Sheets of π-stacked centrosymmetric mol­ecules in N,N′-bis­(3-nitro­benzyl­idene)octane-1,8-diamine

Glidewell, C.; Low, J.N.; Skakle, J.M.S.; Wardell, J.L.

doi:10.1107/S1600536805031065

organic compounds

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ISSN: 2056-9890

Volume 61| Part 11| November 2005| Pages o3551-o3553

https://doi.org/10.1107/S1600536805031065

Sheets of π-stacked centrosymmetric molecules in N,N′-bis(3-nitrobenzylidene)octane-1,8-diamine

Christopher Glidewell,^a ^* John N. Low,^b Janet M. S. Skakle ^b and James L. Wardell ^c

^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

(Received 28 September 2005; accepted 29 September 2005; online 5 October 2005)

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 crystal structure 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 imines, and especially in compounds of the type O₂NC₆H₄CH=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).

The molecules of (I) lie across centres of inversion in the space group P2₁/c, with the reference molecule selected as that lying across ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ) (Fig. 1). The bond distances (Table 1) clearly show the presence of the double bond C11=N11, with typical skeletal bond 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 ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ), is almost parallel with the aryl rings at (x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) and (x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z), which form parts of the molecules centred across ( $[{1\over 2}]$ , 0, 1) and ( $[{1\over 2}]$ , 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 space group 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.

Figure 1
The molecule of compound (I)

, showing the atom-labelling scheme. The atoms marked `a' are at the symmetry position (1 − x, 1 − y, 1 − z) and displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Stereoview of part of the crystal structure of compound (I)

, showing the formation of a π-stacked (100) sheet. For the sake of clarity, the H atoms have been omitted.

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

C₂₂H₂₆N₄O₄
M_r = 410.47
Monoclinic, P 2₁ /c
a = 8.1297 (5) Å
b = 19.2452 (15) Å
c = 7.4113 (4) Å
β = 115.321 (4)°
V = 1048.15 (12) Å³
Z = 2
D_x = 1.301 Mg m⁻³
Mo Kα radiation
Cell parameters from 2407 reflections
θ = 3.2–27.6°
μ = 0.09 mm⁻¹
T = 120 (2) K
Plate, yellow
0.35 × 0.24 × 0.06 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.978, T_max = 0.995
11275 measured reflections
2407 independent reflections
1284 reflections with I > 2σ(I)
R_int = 0.070
θ_max = 27.6°
h = −10 → 10
k = −24 → 24
l = −9 → 9

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.158
S = 1.01
2407 reflections
136 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0804P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—C11	1.476 (3)
C11—N11	1.268 (2)
N11—C12	1.455 (2)

C1—C11—N11	122.55 (18)
C11—N11—C12	117.28 (17)

C2—C1—C11—N11	−178.68 (19)
C1—C11—N11—C12	−179.34 (18)
C11—N11—C12—C13	113.8 (2)
N11—C12—C13—C14	−64.9 (2)
C12—C13—C14—C15	−175.69 (16)
C13—C14—C15—C15ⁱ	176.9 (2)
C4—C5—N5—O51	−177.60 (19)
Symmetry code: (i) -x+1, -y+1, -z+1.

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 U_iso(H) = 1.2U_eq(C).

Data collection: COLLECT (Hooft, 1999 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805031065/lh6516sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805031065/lh6516Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: 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).

N,N'-bis(3-nitrobenzylidene)octane-1,8-diamine top

Crystal data top

C₂₂H₂₆N₄O₄	F(000) = 436
M_r = 410.47	D_x = 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

Data collection top

Bruker–Nonius KappaCCD diffractometer	2407 independent reflections
Radiation source: Bruker–Nonius FR91 rotating anode	1284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.2°
φ and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −24→24
T_min = 0.978, T_max = 0.995	l = −9→9
11275 measured reflections

Refinement top

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(F_o²) + (0.0804P)²] where P = (F_o² + 2F_c²)/3
2407 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

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