(E,E)-1,4-Bis(2-iodo­phen­yl)-2,3-diaza-1,3-butadiene

Wardell, J.L.; Low, J.N.; Glidewell, C.

doi:10.1107/S1600536806010385

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 4| April 2006| Pages o1565-o1566

https://doi.org/10.1107/S1600536806010385

(E,E)-1,4-Bis(2-iodophenyl)-2,3-diaza-1,3-butadiene

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

^aInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro-RJ, Brazil, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen, AB24 3UE, UK, and ^cSchool of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 20 March 2006; accepted 21 March 2006; online 25 March 2006)

The molecules of the title compound C₁₄H₁₀I₂N₂, which are almost planar, lie across centres of inversion. The structure contains no direction-specific intermolecular interactions of any kind.

Comment

We recently reported that small quantities (ca 10%) of the title compound (I) (Fig.1) readily co-crystallized with (E,E)-1-(2-iodophenyl)-4-(2-nitrophenyl)-2,3-diaza-1,3-butadiene (II), and that the presence of (I) probably arose from some minor reorganization of the substituted aryl groups during either the synthesis or the recrystallization of (II) (Glidewell et al., 2005 ). In order to assess the relationship between the structures of (I) and (II), we now report the structure of (I).

The molecules of (I) lie across inversion centres in space group P2₁/n, and they are almost planar, as shown by the key torsion angles (Table 1). The bond lengths and angles present no unusual features, apart from the exocyclic bond angles at C2, most plausibly associated with the repulsive intramolecular contact between atoms I2 and the H atom bonded to C7. There are no direction-specific interactions of any kind in the crystal structure of (I): C—H⋯N and C—H⋯π(arene) hydrogen bonds, aromatic π–π stacking interactions, and short I⋯I interactions are all absent.

The unit-cell dimensions for compounds (I) and (II) are very different, and these compounds also crystallize in different space groups, with molar volumes which differ by some 5%. It is therefore not clear why compound (I) so readily co-crystallizes with compound (II).

Isomeric with (I) is compound (III) where, again, nearly planar molecules lie across centres of inversion (Cho et al., 2005 ).

Figure 1
The molecular structure of compound (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and atoms labelled with suffix `a' are related by the symmetry operator (1 − x, 1 − y, 1 − z).

Experimental

A mixture of 2-iodobenzaldehyde (1 mmol) and hydrazine hydrate (0.5 mmol) in methanol (20 cm³) was heated under reflux for 30 min. The mixture was cooled and the solvent was removed under reduced pressure. The product, (I), was purified by chromatography on alumina, using CHCl₃ as eluent: crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in ethanol.

Crystal data

C₁₄H₁₀I₂N₂
M_r = 460.04
Monoclinic, P 2₁ /n
a = 13.2667 (4) Å
b = 4.1070 (2) Å
c = 13.8207 (4) Å
β = 110.3140 (15)°
V = 706.20 (5) Å³
Z = 2
D_x = 2.163 Mg m⁻³
Mo Kα radiation
Cell parameters from 1818 reflections
θ = 1.0–27.4°
μ = 4.44 mm⁻¹
T = 120 (2) K
Lath, yellow
0.64 × 0.12 × 0.08 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.160, T_max = 0.703
9545 measured reflections
1614 independent reflections
1455 reflections with I > 2σ(I)
R_int = 0.027
θ_max = 27.5°
h = −17 → 15
k = −5 → 5
l = −17 → 17

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.075
S = 1.30
1614 reflections
82 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0439P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.64 e Å⁻³
Δρ_min = −1.16 e Å⁻³

Table 1
Selected bond and torsion angles (°)

C3—C2—C1	121.6 (3)
C3—C2—I2	116.2 (2)
C1—C2—I2	122.2 (2)

C6—C1—C7—N1	−5.2 (5)
C1—C7—N1—N1ⁱ	−179.9 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

All H atoms were located in difference maps and they were then treated as riding atoms with C—H distances 0.95 Å and U_iso(H) = 1.2U_eq(C). The deepest hole is located 0.72 Åfrom atom I2.

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) & COLLECT); data reduction: DENZO & 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/S1600536806010385/lh2027sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806010385/lh2027Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) & COLLECT); data reduction: DENZO & 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).

(E,E)-1,4-Bis(2-iodophenyl)-2,3-diaza-1,3-butadiene top

Crystal data top

C₁₄H₁₀I₂N₂	F(000) = 428
M_r = 460.04	D_x = 2.163 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1818 reflections
a = 13.2667 (4) Å	θ = 1.0–27.4°
b = 4.1070 (2) Å	µ = 4.44 mm⁻¹
c = 13.8207 (4) Å	T = 120 K
β = 110.3140 (15)°	Lath, yellow
V = 706.20 (5) Å³	0.64 × 0.12 × 0.08 mm
Z = 2

Data collection top

Bruker-Nonius KappaCCD diffractometer	1614 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1455 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 1.8°
φ & ω scans	h = −17→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −5→5
T_min = 0.160, T_max = 0.703	l = −17→17
9545 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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.30	w = 1/[σ²(F_o²) + (0.0439P)²] where P = (F_o² + 2F_c²)/3
1614 reflections	(Δ/σ)_max = 0.001
82 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −1.16 e Å⁻³

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

	x	y	z	U_iso*/U_eq
C1	0.7374 (3)	0.4440 (7)	0.5557 (2)	0.0150 (6)
C2	0.8164 (2)	0.3184 (8)	0.5201 (2)	0.0149 (6)
I2	0.777975 (15)	0.09737 (5)	0.373819 (14)	0.01682 (12)
C3	0.9252 (3)	0.3381 (8)	0.5790 (3)	0.0204 (7)
C4	0.9564 (3)	0.4865 (10)	0.6753 (3)	0.0243 (7)
C5	0.8802 (3)	0.6146 (7)	0.7125 (3)	0.0217 (8)
C6	0.7720 (3)	0.5935 (7)	0.6531 (3)	0.0183 (7)
C7	0.6223 (3)	0.4242 (7)	0.4961 (3)	0.0173 (7)
N1	0.5529 (2)	0.5194 (8)	0.5345 (2)	0.0220 (6)
H3	0.9776	0.2510	0.5536	0.025*
H4	1.0305	0.5003	0.7160	0.029*
H5	0.9019	0.7163	0.7783	0.026*
H6	0.7202	0.6823	0.6788	0.022*
H7	0.5991	0.3393	0.4279	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0170 (16)	0.0159 (15)	0.0130 (15)	0.0026 (11)	0.0064 (13)	0.0050 (11)
C2	0.0177 (15)	0.0163 (13)	0.0112 (14)	−0.0006 (12)	0.0056 (12)	0.0030 (12)
I2	0.01818 (16)	0.01792 (16)	0.01565 (16)	0.00262 (6)	0.00751 (11)	−0.00004 (6)
C3	0.0167 (16)	0.0255 (16)	0.0198 (17)	0.0041 (13)	0.0072 (13)	0.0064 (13)
C4	0.0149 (16)	0.0342 (17)	0.0203 (17)	−0.0014 (15)	0.0017 (13)	0.0048 (15)
C5	0.0231 (19)	0.030 (2)	0.0104 (17)	−0.0047 (12)	0.0035 (14)	0.0006 (11)
C6	0.0194 (18)	0.0246 (17)	0.0147 (16)	0.0001 (11)	0.0106 (14)	−0.0001 (11)
C7	0.0148 (16)	0.0243 (17)	0.0116 (16)	0.0018 (11)	0.0033 (13)	−0.0003 (11)
N1	0.0140 (14)	0.0348 (15)	0.0167 (14)	0.0035 (13)	0.0047 (11)	−0.0022 (13)

Geometric parameters (Å, º) top

C1—C2	1.402 (4)	C4—H4	0.95
C1—C6	1.403 (5)	C5—C6	1.387 (5)
C1—C7	1.464 (5)	C5—H5	0.95
C2—C3	1.391 (4)	C6—H6	0.95
C2—I2	2.111 (3)	C7—N1	1.273 (5)
C3—C4	1.391 (5)	C7—H7	0.95
C3—H3	0.95	N1—N1ⁱ	1.407 (6)
C4—C5	1.387 (6)

C2—C1—C6	117.5 (3)	C3—C4—H4	119.7
C2—C1—C7	122.9 (3)	C6—C5—C4	119.6 (3)
C6—C1—C7	119.6 (3)	C6—C5—H5	120.2
C3—C2—C1	121.6 (3)	C4—C5—H5	120.2
C3—C2—I2	116.2 (2)	C5—C6—C1	121.5 (3)
C1—C2—I2	122.2 (2)	C5—C6—H6	119.2
C4—C3—C2	119.3 (3)	C1—C6—H6	119.2
C4—C3—H3	120.4	N1—C7—C1	120.8 (3)
C2—C3—H3	120.4	N1—C7—H7	119.6
C5—C4—C3	120.5 (3)	C1—C7—H7	119.6
C5—C4—H4	119.7	C7—N1—N1ⁱ	112.3 (4)

C6—C1—C2—C3	0.5 (5)	C3—C4—C5—C6	0.2 (5)
C7—C1—C2—C3	−179.4 (3)	C4—C5—C6—C1	0.2 (5)
C6—C1—C2—I2	−178.3 (2)	C2—C1—C6—C5	−0.5 (5)
C7—C1—C2—I2	1.8 (4)	C7—C1—C6—C5	179.4 (3)
C1—C2—C3—C4	−0.2 (5)	C2—C1—C7—N1	174.7 (3)
I2—C2—C3—C4	178.7 (3)	C6—C1—C7—N1	−5.2 (5)
C2—C3—C4—C5	−0.2 (5)	C1—C7—N1—N1ⁱ	−179.9 (3)

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, UK; the authors thank the staff of the Service for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

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