organic papers
Acta Cryst.(2005). E61, o2605–o2606 doi:10.1107/S1600536805021227 Oliveret al. C
16H18N4O2C8H6O4
o2605
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
N
,
N
000-Bis(pyridin-4-ylmethyl)succinamide–
terephthalic acid (1/1)
Clive L. Oliver,* Gareth O. Lloyd and Elise J.C. de Vries
Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa
Correspondence e-mail: oli@sun.ac.za
Key indicators
Single-crystal X-ray study
T= 100 K
Mean(C–C) = 0.002 A˚ Disorder in main residue
Rfactor = 0.054
wRfactor = 0.146
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.
#2005 International Union of Crystallography
Printed in Great Britain – all rights reserved
Alternate molecules of N,N0
-bis(pyridin-4-ylmethyl)-succinamide and terephthalic acid, each of which is located about a centre of inversion, are linked by strong O—H N hydrogen bonds to form strands in the title compound, C16H18N4O2C8H6O4. In addition, strong N—H O hydrogen bonds between the N,N0-bis(pyridin-4-ylmethyl)succinamide
molecules of adjacent strands link the latter to form sheets.
Comment
N,N0-Bis-pyridin-4-ylmethyl-succinamide, (1), forms part of a
series of compounds under investigation by us that possess biologically relevant functional groups, such as aromatic rings and amide groups (Atwoodet al., 1998; Barbouret al., 2000). It has recently been used in the assembly of harmonic single and triple helices in a polymeric coordination complex (Lloyd et al., 2005). Co-crystallization of terephthalic acid, (2), with (1) forms part of a structural study in which various acids were co-crystallized with the latter. The structure of (1) co-co-crystallized with (2) is described here.
Compounds (1) and (2) crystallize in a 1:1 ratio, (I), with each molecule located about a centre of inversion (Fig. 1). Hydrogen bonding plays an important role in the crystal
[image:1.610.218.447.406.456.2] [image:1.610.211.451.534.710.2]Received 21 June 2005 Accepted 4 July 2005 Online 16 July 2005
Figure 1
assembly (Fig. 2). The termini of (1) and (2) are linked to each other via O—H Nii hydrogen bonds [symmetry code: (ii)
x1, y+ 2, z], forming infinite one-dimensional strands; see Table 1 for parameters describing the hydrogen-bonding scheme. Neigbouring strands are in turn linked by two centrosymmetrically related N—H Oihydrogen bonds [symmetry code: (i)x1, y, z] which involve molecule (1). These hydrogen bonds link the strands to form infinite two-dimensional sheets. The sheets stack along the diagonal of the bcplane and the amide hydrogen-bonding pattern displayed is similar to that observed in -sheets of protein molecules (Sasaki & Lieberman, 1996). Hydrogen-bonding patterns of this type have recently been used in the rational design of coordination polymers (Sarkar & Biradha, 2005).
The absence of significant – interactions
[centroid centroid distances are4.8 A˚ ] is ascribed to the more favourable amide hydrogen bonding, which prevents close approach of aromatic rings in the structure.
Experimental
Compound (1) was synthesized in an analogous manner toN,N0
-bis-pyridin-4-ylmethylglutarimide (de Vries et al., 2005), except that succinyl dichloride instead of glutaryl dichloride was reacted with 4-aminomethylpyridine. Equimolar amounts of compounds (1) and (2) were dissolved in an excess of dimethylformamide, after which crystallization proceeded by slow evaporation. Colourless plate-like crystals formed after several weeks.
Crystal data
C16H18N4O2C8H6O4
Mr= 464.47
Triclinic,P1 a= 4.8721 (13) A˚ b= 9.550 (3) A˚ c= 11.547 (3) A˚
= 96.582 (4)
= 95.944 (4)
= 94.753 (4) V= 528.4 (3) A˚3
Z= 1
Dx= 1.460 Mg m
3
MoKradiation Cell parameters from 2080
reflections
= 2.6–28.3
= 0.11 mm1 T= 100 (2) K Plates, colourless 0.300.300.10 mm
Data collection
Bruker APEX CCD area-detector diffractometer
!scans
Absorption correction: multi-scan (Blessing, 1995)
Tmin= 0.973,Tmax= 0.989
3480 measured reflections
2330 independent reflections 2156 reflections withI> 2(I) Rint= 0.028
max= 28.2
h=6!6 k=12!11 l=15!11
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.054 wR(F2) = 0.146
S= 1.07 2330 reflections 155 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0704P)2
+ 0.3562P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.49 e A˚
3 min=0.36 e A˚
3
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
N8B—H5 O9Bi
0.88 2.01 2.875 (2) 166
O1A—H3 N4Bii
0.84 1.82 2.654 (2) 175
Symmetry codes: (i)x1;y;z; (ii)x1;yþ2;z.
All aromatic and methylene H atoms were positioned using the riding-model approximation, with C—H = 0.95 and 0.99 A˚ , respec-tively, and withUiso(H) = 1.2Ueq(C). The amide H atom was placed in an idealized trigonal–planar position, N—H = 0.88 A˚ , based on its initial peak position in the difference Fourier map, andUiso(H) = 1.2Ueq(N). The hydroxyl H atom was positioned using a hydrogen-bond searching model, with O—H = 0.82 A˚ andUiso(H) = 1.2Ueq(O). Atom C10 of molecule (1) is disordered over two positions, with the major disordered component having a site-occupancy factor of 0.86 (1), as determined from the refinement.
Data collection:SMART(Bruker, 2001); cell refinement:SAINT
(Bruker, 2002); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
X-SEED (Barbour, 2001); software used to prepare material for publication:X-SEED(Atwood & Barbour, 2003).
The authors thank the National Research Foundation of South Africa for financial assistance.
References
Atwood, J. L. & Barbour, L. J. (2003).Cryst. Growth Des.3, 3–8.
Atwood, J. L., Barbour, L. J. & Orr, G. W. (1998).Nature (London),393, 671– 672.
Barbour, L. J. (2001).J. Supramol. Chem.1, 189–191.
Barbour, L. J., Orr, G. W. & Atwood, J. L.(2000).Chem. Commun.pp. 859–860. Blessing, R. H. (1995).Acta Cryst.A51, 33–38.
Bruker (2001).SMART. Version 5.625. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2002).SAINT. Version 6.36a. Bruker AXS Inc., Madison, Wisconsin, USA.
Lloyd, G. O., Atwood, J. L. & Barbour, L. J. (2005).Chem. Commun.pp. 1845– 1845.
Sarkar, M. & Biradha, K. (2005).Chem. Commun.pp. 2229–2231.
Sasaki, T. & Lieberman, M. (1996).Comprehensive Supramolecular Chemistry, edited by J. L. Atwood, J. E. D. Davies, D. D. MacNicol & F. Vo¨gtle, Vol, 4, pp. 193–242. Oxford: Elsevier Science, Oxford.
[image:2.610.43.296.415.679.2]Sheldrick, G. M. (1997).SHELXS97,SHELXL97 andSADABS(Version 2.05). University of Go¨ttingen, Germany.
Figure 2
hydrogen-supporting information
sup-1 Acta Cryst. (2005). E61, o2605–o2606
supporting information
Acta Cryst. (2005). E61, o2605–o2606 [https://doi.org/10.1107/S1600536805021227]
N
,
N
′
-Bis(pyridin-4-ylmethyl)succinamide
–
terephthalic acid (1/1)
Clive L. Oliver, Gareth O. Lloyd and Elise J.C. de Vries
N,N′-bis(pyridin-4-ylmethyl)succinamide–terephthalic acid (1/1)
Crystal data
C16H18N4O2·C8H6O4
Mr = 464.47
Triclinic, P1 Hall symbol: -P1
a = 4.8721 (13) Å
b = 9.550 (3) Å
c = 11.547 (3) Å
α = 96.582 (4)°
β = 95.944 (4)°
γ = 94.753 (4)°
V = 528.4 (3) Å3
Z = 1
F(000) = 244
Dx = 1.460 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2080 reflections
θ = 2.6–28.3°
µ = 0.11 mm−1
T = 100 K Plates, colourless 0.30 × 0.30 × 0.10 mm
Data collection
Bruker APEX CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
Absorption correction: multi-scan (Blessing, 1995)
Tmin = 0.973, Tmax = 0.989
3480 measured reflections 2330 independent reflections 2156 reflections with I > 2σ(I)
Rint = 0.028
θmax = 28.2°, θmin = 1.8°
h = −6→6
k = −12→11
l = −15→11
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.054
wR(F2) = 0.146
S = 1.07 2330 reflections 155 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-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0704P)2 + 0.3562P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.49 e Å−3
Δρmin = −0.36 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 Occ. (<1)
O9B 0.2812 (2) 0.67174 (13) 0.39791 (11) 0.0206 (3) N4B −0.6616 (3) 1.14377 (14) 0.23942 (12) 0.0171 (3) N8B −0.1477 (3) 0.74241 (14) 0.36740 (12) 0.0159 (3) H5 −0.3203 0.7349 0.3838 0.019* C1B −0.2717 (3) 0.94885 (17) 0.27306 (14) 0.0154 (3) C5B −0.5089 (3) 1.14620 (18) 0.34315 (15) 0.0192 (4) H11 −0.5347 1.2166 0.4052 0.023* C2B −0.4285 (3) 0.94767 (17) 0.16569 (14) 0.0169 (3) H12 −0.4041 0.8802 0.1014 0.020* C3B −0.6207 (3) 1.04521 (17) 0.15246 (14) 0.0178 (3) H13 −0.7282 1.0420 0.0785 0.021* C9B 0.0341 (3) 0.66138 (17) 0.41422 (15) 0.0178 (3) C6B −0.3153 (3) 1.05104 (18) 0.36435 (15) 0.0189 (4) H15 −0.2139 1.0552 0.4397 0.023* C7B −0.0619 (3) 0.84318 (17) 0.28929 (15) 0.0181 (4) H16A −0.0393 0.7914 0.2121 0.022* H16B 0.1197 0.8940 0.3224 0.022* O1B 0.0119 (3) 0.77301 (13) −0.00313 (11) 0.0215 (3) O1A 0.0453 (2) 0.68403 (12) −0.18870 (10) 0.0192 (3) H3 −0.0690 0.7425 −0.2038 0.023* C1A 0.1078 (3) 0.69211 (16) −0.07418 (14) 0.0155 (3) C3A 0.3680 (3) 0.57972 (17) 0.08183 (14) 0.0166 (3) H8 0.2768 0.6345 0.1374 0.020* C2A 0.3118 (3) 0.59200 (16) −0.03722 (14) 0.0147 (3) C4A 0.5558 (2) 0.48835 (14) 0.12034 (12) 0.0161 (3) H10 0.5938 0.4805 0.2016 0.019*
C10B −0.0778 (2) 0.56377 (14) 0.49584 (12) 0.0227 (7) 0.858 (7) H10A −0.0698 0.6170 0.5751 0.027* 0.858 (7) H10B −0.2748 0.5325 0.4681 0.027* 0.858 (7) C11B −0.098 (4) 0.511 (2) 0.4419 (17) 0.040* 0.142 (7) H11A −0.0852 0.4348 0.3771 0.048* 0.142 (7) H11B −0.2934 0.5137 0.4570 0.048* 0.142 (7)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2005). E61, o2605–o2606
C5B 0.0194 (8) 0.0186 (8) 0.0196 (8) 0.0054 (6) 0.0012 (6) 0.0005 (6) C2B 0.0179 (7) 0.0169 (8) 0.0168 (8) 0.0039 (6) 0.0034 (6) 0.0027 (6) C3B 0.0168 (7) 0.0194 (8) 0.0177 (8) 0.0021 (6) 0.0005 (6) 0.0048 (6) C9B 0.0138 (7) 0.0191 (8) 0.0220 (8) 0.0031 (6) 0.0020 (6) 0.0079 (6) C6B 0.0179 (8) 0.0219 (8) 0.0173 (8) 0.0053 (6) −0.0001 (6) 0.0035 (6) C7B 0.0162 (7) 0.0204 (8) 0.0212 (8) 0.0067 (6) 0.0067 (6) 0.0094 (6) O1B 0.0231 (6) 0.0207 (6) 0.0214 (6) 0.0120 (5) 0.0000 (5) 0.0006 (5) O1A 0.0192 (6) 0.0215 (6) 0.0186 (6) 0.0110 (5) 0.0001 (5) 0.0050 (5) C1A 0.0134 (7) 0.0142 (7) 0.0191 (8) 0.0025 (5) 0.0006 (6) 0.0034 (6) C3A 0.0161 (7) 0.0157 (7) 0.0186 (8) 0.0050 (6) 0.0027 (6) 0.0012 (6) C2A 0.0117 (7) 0.0127 (7) 0.0199 (8) 0.0026 (5) 0.0009 (6) 0.0032 (6) C4A 0.0165 (7) 0.0165 (7) 0.0156 (7) 0.0043 (6) 0.0003 (6) 0.0027 (6) C10B 0.0161 (9) 0.0238 (12) 0.0352 (15) 0.0101 (8) 0.0114 (9) 0.0196 (11)
Geometric parameters (Å, º)
O9B—C9B 1.235 (2) C7B—H16B 0.9900 N4B—C3B 1.338 (2) O1B—C1A 1.217 (2) N4B—C5B 1.340 (2) O1A—C1A 1.318 (2) N8B—C9B 1.337 (2) O1A—H3 0.8400 N8B—C7B 1.458 (2) C1A—C2A 1.499 (2) N8B—H5 0.8800 C3A—C4A 1.391 (2) C1B—C2B 1.386 (2) C3A—C2A 1.394 (2) C1B—C6B 1.398 (2) C3A—H8 0.9500 C1B—C7B 1.508 (2) C2A—C4Ai 1.403 (2)
C5B—C6B 1.386 (2) C4A—C2Ai 1.403 (2)
C5B—H11 0.9500 C4A—H10 0.9500 C2B—C3B 1.384 (2) C10B—C10Bii 1.494 (2)
C2B—H12 0.9500 C10B—H10A 0.9900 C3B—H13 0.9500 C10B—H10B 0.9900 C9B—C10B 1.509 (2) C11B—C11Bii 1.60 (4)
C9B—C11B 1.607 (18) C11B—H11A 0.9900 C6B—H15 0.9500 C11B—H11B 0.9900 C7B—H16A 0.9900
C3B—N4B—C5B 117.75 (14) C1B—C7B—H16B 109.4 C9B—N8B—C7B 120.40 (13) H16A—C7B—H16B 108.0 C9B—N8B—H5 119.8 C1A—O1A—H3 109.5 C7B—N8B—H5 119.8 O1B—C1A—O1A 124.10 (14) C2B—C1B—C6B 117.61 (14) O1B—C1A—C2A 121.93 (15) C2B—C1B—C7B 120.55 (14) O1A—C1A—C2A 113.97 (13) C6B—C1B—C7B 121.84 (15) C4A—C3A—C2A 120.83 (14) N4B—C5B—C6B 123.18 (15) C4A—C3A—H8 119.6 N4B—C5B—H11 118.4 C2A—C3A—H8 119.6 C6B—C5B—H11 118.4 C3A—C2A—C4Ai 120.28 (13)
C3B—C2B—C1B 119.78 (15) C3A—C2A—C1A 118.75 (14) C3B—C2B—H12 120.1 C4Ai—C2A—C1A 120.97 (14)
N4B—C3B—C2B 122.75 (15) C3A—C4A—H10 120.6 N4B—C3B—H13 118.6 C2Ai—C4A—H10 120.6
C2B—C3B—H13 118.6 C10Bii—C10B—C9B 113.25 (14)
O9B—C9B—N8B 122.42 (15) C10Bii—C10B—H10A 108.9
O9B—C9B—C10B 121.97 (14) C9B—C10B—H10A 108.9 N8B—C9B—C10B 115.46 (13) C10Bii—C10B—H10B 108.9
O9B—C9B—C11B 117.4 (7) C9B—C10B—H10B 108.9 N8B—C9B—C11B 115.0 (7) H10A—C10B—H10B 107.7 C5B—C6B—C1B 118.92 (15) C9B—C11B—C11Bii 101.2 (16)
C5B—C6B—H15 120.5 C9B—C11B—H11A 111.5 C1B—C6B—H15 120.5 C11Bii—C11B—H11A 111.5
N8B—C7B—C1B 111.26 (12) C9B—C11B—H11B 111.5 N8B—C7B—H16A 109.4 C11Bii—C11B—H11B 111.5
C1B—C7B—H16A 109.4 H11A—C11B—H11B 109.3 N8B—C7B—H16B 109.4
C3B—N4B—C5B—C6B −0.8 (2) C4A—C3A—C2A—C4Ai 0.1 (2)
C6B—C1B—C2B—C3B −0.3 (2) C4A—C3A—C2A—C1A −179.95 (13) C7B—C1B—C2B—C3B 179.81 (14) O1B—C1A—C2A—C3A 7.6 (2) C5B—N4B—C3B—C2B −0.3 (2) O1A—C1A—C2A—C3A −172.59 (14) C1B—C2B—C3B—N4B 0.8 (2) O1B—C1A—C2A—C4Ai −172.45 (15)
C7B—N8B—C9B—O9B 3.0 (3) O1A—C1A—C2A—C4Ai 7.3 (2)
C7B—N8B—C9B—C10B 178.62 (14) C2A—C3A—C4A—C2Ai −0.1 (2)
C7B—N8B—C9B—C11B −150.8 (8) O9B—C9B—C10B—C10Bii −29.7 (2)
N4B—C5B—C6B—C1B 1.3 (3) N8B—C9B—C10B—C10Bii 154.72 (16)
C2B—C1B—C6B—C5B −0.7 (2) C11B—C9B—C10B—C10Bii 59.0 (14)
C7B—C1B—C6B—C5B 179.20 (15) O9B—C9B—C11B—C11Bii 58.8 (19)
C9B—N8B—C7B—C1B −164.72 (15) N8B—C9B—C11B—C11Bii −145.9 (13)
C2B—C1B—C7B—N8B −111.52 (17) C10B—C9B—C11B—C11Bii −48.4 (13)
C6B—C1B—C7B—N8B 68.62 (19)
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N8B—H5···O9Biii 0.88 2.01 2.875 (2) 166
O1A—H3···N4Biv 0.84 1.82 2.654 (2) 175
