π-Stacked hydrogen-bonded sheets in N,N′-bis(4-nitro­benzyl­idene)­ethane-1,2-di­amine and π-stacked hydrogen-bonded chains in N,N′-bis(4-nitro­benzyl­idene)­propane-1,3-di­amine

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

doi:10.1107/S0108270104030719

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 1| January 2005| Pages o53-o56

doi:10.1107/S0108270104030719

π-Stacked hydrogen-bonded sheets in N,N′-bis(4-nitrobenzylidene)ethane-1,2-diamine and π-stacked hydrogen-bonded chains in N,N′-bis(4-nitrobenzylidene)propane-1,3-diamine

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

^aInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 17 November 2004; accepted 23 November 2004; online 18 December 2004)

Molecules of N,N′-bis(4-nitrobenzylidene)ethane-1,2-diamine, C₁₆H₁₄N₄O₄, (I), lie across centres of inversion in space group P2₁/n and are linked into (10 $[\overline 1]$ ) sheets by a single C—H⋯O hydrogen bond [H⋯O = 2.40 Å, C⋯O = 3.2166 (13) Å and C—H⋯O = 146°]; these sheets are linked into a three-dimensional array by a single aromatic π–π stacking interaction. Molecules of N,N′-bis(4-nitrobenzylidene)propane-1,3-diamine, C₁₇H₁₆N₄O₄, (II), lie across twofold rotation axes in space group C2/c and are linked into chains of spiro-fused rings by a single C—H⋯O hydrogen bond [H⋯O = 2.54 Å, C⋯O = 3.267 (2) Å and C—H⋯O = 130°]; these chains are linked into sheets by a single aromatic π–π stacking interaction.

Comment

As part of a study of the supramolecular structures of compounds containing nitro groups, the structures of the title compounds were determined. The structure of N,N′-bis(4-nitrobenzylidene)ethane-1,2-diamine, (I), has been reported very recently (Sun et al., 2004 ) and it is clear that the determination reported here refers to the same phase as that in the previous report. A larger data set is employed here (2717 reflections as opposed to 1635), leading to slightly higher precision. Although Sun et al. (2004) drew attention to the presence in the structure of a C—H⋯O hydrogen bond and to the occurrence of an aromatic π–π stacking interaction, the structural consequences of these interactions were not analysed or discussed in detail. In particular, the dimensionality of the resulting supramolecular structure was not specified. Accordingly, we feel it is justifiable to discuss this structure in detail along with that of its homologue N,N′-bis(4-nitrobenzylidene)propane-1,3-diamine, (II).

Molecules of (I) (Fig. 1) lie across centres of inversion in space group P2₁/n, and the reference molecule was selected to lie across ( $[1\over2]$ , $[1\over2]$ , $[1\over2]$ ). The key torsion angles (Table 1) show that the N11—C11 bond almost eclipses the C12—H12A bond; the C11—N11—C12—H12A angle is only 2.3°. The two halves of the molecule are otherwise each nearly planar. The bond lengths and interbond angles agree closely with those found by Sun et al. (2004) and show no unusual values.

The molecules of (I) are linked into sheets by a single, fairly short, C—H⋯O hydrogen bond (Table 2). Atoms C6 at (x, y, z) and (1 − x, 1 − y 1 − z), which lie in the molecule centred at ( $[1\over2]$ , $[1\over2]$ , $[1\over2]$ ), act as hydrogen-bond donors, respectively, to atoms O41 at (− $[1\over2]$ + x, $[3\over2]$ − y, − $[1\over2]$ + z) and ( $[3\over2]$ − x, − $[1\over2]$ + y, $[3\over2]$ − z), which themselves lie in the molecules centred at (0, 1, 0) and (1, 0, 1). In a similar way, atoms O41 at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms C6 at ( $[1\over2]$ + x, $[3\over2]$ − y, $[1\over2]$ + z) and ( $[1\over2]$ − x, − $[1\over2]$ + y, $[1\over2]$ − z), respectively, which lie in the molecules centred at (1, 1, 1) and (0, 0, 0), respectively. In this manner, each molecule is linked to four others, forming a (10 $[\overline1]$ ) sheet (Fig. 2) in the form of a (4,4)-net (Batten & Robson, 1998 ), built from a single type of R₄⁴(42) ring (Bernstein et al., 1995 ).

A single π–π stacking interaction links adjacent sheets. The aryl rings at (x, y, z) and (1 − x, 1 − y, 2 − z) are components of the molecules centred at ( $[1\over2]$ , $[1\over2]$ , $[1\over2]$ ) and ( $[1\over2]$ , $[1\over2]$ , $[3\over2]$ ), respectively. These rings are strictly parallel, with an interplanar separation of 3.419 (2) Å; the ring-centroid separation is 3.696 (2) Å, corresponding to a near-ideal ring-centroid offset of 1.404 (2) Å. Propagation of this stacking interaction by translation and inversion links the molecules into a molecular ladder running parallel to the [001] direction (Fig. 3), and this ladder suffices to link each (10 $[\overline1]$ ) sheet to the two adjacent sheets, hence forming a continuous three-dimensional array.

Molecules of (II) (Fig. 4) lie across twofold rotation axes in space group C2/c, and the reference molecule was selected to lie across the axis along ( $[1\over2]$ , y, $[1\over4]$ ). The central spacer unit has a conformation exhibiting almost perfect staggering about the C—C bonds (Table 3) and, as in (I), the outer portions of the molecule are nearly planar.

Molecules of (II) are linked into chains of spiro-fused rings by a single C—H⋯O hydrogen bond (Table 4). Atom C13 at ( $[1\over2]$ , y, $[1\over4]$ ) acts as a hydrogen-bond donor to nitro atoms O41 at (x, 1 − y, − $[1\over2]$ + z) and (1 − x, 1 − y, 1 −z), which themselves are components of the molecules across the twofold rotation axes ( $[1\over2]$ , −y, − $[1\over4]$ ) and ( $[1\over2]$ , −y, $[3\over4]$ ), respectively. Propagation by rotation of this single hydrogen bond then generates a chain of spiro-fused centrosymmetric R₂²(22) rings running parallel to the [001] direction, in which atom C13 is the spiro atom (Fig. 5).

Two chains of this type, related to one another by the C-centring operation, pass through each unit cell, and the chains are linked into sheets by a single aromatic π–π stacking interaction. The aryl rings at (x, y, z) and ( $[3\over2]$ − x, $[3\over2]$ − y, 1 − z), which lie in molecules across the axes ( $[1\over2]$ , y, $[1\over4]$ ) and (1, −y, $[3\over4]$ ), respectively, are strictly parallel, with an interplanar separation of 3.366 (2) Å; the ring-centroid separation is 3.664 (2) Å, corresponding to a near-ideal centroid offset of 1.447 (2) Å. Propagation of this interaction by inversion and rotation then generates a π-stacked [101] chain (Fig. 6). Since each molecule in this chain is also a component of a hydrogen-bonded chain along [001], the overall supramolecular structure takes the form of a (010) sheet.

Figure 1
The molecule of (I

), showing the atom-labelling scheme. Atoms labelled with the suffix `A' are at the symmetry position (1 − x, 1 − y, 1 − z), and displacement ellipsoids are drawn at the 30% probability level.

Figure 2
A stereoview of part of the crystal structure of (I

), showing the formation of a (10 $[\overline1]$ ) sheet. For clarity, H atoms not involved in hydrogen bonding have been omitted.

Figure 3
A stereoview of part of the crystal structure of (I

), showing the formation of a π-stacked molecular ladder along [001]. For clarity, all of the H atoms have been omitted.

Figure 4
The molecule of (II

), showing the atom-labelling scheme. Atoms labelled with the suffix `A' are at the symmetry position (1 − x, y, $[1\over2]$ − z), and displacement ellipsoids are drawn at the 30% probability level.

Figure 5
A stereoview of part of the crystal structure of (II

), showing the formation of a [001] chain of spiro-fused R₂²(22) rings. For clarity, H atoms not involved in hydrogen bonding have been omitted.

Figure 6
A stereoview of part of the crystal structure of (II

), showing the formation of a [101] π-stacked chain, which links the hydrogen-bonded chains into (010) sheets. For clarity, all of the H atoms have been omitted.

Experimental

The title compounds were prepared by the reactions of 4-nitrobenzaldehyde with the appropriate α,ω-diaminoalkane (2:1 molar ratio) in refluxing methanol; crystals suitable for single-crystal X-ray diffraction were grown from solutions in ethanol. For (I), m.p. 470–474 K; IR: 1640 (C $[\equiv]$ N), 1520 and 1340 cm^—1 (NO₂); for (II), m.p. 466–467 K (melts with decomposition to black liquid): IR: 1644 (C $[\equiv]$ N), 1518 and 1341 cm^—1 (NO₂).

Compound (I)

Crystal data

C₁₆H₁₄N₄O₄
M_r = 326.31
Monoclinic, P2₁/n
a = 9.1606 (5) Å
b = 7.2295 (4) Å
c = 11.5201 (6) Å
β = 97.515 (1)°
V = 756.38 (7) Å³
Z = 2
D_x = 1.433 Mg m⁻³
Mo Kα radiation
Cell parameters from 2717 reflections
θ = 2.7–32.6°
μ = 0.11 mm⁻¹
T = 291 (2) K
Block, colourless
0.47 × 0.37 × 0.25 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.946, T_max = 0.974
7869 measured reflections
2717 independent reflections
2008 reflections with I > 2σ(I)
R_int = 0.020
θ_max = 32.6°
h = −13 → 13
k = −10 → 10
l = −13 → 17

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.158
S = 1.05
2717 reflections
109 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.095P)² + 0.0285P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Selected torsion angles (°) for (I)

C12ⁱ—C12—N11—C11	118.31 (13)
C12—N11—C11—C1	−176.58 (8)
N11—C11—C1—C2	177.91 (9)
C3—C4—N4—O41	−5.86 (15)
Symmetry code: (i) 1-x,1-y,1-z.

Table 2
Hydrogen-bonding geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O41ⁱⁱ	0.93	2.40	3.2166 (13)	146
Symmetry code: (ii) $[x-{\script{1\over 2}},{\script{3\over 2}}-y,z-{\script{1\over 2}}]$ .

Compound (II)

Crystal data

C₁₇H₁₆N₄O₄
M_r = 340.34
Monoclinic, C2/c
a = 12.9412 (6) Å
b = 7.3062 (3) Å
c = 16.9061 (8) Å
β = 99.559 (2)°
V = 1576.29 (12) Å³
Z = 4
D_x = 1.434 Mg m⁻³
Mo Kα radiation
Cell parameters from 1827 reflections
θ = 3.2–27.6°
μ = 0.11 mm⁻¹
T = 120 (2) K
Needle, orange
0.20 × 0.09 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.984, T_max = 0.996
8695 measured reflections
1827 independent reflections
1306 reflections with I > 2σ(I)
R_int = 0.052
θ_max = 27.6°
h = −16 → 16
k = −9 → 9
l = −21 → 21

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.158
S = 1.06
1827 reflections
114 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0884P)² + 0.3187P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 3
Selected torsion angles (°) for (II)

C12ⁱⁱⁱ—C13—C12—N11	67.65 (11)
C13—C12—N11—C11	−121.50 (17)
C12—N11—C11—C1	179.33 (14)
N11—C11—C1—C2	174.52 (17)
C3—C4—N4—O41	2.4 (2)
Symmetry code: (iii) $[1-x,y,{\script{1\over 2}}-z]$ .

Table 4
Hydrogen-bonding geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O42^iv	0.99	2.54	3.267 (2)	130
Symmetry code: (iv) $[x,1-y,z-{\script{1\over 2}}]$ .

For compound (I), the space group P2₁/n was uniquely assigned from the systematic absences. For compound (II), the systematic absences permitted Cc and C2/c as possible space groups; C2/c was selected and confirmed by the successful structure analysis. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances in (I) of 0.97 (CH₂) or 0.93 Å (all other H atoms) and in (II) of 0.99 (CH₂) or 0.95 Å (all other H atoms), and with U_iso(H) values of 1.2U_eq(C).

For compound (I), data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus. For compound (II), data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT. For both compounds, 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, II. DOI: 10.1107/S0108270104030719/sk1795sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104030719/sk1795Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270104030719/sk1795IIsup3.hkl

Comment top

As part of a study on the supramolecular structures of compounds containing nitro groups, the structures of the title compounds were determined. The structure of ethane-1,2-diylbis(4-nitrobenzaldimine), (I), has been reported very recently (Sun et al., 2004), and it is clear that the determination reported here refers to the same phase as that in the previous report. A larger data set is employed here (2717 reflections as opposed to 1635), leading to slightly higher precision. Although Sun et al. (2004) drew attention to the presence in the structure of a C—H···O hydrogen bond and to the occurrence of an aromatic π–π stacking interaction, the structural consequences of these interactions were not analysed or discussed in detail. In particular, the dimensionality of the resulting supramolecular structure was not specified. Accordingly, we feel it is justifiable to discuss this structure in detail along with that of its homologue propane-1,3-diylbis(4-nitrobenzaldimine), (II).

Molecules of ethane-1,2-diylbis(4-nitrobenzaldimine), (I) (Fig. 1), lie across centres of inversion in space group P2₁/n, and the reference molecule was selected to lie across (1/2, 1/2, 1/2). The key torsion angles (Table 1) show that the N11—C11 bond almost eclipses the C12—H12A bond; the C11—N11—C12—H12A angle is only 2.3°. The two halves of the molecule are otherwise each nearly planar. The bond lengths and interbond angles agree closely with those found by Sun et al. (2004) and show no unusual values.

The molecules of (I) are linked into sheets by a single, fairly short C—H···O hydrogen bond (Table 2). The atoms C6 at (x, y, z) and (1 − x, 1 − y 1 − z), which lie in the molecule centred at (1/2, 1/2, 1/2) act as hydrogen-bond donors respectively to the atoms O41 at (−0.5 + x, 1.5 − y, −0.5 + z) and (1.5 − x, −0.5 + y, 1.5 − z), which themselves lie in the molecules centred at (0, 1, 0) and (1, 0, 1). In a similar way, the atoms O41 at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms C6 at (0.5 + x, 1.5 − y, 0.5 + z) and (0.5 − x, −0.5 + y, 0.5 − z) respectively, which lie in the molecules centred at (1, 1, 1) and (0, 0, 0) respectively. In this manner, each molecule is linked to four others, forming a (10–1) sheet (Fig. 2) in the form of a (4, 4) net (Batten & Robson, 1998), built from a single type of R⁴₄(42) ring (Bernstein et al., 1995).

A single π–π stacking interaction links adjacent sheets. The aryl rings at (x, y, z) and (1 − x, 1 − y, 2 − z) are components of the molecules centred at (1/2, 1/2, 1/2) and (1/2, 1/2, 1.5), respectively. These rings are strictly parallel, with an interplanar separation of 3.419 (2) Å; the ring-centroid separation is 3.696 (2) Å, corresponding to a near-ideal ring-centroid offset of 1.404 (2) Å. Propagation of this stacking interaction by translation and inversion links the molecules into a molecular ladder running parallel to the [001] direction (Fig. 3), and this ladder suffices to link each (10–1) sheet to the two adjacent sheets, hence forming a continuous three-dimensional array.

Molecules of propane-1,3-diylbis(4-nitrobenzaldimine), (II) (Fig. 4), lie across twofold rotation axes in space group C2/c, and the reference molecule was selected to lie across the axis along (1/2, y, 1/4). The central spacer unit has a conformation exhibiting almost perfect staggering about the C—C bonds (Table 3) and, as in (I), the outer portions of the molecule are nearly planar.

Molecules of (II) are linked into chains of spiro-fused rings by a single C—H···O hydrogen bond (Table 4). Atom C13 at (1/2, y, 1/4) acts as a hydrogen-bond donor to nitro atoms O41 at (x, 1 − y, −0.5 + z) and (1 − x, 1 − y, 1 − z), which themselves are components of the molecules across the twofold rotation axes (1/2, −y, −0.25) and (1/2, −y, 3/4), respectively. Propagation by rotation of this single hydrogen bond then generates a chain of spiro-fused centrosymmetric R²₂(22) rings running parallel to the [001] direction, in which atom C13 is the spiro atom (Fig. 5).

Two chains of this type, related to one another by the C-centring operation, pass through each unit cell, and the chains are linked into sheets by a single aromatic π–π stacking interaction. The aryl rings at (x, y, z) and (1.5 − x, 1.5 − y, 1 − z), which lie in molecules across the axes (1/2, y, 1/4) and (1, −y, 3/4), respectively, are strictly parallel, with an interplanar separation of 3.366 (2) Å; the ring-centroid separation is 3.664 (2) Å, corresponding to a near-ideal centroid offset of 1.447 (2) Å. Propagation of this interaction by inversion and rotation then generates a π-stacked [101] chain (Fig. 6). Since each molecule in this chain is also a component of a hydrogen-bonded chain along [001], the overall supramolecular structure takes the form of a (010) sheet.

Experimental top

Computing details top

Data collection: SMART (Bruker, 2000) for (I); COLLECT (Hooft, 1999) for (II). Cell refinement: SAINT (Bruker, 2000) for (I); DENZO (Otwinowski & Minor, 1997) and COLLECT for (II). Data reduction: SAINT for (I); DENZO and COLLECT for (II). For both compounds, 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).

Figures top

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Atoms labelled with the suffix `a' are at the symmetry position (1 − x, 1 − y, 1 − z), and displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of (I), showing the formation of a (10–1) sheet. For clarity, H atoms not involved in hydrogen bonding have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a π-stacked molecular ladder along [001]. For clarity, all of the H atoms have been omitted.
	Fig. 4. The molecule of (II), showing the atom-labelling scheme. Atoms labelled with the suffix `a' are at the symmetry position (1 − x, y, 0.5 − z), and displacement ellipsoids are drawn at the 30% probability level.
	Fig. 5. A stereoview of part of the crystal structure of (II), showing the formation of a [001] chain of spiro-fused R²₂(22) rings For clarity, H atoms not involved in hydrogen bonding have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a [101] π-stacked chain, which links the hydrogen-bonded chains into (010) sheets. For clarity, all of the H atoms have been omitted.

(I) N,N'-bis(4-nitrobenzylidene)ethane-1,2-diamine top

Crystal data top

C₁₆H₁₄N₄O₄	F(000) = 340
M_r = 326.31	D_x = 1.433 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2717 reflections
a = 9.1606 (5) Å	θ = 2.7–32.6°
b = 7.2295 (4) Å	µ = 0.11 mm⁻¹
c = 11.5201 (6) Å	T = 291 K
β = 97.515 (1)°	Block, colourless
V = 756.38 (7) Å³	0.47 × 0.37 × 0.25 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2717 independent reflections
Radiation source: fine-focus sealed X-ray tube	2008 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ–ω scans	θ_max = 32.6°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
T_min = 0.946, T_max = 0.974	k = −10→10
7869 measured reflections	l = −13→17

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.095P)² + 0.0285P] where P = (F_o² + 2F_c²)/3
2717 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₆H₁₄N₄O₄	V = 756.38 (7) Å³
M_r = 326.31	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.1606 (5) Å	µ = 0.11 mm⁻¹
b = 7.2295 (4) Å	T = 291 K
c = 11.5201 (6) Å	0.47 × 0.37 × 0.25 mm
β = 97.515 (1)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2717 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2008 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.974	R_int = 0.020
7869 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.05	Δρ_max = 0.21 e Å⁻³
2717 reflections	Δρ_min = −0.24 e Å⁻³
109 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.65651 (10)	0.61482 (12)	0.84386 (8)	0.0394 (2)
C2	0.76610 (11)	0.55056 (15)	0.92992 (9)	0.0455 (2)
C3	0.75854 (11)	0.58513 (15)	1.04745 (9)	0.0480 (2)
C4	0.64019 (10)	0.68550 (13)	1.07645 (8)	0.0428 (2)
C5	0.53105 (11)	0.75438 (14)	0.99337 (9)	0.0452 (2)
C6	0.54022 (10)	0.71854 (13)	0.87660 (8)	0.0440 (2)
N4	0.62729 (11)	0.71766 (14)	1.20096 (8)	0.0538 (3)
O41	0.71543 (10)	0.64149 (18)	1.27437 (7)	0.0762 (3)
O42	0.52630 (12)	0.81622 (15)	1.22517 (8)	0.0737 (3)
C11	0.66027 (11)	0.56711 (14)	0.71954 (8)	0.0438 (2)
N11	0.56005 (11)	0.61914 (13)	0.64048 (7)	0.0497 (2)
C12	0.56739 (13)	0.55764 (17)	0.52097 (9)	0.0532 (3)
H2	0.8450	0.4838	0.9083	0.055*
H3	0.8311	0.5419	1.1051	0.058*
H5	0.4534	0.8231	1.0155	0.054*
H6	0.4681	0.7640	0.8194	0.053*
H11	0.7382	0.4972	0.6991	0.053*
H12A	0.6557	0.4846	0.5182	0.064*
H12B	0.5716	0.6640	0.4702	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0442 (4)	0.0389 (4)	0.0352 (4)	−0.0029 (3)	0.0052 (3)	−0.0012 (3)
C2	0.0447 (5)	0.0504 (5)	0.0416 (5)	0.0043 (4)	0.0062 (4)	0.0002 (4)
C3	0.0458 (5)	0.0576 (6)	0.0391 (5)	−0.0014 (4)	0.0002 (4)	0.0040 (4)
C4	0.0477 (5)	0.0471 (5)	0.0340 (4)	−0.0109 (4)	0.0071 (3)	−0.0042 (3)
C5	0.0465 (5)	0.0462 (5)	0.0434 (5)	0.0000 (4)	0.0080 (4)	−0.0069 (4)
C6	0.0461 (5)	0.0471 (5)	0.0378 (4)	0.0030 (4)	0.0015 (3)	−0.0017 (4)
N4	0.0557 (5)	0.0685 (6)	0.0379 (4)	−0.0184 (4)	0.0092 (4)	−0.0077 (4)
O41	0.0651 (5)	0.1246 (9)	0.0378 (4)	−0.0088 (5)	0.0026 (4)	0.0041 (5)
O42	0.0873 (7)	0.0845 (7)	0.0534 (5)	0.0000 (5)	0.0240 (5)	−0.0194 (4)
C11	0.0503 (5)	0.0442 (5)	0.0378 (4)	−0.0007 (3)	0.0094 (4)	−0.0036 (3)
N11	0.0622 (5)	0.0531 (5)	0.0336 (4)	0.0032 (4)	0.0053 (3)	−0.0064 (3)
C12	0.0685 (6)	0.0585 (6)	0.0331 (4)	−0.0018 (5)	0.0091 (4)	−0.0064 (4)

Geometric parameters (Å, º) top

C1—C6	1.3945 (13)	C5—H5	0.93
C1—C2	1.3951 (13)	C6—H6	0.93
C1—C11	1.4778 (12)	N4—O41	1.2213 (14)
C2—C3	1.3874 (13)	N4—O42	1.2283 (14)
C2—H2	0.93	C11—N11	1.2630 (13)
C3—C4	1.3814 (14)	C11—H11	0.93
C3—H3	0.93	N11—C12	1.4566 (12)
C4—C5	1.3833 (15)	C12—C12ⁱ	1.515 (2)
C4—N4	1.4730 (12)	C12—H12A	0.97
C5—C6	1.3832 (13)	C12—H12B	0.97

C6—C1—C2	119.41 (8)	C5—C6—H6	119.7
C6—C1—C11	120.20 (8)	C1—C6—H6	119.7
C2—C1—C11	120.34 (8)	O41—N4—O42	123.62 (10)
C3—C2—C1	120.69 (9)	O41—N4—C4	118.24 (10)
C3—C2—H2	119.7	O42—N4—C4	118.12 (10)
C1—C2—H2	119.7	N11—C11—C1	121.50 (9)
C4—C3—C2	118.14 (9)	N11—C11—H11	119.3
C4—C3—H3	120.9	C1—C11—H11	119.2
C2—C3—H3	120.9	C11—N11—C12	118.14 (9)
C3—C4—C5	122.74 (9)	N11—C12—C12ⁱ	109.44 (11)
C3—C4—N4	118.94 (9)	N11—C12—H12A	109.8
C5—C4—N4	118.31 (9)	C12ⁱ—C12—H12A	109.8
C6—C5—C4	118.37 (9)	N11—C12—H12B	109.8
C6—C5—H5	120.8	C12ⁱ—C12—H12B	109.8
C4—C5—H5	120.8	H12A—C12—H12B	108.2
C5—C6—C1	120.63 (9)

C6—C1—C2—C3	1.52 (15)	C11—C1—C6—C5	176.06 (9)
C11—C1—C2—C3	−176.01 (9)	C12ⁱ—C12—N11—C11	118.31 (13)
C1—C2—C3—C4	−0.35 (16)	C12—N11—C11—C1	−176.58 (8)
C2—C3—C4—C5	−0.92 (15)	N11—C11—C1—C2	177.91 (9)
C2—C3—C4—N4	177.73 (9)	C3—C4—N4—O41	−5.86 (15)
C3—C4—C5—C6	0.97 (15)	C5—C4—N4—O41	172.85 (10)
N4—C4—C5—C6	−177.69 (8)	C3—C4—N4—O42	175.80 (10)
C4—C5—C6—C1	0.25 (15)	C5—C4—N4—O42	−5.49 (14)
C2—C1—C6—C5	−1.47 (15)	C6—C1—C11—N11	0.41 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O41ⁱⁱ	0.93	2.40	3.2166 (13)	146

Symmetry code: (ii) x−1/2, −y+3/2, z−1/2.

(II) N,N'-bis(4-nitrobenzylidene)propane-1,3-diamine top

Crystal data top

C₁₇H₁₆N₄O₄	F(000) = 712
M_r = 340.34	D_x = 1.434 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1827 reflections
a = 12.9412 (6) Å	θ = 3.2–27.6°
b = 7.3062 (3) Å	µ = 0.11 mm⁻¹
c = 16.9061 (8) Å	T = 120 K
β = 99.559 (2)°	Needle, orange
V = 1576.29 (12) Å³	0.20 × 0.09 × 0.04 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer, Bruker–Nonius 95mm CCD camera on κ-goniostat	1827 independent reflections
Radiation source: Bruker–Nonius FR591 rotating-anode	1306 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.2°
ϕ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
T_min = 0.984, T_max = 0.996	l = −21→21
8695 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0884P)² + 0.3187P] where P = (F_o² + 2F_c²)/3
1827 reflections	(Δ/σ)_max < 0.001
114 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₇H₁₆N₄O₄	V = 1576.29 (12) Å³
M_r = 340.34	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.9412 (6) Å	µ = 0.11 mm⁻¹
b = 7.3062 (3) Å	T = 120 K
c = 16.9061 (8) Å	0.20 × 0.09 × 0.04 mm
β = 99.559 (2)°

Data collection top

Nonius KappaCCD diffractometer, Bruker–Nonius 95mm CCD camera on κ-goniostat	1827 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1306 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.996	R_int = 0.052
8695 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
1827 reflections	Δρ_min = −0.25 e Å⁻³
114 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O41	0.65464 (11)	1.27888 (18)	0.60355 (8)	0.0389 (4)
O42	0.64118 (11)	1.04371 (18)	0.67879 (8)	0.0387 (4)
N4	0.64425 (11)	1.1139 (2)	0.61311 (9)	0.0292 (4)
N11	0.60720 (11)	0.47737 (19)	0.34231 (8)	0.0262 (4)
C1	0.62024 (13)	0.7665 (2)	0.41140 (10)	0.0232 (4)
C2	0.63638 (14)	0.9535 (2)	0.40363 (10)	0.0247 (4)
C3	0.64361 (13)	1.0696 (2)	0.46909 (10)	0.0256 (4)
C4	0.63569 (13)	0.9936 (2)	0.54262 (10)	0.0241 (4)
C5	0.61994 (14)	0.8077 (2)	0.55255 (10)	0.0260 (4)
C6	0.61140 (13)	0.6944 (2)	0.48661 (10)	0.0239 (4)
C11	0.61378 (13)	0.6499 (2)	0.33954 (10)	0.0251 (4)
C12	0.60014 (14)	0.3797 (2)	0.26587 (10)	0.0266 (4)
C13	0.5000	0.2671 (3)	0.2500	0.0265 (6)
H2	0.6426	1.0024	0.3526	0.030*
H3	0.6537	1.1974	0.4636	0.031*
H5	0.6151	0.7594	0.6040	0.031*
H6	0.5995	0.5672	0.4923	0.029*
H11	0.6146	0.7067	0.2891	0.030*
H12A	0.6615	0.2980	0.2676	0.032*
H12B	0.6007	0.4688	0.2218	0.032*
H13A	0.5026	0.1871	0.2031	0.032*	0.50
H13B	0.4974	0.1871	0.2969	0.032*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0193 (9)	0.0245 (9)	0.0247 (9)	0.0022 (7)	0.0005 (7)	−0.0003 (7)
C11	0.0238 (9)	0.0289 (10)	0.0218 (9)	−0.0005 (7)	0.0018 (7)	0.0037 (7)
N11	0.0297 (9)	0.0255 (8)	0.0228 (8)	−0.0010 (6)	0.0028 (6)	−0.0008 (6)
C12	0.0296 (10)	0.0279 (9)	0.0228 (9)	−0.0009 (7)	0.0054 (7)	−0.0017 (7)
C13	0.0286 (14)	0.0269 (13)	0.0242 (12)	0.000	0.0051 (10)	0.000
C2	0.0232 (9)	0.0267 (9)	0.0234 (9)	0.0015 (7)	0.0013 (7)	0.0042 (7)
C3	0.0223 (9)	0.0233 (9)	0.0305 (10)	0.0006 (7)	0.0021 (7)	0.0013 (7)
C4	0.0183 (9)	0.0268 (10)	0.0271 (9)	−0.0001 (7)	0.0035 (7)	−0.0051 (7)
N4	0.0246 (8)	0.0311 (9)	0.0325 (9)	−0.0039 (6)	0.0072 (6)	−0.0069 (7)
O42	0.0462 (9)	0.0445 (8)	0.0278 (7)	−0.0105 (6)	0.0130 (6)	−0.0059 (6)
O41	0.0450 (9)	0.0278 (8)	0.0452 (9)	−0.0040 (6)	0.0116 (7)	−0.0090 (6)
C5	0.0244 (10)	0.0312 (10)	0.0232 (9)	−0.0008 (7)	0.0057 (7)	0.0008 (7)
C6	0.0228 (10)	0.0225 (9)	0.0267 (9)	−0.0010 (7)	0.0047 (7)	0.0011 (7)

Geometric parameters (Å, º) top

C1—C2	1.391 (2)	C2—C3	1.385 (2)
C1—C6	1.398 (2)	C2—H2	0.95
C1—C11	1.475 (2)	C3—C4	1.381 (2)
C11—N11	1.265 (2)	C3—H3	0.95
C11—H11	0.95	C4—C5	1.387 (2)
N11—C12	1.466 (2)	C4—N4	1.470 (2)
C12—C13	1.520 (2)	N4—O41	1.2265 (19)
C12—H12A	0.99	N4—O42	1.2296 (19)
C12—H12B	0.99	C5—C6	1.378 (2)
C13—C12ⁱ	1.520 (2)	C5—H5	0.95
C13—H13A	0.99	C6—H6	0.95
C13—H13B	0.99

C2—C1—C6	119.45 (15)	C3—C2—C1	121.14 (15)
C2—C1—C11	118.57 (15)	C3—C2—H2	119.4
C6—C1—C11	121.97 (15)	C1—C2—H2	119.4
N11—C11—C1	122.69 (15)	C4—C3—C2	117.90 (15)
N11—C11—H11	118.7	C4—C3—H3	121.1
C1—C11—H11	118.7	C2—C3—H3	121.1
C11—N11—C12	116.57 (14)	C3—C4—C5	122.46 (15)
N11—C12—C13	110.20 (12)	C3—C4—N4	118.85 (15)
N11—C12—H12A	109.6	C5—C4—N4	118.68 (15)
C13—C12—H12A	109.6	O41—N4—O42	123.34 (15)
N11—C12—H12B	109.6	O41—N4—C4	118.42 (14)
C13—C12—H12B	109.6	O42—N4—C4	118.24 (15)
H12A—C12—H12B	108.1	C6—C5—C4	118.93 (16)
C12ⁱ—C13—C12	114.5 (2)	C6—C5—H5	120.5
C12ⁱ—C13—H13A	108.6	C4—C5—H5	120.5
C12—C13—H13A	108.6	C5—C6—C1	120.11 (16)
C12ⁱ—C13—H13B	108.6	C5—C6—H6	119.9
C12—C13—H13B	108.6	C1—C6—H6	119.9
H13A—C13—H13B	107.6

C12ⁱ—C13—C12—N11	67.65 (11)	C2—C3—C4—N4	179.36 (14)
C13—C12—N11—C11	−121.50 (17)	C5—C4—N4—O41	−177.59 (16)
C12—N11—C11—C1	179.33 (14)	C3—C4—N4—O42	−177.19 (16)
N11—C11—C1—C2	174.52 (17)	C5—C4—N4—O42	2.8 (2)
C3—C4—N4—O41	2.4 (2)	C3—C4—C5—C6	−0.3 (3)
C6—C1—C11—N11	−5.0 (3)	N4—C4—C5—C6	179.72 (15)
C6—C1—C2—C3	−0.2 (3)	C4—C5—C6—C1	1.0 (3)
C11—C1—C2—C3	−179.69 (15)	C2—C1—C6—C5	−0.8 (3)
C1—C2—C3—C4	0.8 (3)	C11—C1—C6—C5	178.73 (16)
C2—C3—C4—C5	−0.6 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O42ⁱⁱ	0.99	2.54	3.267 (2)	130

Symmetry code: (ii) x, −y+1, z−1/2.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₆H₁₄N₄O₄	C₁₇H₁₆N₄O₄
M_r	326.31	340.34
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, C2/c
Temperature (K)	291	120
a, b, c (Å)	9.1606 (5), 7.2295 (4), 11.5201 (6)	12.9412 (6), 7.3062 (3), 16.9061 (8)
β (°)	97.515 (1)	99.559 (2)
V (Å³)	756.38 (7)	1576.29 (12)
Z	2	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.11	0.11
Crystal size (mm)	0.47 × 0.37 × 0.25	0.20 × 0.09 × 0.04

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer	Nonius KappaCCD diffractometer, Bruker–Nonius 95mm CCD camera on κ-goniostat
Absorption correction	Multi-scan (SADABS; Bruker, 2000)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.946, 0.974	0.984, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	7869, 2717, 2008	8695, 1827, 1306
R_int	0.020	0.052
(sin θ/λ)_max (Å⁻¹)	0.758	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.158, 1.05	0.052, 0.158, 1.06
No. of reflections	2717	1827
No. of parameters	109	114
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24	0.21, −0.25

Computer programs: SMART (Bruker, 2000), COLLECT (Hooft, 1999), SAINT (Bruker, 2000), DENZO (Otwinowski & Minor, 1997) and COLLECT, SAINT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected torsion angles (º) for (I) top

C12ⁱ—C12—N11—C11	118.31 (13)	N11—C11—C1—C2	177.91 (9)
C12—N11—C11—C1	−176.58 (8)	C3—C4—N4—O41	−5.86 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O41ⁱⁱ	0.93	2.40	3.2166 (13)	146

Symmetry code: (ii) x−1/2, −y+3/2, z−1/2.

Selected torsion angles (º) for (II) top

C12ⁱ—C13—C12—N11	67.65 (11)	N11—C11—C1—C2	174.52 (17)
C13—C12—N11—C11	−121.50 (17)	C3—C4—N4—O41	2.4 (2)
C12—N11—C11—C1	179.33 (14)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O42ⁱⁱ	0.99	2.54	3.267 (2)	130

Symmetry code: (ii) x, −y+1, z−1/2.

Acknowledgements

X-ray data for (I) were collected at the University of Aberdeen; the authors thank the University of Aberdeen for funding the purchase of the diffractometer. X-ray data for (II) were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work. JLW thanks CNPq and FAPERJ for financial support.

References

Batten, S, R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494. Web of Science CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2000). SMART (Version 5.624), SAINT-Plus (Version 6.02A) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. 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
Sun, Y.-X., You, Z.-L. & Zhu, H.-L. (2004). Acta Cryst. E60, o1707–o1708. Web of Science CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2053-2296

Volume 61| Part 1| January 2005| Pages o53-o56

doi:10.1107/S0108270104030719

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

π-Stacked hydrogen-bonded sheets in N,N′-bis­(4-nitro­benzyl­­idene)­ethane-1,2-di­amine and π-stacked hydrogen-bonded chains in N,N′-bis­(4-nitro­benzyl­­idene)­propane-1,3-di­amine

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

π-Stacked hydrogen-bonded sheets in N,N′-bis(4-nitrobenzylidene)ethane-1,2-diamine and π-stacked hydrogen-bonded chains in N,N′-bis(4-nitrobenzylidene)propane-1,3-diamine