Acta Cryst.(2003). E59, o1697±o1699 DOI: 10.1107/S1600536803021676 Jin-Long Genget al. C11H13N4+ClO4ÿ
o1697
organic papers
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
4-[
N,N
-Bis(2-cyanoethyl)amino]pyridinium
perchlorate
Jin-Long Geng,aJun Ni,b
Rui Liu,b Hui-Lan Chenband
Zhi-Lin Wangb*
aCollege of Science, Nanjing Agricultural
University, Nanjing 210095, People's Republic of China, andbCoordination Chemistry Institute,
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, People's Republic of China
Correspondence e-mail: dpxue23@nju.edu.cn
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.004 AÊ
Rfactor = 0.049
wRfactor = 0.118
Data-to-parameter ratio = 12.7
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
In the title compound, C11H13N4+ClO4ÿ, the planar geometry
around the amino N atom in the cation suggests conjugation with the-system of the pyridine ring. NÐH O, CÐH O and CÐH N hydrogen-bonding interactions play a key role in the crystal packing.
Comment
The synthesis of 4-(N,N-dimethylamino)pyridine (DMAP) has attracted much attention for its excellent catalytic prop-erties in many organic reactions (Hoȯeet al., 1978; Scriven, 1983; Steglich & Hoe¯e, 1969). Its derivatives also display catalytic properties (Huanget al., 1994; Scriven, 1983). In our present research, we ®nd that 4-[N,N -bis(2-cyanoethyl)-amino]pyridine (CEAP) can catalyse an acylation reaction. As part of our research on CEAP and its derivatives, we prepared the title compound, (I). As a derivative of DMAP, compound (I) also has potential catalytic properties in organic reactions.
The title compound, (I), consists of a protonated 4-[N,N -bis(2-cyanoethyl)amino]pyridinium cation and a ClO4ÿanion
(Fig. 1). The sum of the bond angles around amino atom N2 is 360(Table 1), as observed in aminopyridines and their
deri-vatives (Chaoet al., 1977; Ohms & Guth, 1983). The N2ÐC3 bond length of 1.340 (3) AÊ is shorter than the corresponding bond length in CEAP [1.374 (3) AÊ; Ni, Li, Qiet al., 2003] and in its Ag complex [1.358 (5)±1.385 (5) AÊ; Ni, Li, Xue et al., 2003]. This geometric conformation re¯ects conjugation between the lone pair of N2 and thesystem of the pyridine ring (Chao & Schempp, 1977). The protonation makes this conjugation more strong. The ClÐO distances in the ClO4ÿ
are in the range 1.403 (3)±1.430 (3) AÊ, which is within the range of typical values (Rieraet al., 1998). The ClO4ÿanion
and the cation are connected by C5ÐH5 O4 and N1Ð H11 O2 interactions.
Atoms H9aand H10aon the cation interact with N4 on an adjacent cation at (xÿ1,y, z) through CÐH N hydrogen bonds (Table 2). Furthermore, atom H7a also interacts with N3 on an adjacent cation at (x+ 1,y, z). The propagation of
organic papers
o1698
Jin-Long Genget al. C11H13N4+ClO4ÿ Acta Cryst.(2003). E59, o1697±o1699molecules and the hydrogen bonds produces a chain along the
aaxis (Fig. 2). The molecules in a chain are parallel with each other and the angle between the molecular chain and the pyridine plane is 40.6 (2). Many chains are arranged along the
caxis forming a layer. We can see in Fig. 3 that all chains in a layer are parallel with each other. The molecules in adjacent chains have the opposite direction and the dihedral angle between the pyridine planes in adjacent chains is 8.5 (2). This
makes it easy for them to bond together through CÐH O hydrogen bonds between cations and ClO4ÿanions. As shown
in Fig. 4, atoms H1 and H2 on the cation interact with O4 and O1 of the ClO4ÿ anion at (1 +x, 32ÿy, zÿ12) through C1Ð
H1 O4 and C2ÐH2 O1 hydrogen bonds. The adjacent layers are also linked by a C6ÐH6b N4(1ÿx, 2ÿy, 2ÿz) hydrogen bond.
Figure 2
(a) View of one molecular chain down the a axis. (b) View of one molecular chain along theaaxis. [Symmetry code: (a)x+ 1,y, z.]
Figure 3
The crystal packing of (I), viewed along theaaxis.
Figure 4
The hydrogen-bond interactions between adjacent chains. H atoms not participating in the hydrogen bonds have been omitted for clarity. [Symmetry code: (A)xÿ1,3
2ÿy,12+z.]
Figure 1
Experimental
FeSO4 (152 mg, 1 mmol) and 4-[N,N
-bis(2-cyanoethyl)amino]-pyridine (200 mg, 1 mmol) were added to 40 ml ethanol. The reaction mixture was re¯uxed for 1.5 h. NaClO4(122.5 mg) was then added to
the reaction mixture and stirred for 15 min. White powder of (I) was ®ltered, washed with ethanol and dried in a vacuum desiccator, yielding 246 mg (82%). Colorless crystals of (I) were obtained by recrystallization from ethanol. The elemental analysis data for C11H13N4+ClO4ÿ are as follows, calculated: C 43.90, H 4.23, N
18.62%; found: C 43.78, H 4.27, N 18.49%. Crystal data
C11H13N4+ClO4ÿ
Mr= 300.70 Monoclinic,P21=c
a= 5.403 (1) AÊ b= 30.252 (5) AÊ c= 8.293 (2) AÊ = 99.24 (1)
V= 1337.9 (5) AÊ3
Z= 4
Dx= 1.493 Mg mÿ3 MoKradiation Cell parameters from 2473
re¯ections = 2.6±25.9
= 0.31 mmÿ1
T= 293 (2) K Needle, colorless 0.400.200.15 mm Data collection
Bruker SMART APEX CCD area-detector diffractometer 'and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2000) Tmin= 0.925,Tmax= 0.957
6812 measured re¯ections
2345 independent re¯ections 1848 re¯ections withI> 2(I) Rint= 0.062
max= 25.0
h=ÿ6!6 k=ÿ35!35 l=ÿ8!9 Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.049
wR(F2) = 0.118
S= 1.00 2345 re¯ections 185 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.044P)2 + 0.8P]
whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001
max= 0.36 e AÊÿ3
min=ÿ0.35 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
Cl1ÐO1 1.403 (2)
Cl1ÐO3 1.406 (3)
Cl1ÐO4 1.426 (2)
Cl1ÐO2 1.430 (2)
N1ÐC5 1.329 (4)
N1ÐC1 1.331 (4)
N2ÐC3 1.340 (3)
N3ÐC8 1.134 (3)
N4ÐC11 1.134 (4)
O1ÐCl1ÐO3 111.29 (18)
O1ÐCl1ÐO4 108.99 (15)
O3ÐCl1ÐO4 108.6 (2)
O1ÐCl1ÐO2 110.28 (14)
O3ÐCl1ÐO2 109.26 (19)
O4ÐCl1ÐO2 108.38 (14)
C5ÐN1ÐC1 120.8 (3)
C3ÐN2ÐC9 121.3 (2)
C3ÐN2ÐC6 121.92 (19)
C9ÐN2ÐC6 116.71 (19)
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N1ÐH11 O2 0.84 (3) 2.09 (3) 2.913 (4) 164 (3)
C1ÐH1 O4i 0.93 2.69 3.326 (4) 126
C2ÐH2 O1i 0.93 2.66 3.579 (3) 168
C5ÐH5 O4 0.93 2.44 3.169 (4) 135
C6ÐH6b N4ii 0.97 2.65 3.487 (3) 145
C7ÐH7a N3iii 0.97 2.73 3.407 (4) 127
C9ÐH9a N4iv 0.97 2.65 3.163 (4) 113
C10ÐH10a N4iv 0.97 2.57 3.257 (4) 128
Symmetry codes: (i) 1x;3
2ÿy;zÿ12; (ii) 1ÿx;2ÿy;2ÿz; (iii) 1x;y;z; (iv)
xÿ1;y;z.
Atom H11 am bonded to N1 was located in a difference Fourier map and re®ned isotropically. The positions of the other H atoms were ®xed geometrically (CÐH = 0.93±0.97 AÊ) and re®ned using the riding-model approximation (Uiso= 1.2 timesUeqofthe parent atom).
Data collection:SMART(Bruker, 2000); cell re®nement:SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to re®ne structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.
This project was supported by the Natural Science Found-ation of China (No. 20171021) and Specialized Research Fund for the Doctoral Program of Higher Education (No. 2000028436).
References
Bruker (2000).SMART, SAINT, SADABSandSHELXTL.Bruker AXS Inc., Madison, Wisconsin, USA.
Chao, M. & Schempp, E. (1977).Acta Cryst.B33, 1557±1564.
Chao, M., Schempp, E. & Rosenstein, R. D. (1977).Acta Cryst.B33, 1820± 1823.
Hoȯe, G., Steglich, W. & VorbruÈggen, H. (1978).Angew. Chem. Int. Ed. Engl. 17, 569±583.
Huang, J. T., Cao, A. H., Shao, S. X., Sun, J. W. & Liu, Z. H. (1994).Huaxue Shijie,4, 188±190. (In Chinese.)
Ni, J., Li, Y. Z., Qi, W. B., Liu, Y. J., Chen, H. L. & Wang, Z. L. (2003).Acta Cryst.C59, o470±o472.
Ni, J., Li, Y. Z., Xue, Z., Chen, H. L. & Wang, Z. L. (2003).Acta Cryst.C59, m201±m203.
Ohms, U. & Guth, H. (1983).Z. Kristallogr.162, 174.
Riera, X., Moreno, V., Font-Bardia, M. & Solans, X. (1998).Polyhedron,18, 65±78.
Scriven, E. F. V. (1983).Chem. Soc. Rev.12, 129±161.
Steglich, W. & Hoe¯e, G. (1969).Angew. Chem. Int. Ed. Engl.8, 981.
supporting information
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Acta Cryst. (2003). E59, o1697–o1699
supporting information
Acta Cryst. (2003). E59, o1697–o1699 [https://doi.org/10.1107/S1600536803021676]
4-[
N,N
-Bis(2-cyanoethyl)amino]pyridinium perchlorate
Jin-Long Geng, Jun Ni, Rui Liu, Hui-Lan Chen and Zhi-Lin Wang
4-[N,N-bis(2-cyanoethyl)amino]pyridine perchlorate
Crystal data
C11H13N4+·ClO4−
Mr = 300.70 Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 5.403 (1) Å
b = 30.252 (5) Å
c = 8.293 (2) Å
β = 99.24 (1)°
V = 1337.9 (5) Å3
Z = 4
F(000) = 624
Dx = 1.493 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2473 reflections
θ = 2.6–25.9°
µ = 0.31 mm−1
T = 293 K Needle, colorless 0.40 × 0.20 × 0.15 mm
Data collection
Bruker SMART APEX CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2000)
Tmin = 0.925, Tmax = 0.957
6812 measured reflections 2345 independent reflections 1848 reflections with I > 2σ(I)
Rint = 0.062
θmax = 25.0°, θmin = 2.6°
h = −6→6
k = −35→35
l = −8→9
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.049
wR(F2) = 0.118
S = 1.00 2345 reflections 185 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) + (0.044P)2 + 0.8P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.36 e Å−3
supporting information
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Acta Cryst. (2003). E59, o1697–o1699
Special details
Refinement. The structure was solved by direct methods(Bruker, 2000) and successive difference Fourier syntheses. 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
Cl1 −0.29800 (12) 0.67181 (2) 0.89840 (9) 0.0525 (2)
O1 −0.3531 (5) 0.63189 (6) 0.9712 (3) 0.0871 (8)
O2 −0.0382 (4) 0.67343 (6) 0.8831 (3) 0.0731 (6)
O3 −0.4441 (6) 0.67699 (11) 0.7432 (4) 0.1311 (12)
O4 −0.3501 (5) 0.70762 (7) 0.9995 (4) 0.1000 (9)
N1 0.1321 (5) 0.76466 (9) 0.8764 (3) 0.0655 (8)
N2 0.2172 (4) 0.89903 (6) 0.8803 (2) 0.0369 (5)
N3 −0.2007 (4) 0.97220 (8) 0.6239 (3) 0.0559 (6)
N4 0.6700 (5) 0.96439 (9) 1.1714 (3) 0.0719 (8)
C1 0.2853 (6) 0.78309 (9) 0.7850 (3) 0.0567 (7)
H1 0.3739 0.7652 0.7232 0.068*
C2 0.3144 (5) 0.82742 (7) 0.7806 (3) 0.0437 (6)
H2 0.4181 0.8398 0.7134 0.052*
C3 0.1880 (4) 0.85505 (7) 0.8777 (3) 0.0369 (5)
C4 0.0295 (5) 0.83360 (9) 0.9730 (3) 0.0495 (6)
H4 −0.0578 0.8501 1.0400 0.059*
C5 0.0048 (6) 0.78943 (10) 0.9670 (4) 0.0614 (8)
H5 −0.1042 0.7758 1.0278 0.074*
C6 0.3622 (4) 0.92171 (7) 0.7706 (3) 0.0380 (5)
H6A 0.5084 0.9041 0.7594 0.046*
H6B 0.4206 0.9498 0.8186 0.046*
C7 0.2105 (5) 0.92984 (8) 0.6018 (3) 0.0426 (6)
H7A 0.3108 0.9468 0.5368 0.051*
H7B 0.1709 0.9017 0.5477 0.051*
C8 −0.0223 (5) 0.95373 (8) 0.6110 (3) 0.0426 (6)
C9 0.0956 (5) 0.92687 (8) 0.9883 (3) 0.0431 (6)
H9A −0.0738 0.9162 0.9881 0.052*
H9B 0.0843 0.9568 0.9459 0.052*
C10 0.2345 (5) 0.92756 (9) 1.1639 (3) 0.0475 (6)
H10A 0.1374 0.9441 1.2321 0.057*
H10B 0.2530 0.8976 1.2056 0.057*
C11 0.4820 (6) 0.94776 (9) 1.1721 (3) 0.0515 (7)
H11 0.113 (6) 0.7370 (11) 0.878 (4) 0.069 (10)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
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Acta Cryst. (2003). E59, o1697–o1699
O1 0.0981 (18) 0.0494 (12) 0.122 (2) −0.0068 (11) 0.0439 (16) 0.0176 (12)
O2 0.0588 (13) 0.0638 (13) 0.1018 (17) −0.0070 (10) 0.0280 (12) 0.0032 (11)
O3 0.115 (2) 0.160 (3) 0.100 (2) −0.015 (2) −0.0376 (19) 0.033 (2)
O4 0.110 (2) 0.0592 (14) 0.146 (2) −0.0086 (13) 0.0669 (19) −0.0168 (14)
N1 0.085 (2) 0.0397 (14) 0.0638 (17) −0.0161 (13) −0.0115 (14) 0.0090 (12)
N2 0.0416 (11) 0.0380 (11) 0.0323 (10) 0.0009 (8) 0.0091 (9) −0.0001 (8)
N3 0.0490 (15) 0.0591 (14) 0.0590 (16) −0.0010 (12) 0.0067 (12) 0.0109 (11)
N4 0.0530 (17) 0.0823 (18) 0.0798 (19) −0.0008 (14) 0.0086 (14) −0.0245 (15)
C1 0.0694 (19) 0.0429 (14) 0.0537 (17) 0.0038 (13) −0.0025 (14) −0.0040 (13)
C2 0.0471 (15) 0.0410 (13) 0.0428 (14) 0.0002 (11) 0.0066 (11) 0.0007 (11)
C3 0.0357 (13) 0.0419 (13) 0.0311 (12) −0.0025 (10) −0.0008 (10) 0.0036 (10)
C4 0.0467 (15) 0.0604 (17) 0.0414 (14) −0.0088 (13) 0.0072 (12) 0.0060 (12)
C5 0.065 (2) 0.0637 (19) 0.0522 (18) −0.0256 (16) −0.0009 (15) 0.0164 (15)
C6 0.0382 (13) 0.0368 (12) 0.0392 (13) −0.0039 (10) 0.0071 (11) 0.0007 (10)
C7 0.0461 (14) 0.0470 (14) 0.0357 (13) −0.0023 (11) 0.0100 (11) 0.0040 (10)
C8 0.0473 (16) 0.0427 (13) 0.0371 (14) −0.0080 (12) 0.0050 (12) 0.0073 (11)
C9 0.0424 (14) 0.0505 (14) 0.0357 (13) 0.0078 (11) 0.0046 (11) −0.0020 (11)
C10 0.0481 (15) 0.0584 (16) 0.0362 (14) 0.0081 (12) 0.0073 (12) −0.0041 (12)
C11 0.0535 (18) 0.0588 (17) 0.0411 (16) 0.0115 (14) 0.0039 (13) −0.0124 (12)
Geometric parameters (Å, º)
Cl1—O1 1.403 (2) C3—C4 1.413 (3)
Cl1—O3 1.406 (3) C4—C5 1.343 (4)
Cl1—O4 1.426 (2) C4—H4 0.9300
Cl1—O2 1.430 (2) C5—H5 0.9300
N1—C5 1.329 (4) C6—C7 1.524 (3)
N1—C1 1.331 (4) C6—H6A 0.9700
N1—H11 0.84 (3) C6—H6B 0.9700
N2—C3 1.340 (3) C7—C8 1.463 (4)
N2—C9 1.460 (3) C7—H7A 0.9700
N2—C6 1.463 (3) C7—H7B 0.9700
N3—C8 1.134 (3) C9—C10 1.528 (3)
N4—C11 1.134 (4) C9—H9A 0.9700
C1—C2 1.351 (3) C9—H9B 0.9700
C1—H1 0.9300 C10—C11 1.462 (4)
C2—C3 1.410 (3) C10—H10A 0.9700
C2—H2 0.9300 C10—H10B 0.9700
O1—Cl1—O3 111.29 (18) N2—C6—C7 112.58 (19)
O1—Cl1—O4 108.99 (15) N2—C6—H6A 109.1
O3—Cl1—O4 108.6 (2) C7—C6—H6A 109.1
O1—Cl1—O2 110.28 (14) N2—C6—H6B 109.1
O3—Cl1—O2 109.26 (19) C7—C6—H6B 109.1
O4—Cl1—O2 108.38 (14) H6A—C6—H6B 107.8
C5—N1—C1 120.8 (3) C8—C7—C6 111.9 (2)
C5—N1—H11 118 (2) C8—C7—H7A 109.2
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Acta Cryst. (2003). E59, o1697–o1699
C3—N2—C9 121.3 (2) C8—C7—H7B 109.2
C3—N2—C6 121.92 (19) C6—C7—H7B 109.2
C9—N2—C6 116.71 (19) H7A—C7—H7B 107.9
N1—C1—C2 121.1 (3) N3—C8—C7 177.6 (3)
N1—C1—H1 119.4 N2—C9—C10 113.06 (19)
C2—C1—H1 119.4 N2—C9—H9A 109.0
C1—C2—C3 120.2 (3) C10—C9—H9A 109.0
C1—C2—H2 119.9 N2—C9—H9B 109.0
C3—C2—H2 119.9 C10—C9—H9B 109.0
N2—C3—C2 122.1 (2) H9A—C9—H9B 107.8
N2—C3—C4 121.8 (2) C11—C10—C9 110.8 (2)
C2—C3—C4 116.1 (2) C11—C10—H10A 109.5
C5—C4—C3 120.1 (3) C9—C10—H10A 109.5
C5—C4—H4 119.9 C11—C10—H10B 109.5
C3—C4—H4 119.9 C9—C10—H10B 109.5
N1—C5—C4 121.6 (3) H10A—C10—H10B 108.1
N1—C5—H5 119.2 N4—C11—C10 176.7 (3)
C4—C5—H5 119.2
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N1—H11···O2 0.84 (3) 2.09 (3) 2.913 (4) 164 (3)
C1—H1···O4i 0.93 2.69 3.326 (4) 126
C2—H2···O1i 0.93 2.66 3.579 (3) 168
C5—H5···O4 0.93 2.44 3.169 (4) 135
C6—H6b···N4ii 0.97 2.65 3.487 (3) 145
C7—H7a···N3iii 0.97 2.73 3.407 (4) 127
C9—H9a···N4iv 0.97 2.65 3.163 (4) 113
C10—H10a···N4iv 0.97 2.57 3.257 (4) 128
