (8) 0.0062 (8)
C3 0.0206 (9) 0.0426 (11) 0.0311 (10) −0.0001 (8) 0.0072 (7) 0.0095 (9)
C4 0.0253 (9) 0.0281 (10) 0.0260 (9) −0.0034 (8) 0.0028 (7) 0.0020 (8)
C5 0.0238 (8) 0.0205 (8) 0.0178 (8) 0.0020 (7) 0.0036 (6) 0.0038 (7)
C6 0.0291 (9) 0.0205 (9) 0.0264 (9) −0.0036 (7) 0.0103 (7) −0.0029 (7)
O1 0.0348 (7) 0.0205 (6) 0.0253 (6) −0.0015 (5) 0.0110 (5) −0.0025 (5)
O2 0.0394 (8) 0.0256 (7) 0.0358 (7) −0.0061 (6) 0.0031 (6) 0.0124 (6)
O3 0.0800 (11) 0.0351 (8) 0.0205 (7) −0.0064 (7) 0.0118 (7) −0.0032 (6)
supporting information
sup-3
Acta Cryst. (2004). E60, o911–o912 Geometric parameters (Å, º)
N1—C5 1.333 (2) C3—C4 1.378 (2)
N1—C1 1.342 (2) C3—H3 0.9500
N2—C6 1.475 (2) C4—C5 1.384 (2)
N2—H2A 0.96 (2) C4—H4 0.9500
N2—H2B 0.93 (2) C5—C6 1.505 (2)
N2—H2C 0.94 (2) C6—H6A 0.9900
C1—C2 1.373 (2) C6—H6B 0.9900
C1—H1 0.9500 O1—N3 1.2703 (18)
C2—C3 1.377 (3) O2—N3 1.2334 (17)
C2—H2 0.9500 O3—N3 1.2307 (18)
C5—N1—C1 116.90 (15) C3—C4—C5 118.82 (17)
C6—N2—H2A 111.9 (11) C3—C4—H4 120.6
C6—N2—H2B 110.3 (11) C5—C4—H4 120.6
H2A—N2—H2B 107.1 (15) N1—C5—C4 123.12 (15)
C6—N2—H2C 110.6 (11) N1—C5—C6 117.35 (14)
H2A—N2—H2C 108.5 (16) C4—C5—C6 119.52 (15)
H2B—N2—H2C 108.4 (16) N2—C6—C5 112.02 (14)
N1—C1—C2 123.81 (17) N2—C6—H6A 109.2
N1—C1—H1 118.1 C5—C6—H6A 109.2
C2—C1—H1 118.1 N2—C6—H6B 109.2
C1—C2—C3 118.46 (16) C5—C6—H6B 109.2
C1—C2—H2 120.8 H6A—C6—H6B 107.9
C3—C2—H2 120.8 O3—N3—O2 121.72 (15)
C2—C3—C4 118.90 (17) O3—N3—O1 118.72 (14)
C2—C3—H3 120.6 O2—N3—O1 119.56 (13)
C4—C3—H3 120.6
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N2—H2A···O2i 0.958 (19) 2.155 (18) 2.8817 (19) 131.7 (15)
N2—H2A···N1i 0.958 (19) 2.345 (18) 3.037 (2) 128.7 (13)
N2—H2B···O1ii 0.925 (18) 1.931 (18) 2.8237 (19) 161.4 (16)
N2—H2B···O3ii 0.925 (18) 2.440 (19) 3.110 (2) 129.3 (15)
N2—H2C···O1 0.942 (18) 1.923 (18) 2.8412 (18) 164.3 (16)
