organic compounds
Sheets of π-stacked centrosymmetric molecules in N,N′-bis(3-nitrobenzylidene)octane-1,8-diamine
aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
*Correspondence e-mail: cg@st-andrews.ac.uk
In molecules of the title compound, C22H26N4O4, which lie across centres of inversion, the central octane fragment adopts a nearly planar all-trans conformation. There are no hydrogen bonds in the but the molecules are linked into sheets by a single π–π stacking interaction.
Comment
As part of our continuing studies of the supramolecular arrangements in 2NC6H4CH=N—(R)—N=CHC6H4NO2, where R = 1,2-cyclo-C6H10 (Glidewell, Low, Skakle & Wardell, 2005; Glidewell, Low & Wardell, 2005) or R = (CH2)n (Bomfim et al., 2005), we now report the molecular and supramolecular structure of the title compound, (I).
and especially in compounds of the type OThe molecules of (I) lie across centres of inversion in the P21/c, with the reference molecule selected as that lying across (, , ) (Fig. 1). The bond distances (Table 1) clearly show the presence of the double bond C11=N11, with typical angles at C11 and N11. The nitroaryl –CH=N—C fragment is almost planar, as is the eight-carbon fragment of the central spacer, as shown by the leading torsional angles (Table 1); however, the overall molecular conformation is very far from being planar, as shown by the torsion angles around the N11—C11 and C12—C13 bonds, where the non-H substituents are mutually anticlinal and synclinal respectively (Table 1 and Fig. 1).
The supramolecular aggregation is very simple; there are no hydrogen bonds of any kind, but a single aromatic π–π stacking interaction links the molecules into sheets. The aryl ring at (x, y, z), which is part of the molecule centred across (, , ), is almost parallel with the aryl rings at (x, − y, + z) and (x, − y, − + z), which form parts of the molecules centred across (, 0, 1) and (, 0, 0), respectively. The dihedral angle between adjacent rings is only 2.5 (2)°, with the ring-centroid separations both 3.762 (2) Å; the interplanar spacings are ca 3.39 Å and the ring-centroid offsets are ca 1.63 Å. Propagation of this single interaction by the symmetry then generates a (100) sheet in which each molecule is linked to four others (Fig. 2); there are, however, no direction-specific interactions between adjacent sheets.
Experimental
A solution of 3-nitrobenzaldehyde (0.4 mmol) and 1,8-diaminooctane (0.2 mmol) in methanol (20 ml) was heated under reflux for 1 h; the mixture was cooled and the solvent was removed under reduced pressure. The solid residue was recrystallized from 1,2-dichloroethane to yield crystals of compound (I) suitable for single-crystal X-ray diffraction (m.p. 359–361 K). IR (KBr): 3086, 2933–2832, 1646, 1610,1580, 1536, 1468, 1439, 1343, 1270, 1155, 1078, 1027, 971, 983, 931, 828, 805, 734, 684, 675, 629, 508 cm−1.
Crystal data
|
Refinement
|
All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic) or 0.99 Å (aliphatic), and with Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Hooft, 1999); cell DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
Supporting information
https://doi.org/10.1107/S1600536805031065/lh6516sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805031065/lh6516Isup2.hkl
Data collection: COLLECT (Hooft, 1999); cell
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).C22H26N4O4 | F(000) = 436 |
Mr = 410.47 | Dx = 1.301 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2407 reflections |
a = 8.1297 (5) Å | θ = 3.2–27.6° |
b = 19.2452 (15) Å | µ = 0.09 mm−1 |
c = 7.4113 (4) Å | T = 120 K |
β = 115.321 (4)° | Plate, yellow |
V = 1048.15 (12) Å3 | 0.35 × 0.24 × 0.06 mm |
Z = 2 |
Bruker–Nonius KappaCCD diffractometer | 2407 independent reflections |
Radiation source: Bruker–Nonius FR91 rotating anode | 1284 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 3.2° |
φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −24→24 |
Tmin = 0.978, Tmax = 0.995 | l = −9→9 |
11275 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0804P)2] where P = (Fo2 + 2Fc2)/3 |
2407 reflections | (Δ/σ)max < 0.001 |
136 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
x | y | z | Uiso*/Ueq | ||
O51 | −0.4726 (2) | 0.30584 (9) | 0.2452 (2) | 0.0497 (5) | |
O52 | −0.4979 (2) | 0.19476 (9) | 0.2222 (2) | 0.0554 (5) | |
N5 | −0.4146 (2) | 0.24756 (10) | 0.3007 (2) | 0.0337 (5) | |
N11 | 0.0789 (2) | 0.41578 (9) | 0.7670 (2) | 0.0351 (5) | |
C1 | 0.0339 (2) | 0.29242 (11) | 0.7145 (3) | 0.0282 (5) | |
C2 | 0.1051 (3) | 0.22653 (11) | 0.7750 (3) | 0.0320 (5) | |
C3 | 0.0066 (3) | 0.16718 (12) | 0.6830 (3) | 0.0364 (6) | |
C4 | −0.1647 (3) | 0.17372 (11) | 0.5267 (3) | 0.0333 (5) | |
C5 | −0.2334 (2) | 0.23980 (10) | 0.4686 (3) | 0.0272 (5) | |
C6 | −0.1394 (2) | 0.29929 (10) | 0.5582 (3) | 0.0277 (5) | |
C11 | 0.1398 (3) | 0.35460 (11) | 0.8148 (3) | 0.0329 (5) | |
C12 | 0.1973 (3) | 0.47278 (11) | 0.8757 (3) | 0.0385 (6) | |
C13 | 0.2532 (3) | 0.51566 (11) | 0.7389 (3) | 0.0367 (6) | |
C14 | 0.3695 (3) | 0.47560 (11) | 0.6595 (3) | 0.0348 (6) | |
C15 | 0.4381 (3) | 0.51947 (11) | 0.5348 (3) | 0.0365 (6) | |
H2 | 0.2232 | 0.2217 | 0.8810 | 0.038* | |
H3 | 0.0567 | 0.1224 | 0.7275 | 0.044* | |
H4 | −0.2332 | 0.1339 | 0.4612 | 0.040* | |
H6 | −0.1914 | 0.3439 | 0.5146 | 0.033* | |
H11 | 0.2583 | 0.3486 | 0.9193 | 0.039* | |
H12A | 0.3073 | 0.4539 | 0.9870 | 0.046* | |
H12B | 0.1331 | 0.5029 | 0.9332 | 0.046* | |
H13A | 0.1423 | 0.5324 | 0.6247 | 0.044* | |
H13B | 0.3219 | 0.5569 | 0.8129 | 0.044* | |
H14A | 0.2972 | 0.4364 | 0.5770 | 0.042* | |
H14B | 0.4754 | 0.4558 | 0.7737 | 0.042* | |
H15A | 0.3322 | 0.5372 | 0.4165 | 0.044* | |
H15B | 0.5046 | 0.5601 | 0.6147 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O51 | 0.0358 (9) | 0.0453 (11) | 0.0507 (9) | 0.0044 (8) | 0.0019 (7) | 0.0050 (8) |
O52 | 0.0416 (9) | 0.0479 (11) | 0.0538 (10) | −0.0133 (8) | −0.0013 (8) | −0.0069 (8) |
N5 | 0.0295 (9) | 0.0395 (12) | 0.0306 (10) | −0.0026 (9) | 0.0114 (8) | −0.0007 (9) |
N11 | 0.0303 (9) | 0.0348 (12) | 0.0375 (10) | −0.0032 (8) | 0.0119 (8) | 0.0019 (8) |
C1 | 0.0252 (10) | 0.0350 (13) | 0.0259 (10) | −0.0019 (9) | 0.0125 (9) | 0.0017 (9) |
C2 | 0.0261 (10) | 0.0446 (14) | 0.0254 (10) | 0.0023 (10) | 0.0109 (9) | 0.0054 (10) |
C3 | 0.0413 (12) | 0.0348 (13) | 0.0364 (12) | 0.0087 (11) | 0.0198 (11) | 0.0076 (10) |
C4 | 0.0362 (12) | 0.0346 (13) | 0.0319 (11) | −0.0037 (10) | 0.0173 (10) | −0.0004 (9) |
C5 | 0.0240 (10) | 0.0363 (13) | 0.0214 (10) | 0.0001 (9) | 0.0098 (9) | 0.0025 (9) |
C6 | 0.0269 (10) | 0.0317 (12) | 0.0272 (10) | −0.0008 (9) | 0.0140 (9) | 0.0020 (9) |
C11 | 0.0255 (10) | 0.0433 (14) | 0.0287 (11) | −0.0028 (10) | 0.0105 (9) | 0.0025 (10) |
C12 | 0.0366 (11) | 0.0388 (14) | 0.0379 (12) | −0.0059 (10) | 0.0139 (10) | −0.0035 (10) |
C13 | 0.0344 (11) | 0.0322 (13) | 0.0407 (12) | −0.0035 (9) | 0.0135 (10) | −0.0029 (10) |
C14 | 0.0374 (11) | 0.0291 (12) | 0.0368 (11) | −0.0028 (9) | 0.0149 (10) | −0.0023 (9) |
C15 | 0.0393 (12) | 0.0323 (13) | 0.0363 (12) | 0.0004 (10) | 0.0146 (10) | 0.0007 (9) |
C1—C2 | 1.386 (3) | C11—H11 | 0.95 |
C1—C6 | 1.396 (3) | N11—C12 | 1.455 (2) |
C1—C11 | 1.476 (3) | C12—C13 | 1.520 (3) |
C2—C3 | 1.394 (3) | C12—H12A | 0.99 |
C2—H2 | 0.95 | C12—H12B | 0.99 |
C3—C4 | 1.385 (3) | C13—C14 | 1.520 (3) |
C3—H3 | 0.95 | C13—H13A | 0.99 |
C4—C5 | 1.382 (3) | C13—H13B | 0.99 |
C4—H4 | 0.95 | C14—C15 | 1.523 (3) |
C5—C6 | 1.379 (3) | C14—H14A | 0.99 |
C5—N5 | 1.474 (2) | C14—H14B | 0.99 |
C6—H6 | 0.95 | C15—C15i | 1.511 (4) |
N5—O51 | 1.218 (2) | C15—H15A | 0.99 |
N5—O52 | 1.222 (2) | C15—H15B | 0.99 |
C11—N11 | 1.268 (2) | ||
C2—C1—C6 | 119.24 (18) | N11—C12—C13 | 110.84 (17) |
C2—C1—C11 | 120.40 (17) | N11—C12—H12A | 109.5 |
C6—C1—C11 | 120.36 (18) | C13—C12—H12A | 109.5 |
C1—C2—C3 | 121.21 (17) | N11—C12—H12B | 109.5 |
C1—C2—H2 | 119.4 | C13—C12—H12B | 109.5 |
C3—C2—H2 | 119.4 | H12A—C12—H12B | 108.1 |
C4—C3—C2 | 119.8 (2) | C14—C13—C12 | 113.33 (18) |
C4—C3—H3 | 120.1 | C14—C13—H13A | 108.9 |
C2—C3—H3 | 120.1 | C12—C13—H13A | 108.9 |
C5—C4—C3 | 118.18 (19) | C14—C13—H13B | 108.9 |
C5—C4—H4 | 120.9 | C12—C13—H13B | 108.9 |
C3—C4—H4 | 120.9 | H13A—C13—H13B | 107.7 |
C6—C5—C4 | 123.19 (17) | C13—C14—C15 | 113.80 (18) |
C6—C5—N5 | 118.05 (18) | C13—C14—H14A | 108.8 |
C4—C5—N5 | 118.76 (17) | C15—C14—H14A | 108.8 |
C5—C6—C1 | 118.40 (18) | C13—C14—H14B | 108.8 |
C5—C6—H6 | 120.8 | C15—C14—H14B | 108.8 |
C1—C6—H6 | 120.8 | H14A—C14—H14B | 107.7 |
O51—N5—O52 | 123.31 (16) | C15i—C15—C14 | 113.7 (2) |
O51—N5—C5 | 118.76 (17) | C15i—C15—H15A | 108.8 |
O52—N5—C5 | 117.91 (17) | C14—C15—H15A | 108.8 |
C1—C11—N11 | 122.55 (18) | C15i—C15—H15B | 108.8 |
N11—C11—H11 | 118.7 | C14—C15—H15B | 108.8 |
C1—C11—H11 | 118.7 | H15A—C15—H15B | 107.7 |
C11—N11—C12 | 117.28 (17) | ||
C6—C1—C2—C3 | −0.2 (3) | C6—C1—C11—N11 | 1.0 (3) |
C11—C1—C2—C3 | 179.51 (18) | C1—C11—N11—C12 | −179.34 (18) |
C1—C2—C3—C4 | 0.8 (3) | C11—N11—C12—C13 | 113.8 (2) |
C2—C3—C4—C5 | −0.8 (3) | N11—C12—C13—C14 | −64.9 (2) |
C3—C4—C5—C6 | 0.2 (3) | C12—C13—C14—C15 | −175.69 (16) |
C3—C4—C5—N5 | 179.22 (17) | C13—C14—C15—C15i | 176.9 (2) |
C4—C5—C6—C1 | 0.4 (3) | C6—C5—N5—O51 | 1.4 (3) |
N5—C5—C6—C1 | −178.64 (16) | C4—C5—N5—O51 | −177.60 (19) |
C2—C1—C6—C5 | −0.4 (3) | C6—C5—N5—O52 | −179.66 (18) |
C11—C1—C6—C5 | 179.92 (18) | C4—C5—N5—O52 | 1.3 (3) |
C2—C1—C11—N11 | −178.68 (19) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England. The authors thank the staff for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.
References
Bomfim, J. A. S., Wardell, J. L., Low, J. N., Skakle, J. M. S. & Glidewell, C. (2005). Acta Cryst. C61, o53–o56. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005). Acta Cryst. E61, o1699–o1701. Web of Science CSD CrossRef IUCr Journals Google Scholar
Glidewell, C., Low, J. N. & Wardell, J. L. (2005). Acta Cryst. C61, o551–o554. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.