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Three polymorphs of 4,4′-diiodobenzalazine (systematic name: 4-iodo­benzaldehyde azine), C14H10I2N2, have crystallographically imposed inversion symmetry. 4-Chloro-4′-iodobenzalazine [systematic name: 1-(4-chloro­benzyl­idene)-2-(4-iodo­benzyl­idene)diazane], C14H10ClIN2, has a partially disordered pseudocentrosymmetric packing and is not isostructural with any of the polymorphs of 4,4′-diiodo­benzalazine. All structures pack utilizing halogen–halogen inter­actions; some also have weak π (benzene ring) inter­actions. A comparison with previously published methyl­phenyl­ketalazines (which differ by substitution of methyl for H at the azine C atoms) shows a fundamentally different geometry for these two classes, namely planar for the alazines and twisted for the ketalazines. Density functional theory calculations confirm that the difference is fundamental and not an artifact of packing forces.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107034786/ga3056sup1.cif
Contains datablocks global, I,I-A, I,I-B, I,I-C, I,Cl

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107034786/ga3056I,I-Asup2.hkl
Contains datablock I,I-A

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107034786/ga3056I,I-Bsup3.hkl
Contains datablock I,I-B

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107034786/ga3056I,I-Csup4.hkl
Contains datablock I,I-C

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107034786/ga3056I,Clsup5.hkl
Contains datablock I,Cl

CCDC references: 661806; 661807; 661808; 661809

Comment top

In this paper the descriptor (X,Y) is used as an abbreviation for 4-X-4'-Y-benzalazine, with the three title polymorphs designated as (I,I-A),(I,I-B) and (I,I-C). Crystals of the dichloro and dibromo analogs, (Cl,Cl) and (Br,Br), of the (I,I) title compound are not isostructural (Zheng et al., 2005; Marignan et al., 1972). The structure of (I,I) was undertaken to compare the packing with that of (Br,Br). When three polymorphs of (I,I) were found, the study was expanded to include (Br,Cl), (I,Cl) and (I,Br) to see if these were isostructural with one or another of the (X,X) compounds.

Fig. 1 shows the atom labeling and the anisotropic displacement ellipsoid plots for (I,I-A) and (I,Cl). Molecules of (I,I-A) lie on a center of symmetry. (I,Cl) is disordered about a pseudo-center of symmetry, with 0.586 (2) as the fraction for the major component of the disorder. In both structures, the bond lengths and angles are normal. The labelings for all of the compounds described here are the same; the anisotropic displacement ellipsoid plots for (I,I-B) and I,I-C) are similar to those of (I,I-A).

The packing of (I,I-A) is shown in Fig. 2. The molecules assemble in ribbons held together by I···I interactions and parallel to the [102] direction. The ribbons form sheets normal to the b axis, with the essentially planar molecules tilted 33.4 (1)° away from the plane of the sheet. Adjacent sheets form a herringbone pattern. Table 1 gives the geometric data for all of the I···I contacts.

The packing of (I,I-B) is shown in Fig. 3. The molecules assemble in layers held together by I···I interactions and parallel to the (103) plane. The molecules are tilted 34.9 (1)° away from the mean plane of the layer; alternate molecules are tilted in opposite directions away from the plane.

The packing of (I,I-C) is shown in Fig. 4. The molecules assemble in layers held together by I···I interactions and parallel to the (104) plane. The molecules are tilted 58.6 (1)° away from the mean plane of the layer; alternate molecules are tilted in opposite directions away from the plane. There are two kinds of I···I interactions, one lying across a 21 axis and the other lying along the b axis.

The packing of (I,Cl) is shown in Fig. 5. The disordered molecules (as noted above) assemble in layers held together by I···I, I···Cl or Cl···Cl interactions. The molecules are tilted 59.9 (1)° away from the mean plane. All of the molecules in a given layer have the same tilt; those in the adjacent layer tilt in the opposite sense. This leads to a herringbone pattern between the layers. There are two kinds of I···I interactions, one lying across a 21 axis and the other lying along the b axis. There is some similarity in this respect with the packing arrangement of (I,Cl) and (I,I-C).

Schmidt (1971) showed that dichloro aromatic compounds often crystallize with a short, approximately 4 Å axis, presumably, in part, as a consequence of weak intermolecular Cl···Cl interactions. Sakurai et al. (1963) pointed out two other kinds of Cl···Cl interactions, viz. an approximately linear arrangement across a center of symmetry, and an angular arrangement across a 21 axis or a glide plane. These interactions have been discussed by Desiraju (1987, 1989, 1995). Examples of all of these are shown in the four compounds reported here. (I,I-A) has the approximately linear arrangement across a center of symmetry. (I,I-B), (I,I-C), and (I,Cl) all adopt the angular arrangement across a 21 axis. In addition, (I,Cl) and (I,I-C) have short axial contacts of the type pointed out by Schmidt (1971). The distances and angles for all of the X···X interactions are listed in Table 1. Also included in Table 1 are the same data for the compounds (X,X)*, where X = Cl, Br or I and the * refers to the analogous molecules in which the aliphatic H atoms have been replaced by methyl groups (the methylphenylketalazines, hereafter referred to as simply ketalazines). In this latter series, the X···X distances are significantly shorter in every case except for the (I,I) case.

The (X,X) and (X,X)* molecules differ in that the (X,X) molecules are all planar while the (X,X)* molecules are not, even though they all have gauche configurations around the N—N bonds. A comparison of benzalazine structures with ketalazine structures (Chen et al., 1994; Bolte & Ton, 2003; Lewis et al., 1999) confirms the fundamentally different geometry for the two systems. In the benzalazine structures, including the non-para-substituted parent system, the molecules are effectively planar with fully conjugated π systems. By contrast, in the ketalazine structures, again including the parent system, the torsion angle about the central CNNC linkage is large, ranging from 50 to 100° depending on the para substitution.

To better understand this difference, we carried out density functional structure calculations using the M06 density functional (Zhao & Truhlar, 2007) and the MIDI! basis set (Easton et al., 1996). For the case of 4,4'-dichloro substitution, both the benzalazine and ketalazine systems were subjected to constrained optimizations where the CNNC torsion angle was varied and held fixed in increments of 15° (Fig. 7). Interestingly, while the ketalazine is predicted to have a double-well potential characterized by a minimum-energy geometry with a CNNC dihedral angle of 105.3° (in very good agreement with the experimental value of 103.1°), the benzalazine has a triple well potential, with very shallow minima predicted for the symmetrically related twisted geometries and a more stable planar minimum predicted for the fully planar geometry (i.e. having a CNNC torsion angle of 180°). In each instance, the torsional potential is relatively flat over the range of 75 to 285°; the total variation in energy is only about 2 kcal mol-1. The methyl groups in the ketalazine experience unfavorable steric repulsion that causes the energy in this system to rise steeply outside this range. A full rotational coordinate for the benzalazine system was computed; the energy of the system having a CNNC torsion angle of 0° is predicted to be about 15 kcal mol-1 above the trans planar minimum.

The relatively flat potentials are associated with a balance between full π conjugation, available to the planar geometry, and a push–pull resonance available to the rotated system, which also minimizes NN lone-pair–lone-pair repulsions analogous to those in hydrazine, which also adopts a twisted minimum-energy geometry (Fig. 8). The deeper well for the twisted geometry of the ketalazine compared with the benzalazine, relative to the planar structure, is associated with improved hyperconjugative interactions for the nitrogen lone pairs delocalizing into the eclipsed π system when the methyl groups are present. Thus, Natural Bond Orbital analysis (Reed et al., 1988) quantifies the nN π* delocalization for each N lone pair as 16.5 kcal mol-1 in the ketalazine system, but only 13.5 kcal mol-1 in the benzalazine system. This is the largest difference in the filled/empty delocalization energies between the two systems. A consequence of this delocalization is that the NN bond should be shorter (because of some double-bond character) in the twisted systems than in the planar systems, and this is indeed borne out by the experimental structural data (see Table 2).

A second aspect of the packing in the azalazines is the π interaction between the benzene rings. The geometric aspects are given in Table 3, where the perpendicular distances between the rings and the overlap are given. The overlap is given as the percentage overlap of the areas in the adjacent C6 rings. The overlap for (I,I-C) is shown in Fig. 5; the molecules assemble in stacks along the short axis. With two exceptions, the others are similar; in (I,I-A) there is no overlap, and in (I,I-B) the molecules assemble in chains rather than stacks. (Br,Cl) and (Br,Br) appear to be isostructural with each other, as do (I,Cl) and (I,Br). These similarities would require disorder in (Br,Cl) and (I,Br). In view of the disorder in all of the (X,Y) structures, no data are included here for their π overlap. However, they all appear to be similar to that shown in Fig. 5.

The unit-cell dimensions for all of the (X,X) and (X,Y) structures are given in Table 4. The (Cl,Cl) structure is unique. (Br,Cl) and (Br,Br) are isostructural with (I,I-C). (I,Cl) and (I,Br) are isostructural only with each other. Thus there are five different structural types in this series of compounds. When three polymorphs of (I,I) were found, all the remaining compounds in Table 4 were examined to see if other polymorphs could be found. Each compound was recrystallized from acetone, benzene, methylene chloride, chloroform, carbon tetrachloride and acetonitrile. Although a variety of crystal habits were found for each compound, in no case were other polymorphs found.

Each of the five structure types in Table 4 gives a plausible packing arrangment for all of the benzalazine compounds. So this system, which involves only planar molecules, could provide a reasonable test for programs that predict crystal packing. It is surprising that in five of the six compounds no polymorphs were found, even though the search for polymorphs was not exhaustive.

Related literature top

For related literature, see: Bolte & Ton (2003); Chen et al. (1994); Desiraju (1987, 1989, 1995); Easton et al. (1996); Lewis et al. (1999); Marignan et al. (1972); Reed et al. (1988); Sakurai et al. (1963); Schmidt (1971); Zhao & Truhlar (2007); Zheng et al. (2005).

Experimental top

For the preparation of 4-chlorobenzaldehyde hydrazone, a solution of 4-chlorobenzaldehyde (0.5 g, 3.6 mmol) dissolved in approximately 10 ml of ethanol was added dropwise with stirring to an aqueous 8% hydrazine solution (14.25 g, 3.6 mmol hydrazine). The milky solution was stirred for approximately 30 min after the completion of the addition and then cooled in a refrigerator overnight (at 277 K). The solid hydrazone was removed by filtration and used without recrystallization.

For the preparation of 4-chloro-4'-iodobenzalazine, to a solution of 4-iodobenzaldehyde (0.2 g, 0.9 mmol) dissolved in 10 ml of absolute ethanol was added 4-chlorobenzaldehyde hydrazone (0.15 g, 1.0 mmol). The mixture was heated to 323 K with stirring for approximately 1 h, cooled, and then placed in a refrigerator overnight. The crude azine was recrystallized from chloroform.

For the preparation of 4-iodobenzaldehyde azine, a solution of 4-iodobenzaldehyde (0.1 g, 0.4 mmol) dissolved in approximately 5 ml of ethanol was added dropwise with stirring to an aqueous 8% hydrazine solution (3 g, 8 mmol hydrazine). The milky solution was heated (lower than 323 K) with stirring for approximately 1 h and then was allowed to stand at room temperature overnight. The solution was refrigerated and the crude azine was recrystallized from chloroform. All three polymorphs were obtained in the original recrystallization.

Refinement top

The solutions and refinements were straightforward, except for (I,Cl). This structure was solved as an end-for-end disordered molecule in P21/c; the refinement converged with R[F2>2σ(F2)] = 0.043 and wR(F2) = 0.084. To test whether the disorder was complete the structure was solved and partially refined in P1. At this point it appeared that the disorder was not 50/50 and that Pc was the correct space group; the final R and wR2 were 0.038 and 0.072 with 0.586 (2)/0.414 (2) disorder of the Cl and I. In all of the refinements C—Cl was constrained to 1.746 (1) and C—I to 2.095 (1) Å; all of the C6H4—CH—N fragments were constrained to be the same to 0.001 Å. The atoms that would have overlapped in the pseudocentric arrangement were constrained to have the same ADP's.

H atoms were placed at geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.95 Å and with Uiso(H) = 1.2 Ueq(C).

Computing details top

For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Top: (I,I-A) Displacement ellipsoids are shown at the 50% probability level. Only the crystallographically unique atoms are labeled. The labelings for (I,I-B) and (I,I-C) are the same; the displacement ellipsoids are similar. Bottom: (I,Cl) Only the major component of the disorder [fraction equal to 0.586 (2)] is shown in full, with displacement ellipsoids at the 50% probability level. The minor component is shown only in outline. The ellipsoids in the minor component are constrained to be identical to those of the overlapping atoms in the major component. The two components lie on a pseudo-symmetry center in space group Pc.
[Figure 2] Fig. 2. Top: One layer of the structure of (I,I-A), viewed normal to (100). The intermolecular I···I contacts are shown as dashed lines; these interactions lie across centers of symmetry. Bottom: Three layers viewed along [102]. The middle layer in this view is the layer shown in the top view.
[Figure 3] Fig. 3. Top: One layer of the structure of (I,I-B), viewed normal to (103). The intermolecular I···I interactions are shown as dashed lines; they zigzag about a 21 axis. Bottom: Three layers viewed along b. The middle layer in this view is the layer shown in the top view.
[Figure 4] Fig. 4. Top: One layer of the structure of (I,I—C), viewed normal to (104). There are two kinds of intermolecular I···I contacts. One, shown by dashed lines, zigzags about a 21 axis. The other, shown by dotted lines, lies along the b axis. Bottom: Three layers viewed along b. The middle layer in this view is the layer shown in the top view.
[Figure 5] Fig. 5. Top: One layer of the structure of (I,Cl), viewed normal to (101). As a reminder of the disorder, both Cl and I are shown at all positions; the rest of the disordered positions are not shown. Only the I···I contacts are shown. The conventions are the same as in Fig. 4. Bottom: Three layers viewed along b. The middle layer in this view is the layer shown in the top view.
[Figure 6] Fig. 6. The overlap between (I,I-C) molecules (view normal to the molecular plane). The area of the overlap between the C6 rings is 5.7 (3)% of the area of either ring.
[Figure 7] Fig. 7. The energies of the 4,4-dichlorobenzalazine (diamonds) and 4,4-dichloromethylphenylketalazine (squares) geometries relative to the planar structure having a CNNC dihedral angle of 180°.
[Figure 8] Fig. 8. Push–pull resonance in the twisted ketalazine geometry.
(I,I-A) 4-iodobenzaldehyde azine top
Crystal data top
C14H10I2N2F(000) = 428
Mr = 460.04Dx = 2.172 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.854 (2) ÅCell parameters from 2671 reflections
b = 7.7308 (13) Åθ = 2.6–27.5°
c = 7.6827 (13) ŵ = 4.45 mm1
β = 92.407 (3)°T = 174 K
V = 703.5 (2) Å3Plate, pale yellow
Z = 20.45 × 0.35 × 0.06 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1602 independent reflections
Radiation source: fine-focus sealed tube1442 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
h = 1515
Tmin = 0.32, Tmax = 0.77k = 910
7773 measured reflectionsl = 99
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.027P)2 + 0.31P]
where P = (Fo2 + 2Fc2)/3
1602 reflections(Δ/σ)max = 0.001
83 parametersΔρmax = 0.86 e Å3
0 restraintsΔρmin = 0.55 e Å3
Crystal data top
C14H10I2N2V = 703.5 (2) Å3
Mr = 460.04Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.854 (2) ŵ = 4.45 mm1
b = 7.7308 (13) ÅT = 174 K
c = 7.6827 (13) Å0.45 × 0.35 × 0.06 mm
β = 92.407 (3)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1602 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
1442 reflections with I > 2σ(I)
Tmin = 0.32, Tmax = 0.77Rint = 0.031
7773 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.054H-atom parameters constrained
S = 1.11Δρmax = 0.86 e Å3
1602 reflectionsΔρmin = 0.55 e Å3
83 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.114704 (15)0.42460 (2)0.33923 (2)0.03116 (9)
N10.4787 (2)0.4782 (3)0.4157 (3)0.0290 (5)
C10.2062 (2)0.4727 (3)0.1050 (3)0.0225 (5)
C20.1565 (2)0.5669 (3)0.0252 (4)0.0244 (5)
H20.08250.61250.00730.029*
C30.2167 (2)0.5937 (3)0.1822 (3)0.0258 (5)
H30.18370.65890.27170.031*
C40.3251 (2)0.5256 (3)0.2095 (3)0.0245 (5)
C50.3732 (2)0.4320 (3)0.0763 (4)0.0263 (5)
H50.44690.38530.09400.032*
C60.3148 (2)0.4064 (3)0.0814 (4)0.0268 (5)
H60.34850.34420.17240.032*
C70.3853 (2)0.5536 (3)0.3787 (4)0.0276 (6)
H70.35390.62900.46150.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.03674 (14)0.03150 (13)0.02453 (12)0.00061 (7)0.00715 (8)0.00406 (6)
N10.0338 (12)0.0315 (11)0.0212 (11)0.0037 (10)0.0057 (9)0.0010 (9)
C10.0284 (13)0.0192 (10)0.0196 (11)0.0027 (10)0.0030 (10)0.0011 (9)
C20.0259 (13)0.0217 (11)0.0252 (13)0.0016 (9)0.0027 (10)0.0013 (9)
C30.0318 (14)0.0229 (12)0.0226 (13)0.0033 (10)0.0005 (11)0.0028 (9)
C40.0284 (13)0.0229 (11)0.0217 (12)0.0036 (10)0.0038 (10)0.0033 (10)
C50.0236 (13)0.0283 (13)0.0268 (13)0.0015 (10)0.0008 (10)0.0021 (10)
C60.0298 (14)0.0273 (12)0.0235 (13)0.0014 (10)0.0035 (11)0.0001 (10)
C70.0315 (15)0.0269 (13)0.0241 (13)0.0034 (10)0.0034 (11)0.0000 (10)
Geometric parameters (Å, º) top
I1—C12.095 (2)C3—H30.9500
N1—C71.273 (4)C4—C51.395 (4)
N1—N1i1.411 (4)C4—C71.472 (4)
C1—C21.389 (4)C5—C61.384 (4)
C1—C61.391 (4)C5—H50.9500
C2—C31.391 (4)C6—H60.9500
C2—H20.9500C7—H70.9500
C3—C41.396 (4)
C7—N1—N1i111.7 (3)C5—C4—C7121.7 (2)
C2—C1—C6121.2 (2)C3—C4—C7119.1 (2)
C2—C1—I1119.47 (19)C6—C5—C4120.8 (2)
C6—C1—I1119.32 (18)C6—C5—H5119.6
C1—C2—C3119.0 (2)C4—C5—H5119.6
C1—C2—H2120.5C5—C6—C1119.2 (2)
C3—C2—H2120.5C5—C6—H6120.4
C2—C3—C4120.6 (2)C1—C6—H6120.4
C2—C3—H3119.7N1—C7—C4121.0 (3)
C4—C3—H3119.7N1—C7—H7119.5
C5—C4—C3119.2 (2)C4—C7—H7119.5
C6—C1—C2—C30.5 (4)C4—C5—C6—C11.1 (4)
I1—C1—C2—C3178.09 (18)C2—C1—C6—C51.4 (4)
C1—C2—C3—C40.6 (4)I1—C1—C6—C5177.25 (18)
C2—C3—C4—C50.8 (4)N1i—N1—C7—C4179.4 (3)
C2—C3—C4—C7178.8 (2)C5—C4—C7—N17.3 (4)
C3—C4—C5—C60.0 (4)C3—C4—C7—N1172.3 (2)
C7—C4—C5—C6179.6 (2)
Symmetry code: (i) x+1, y+1, z+1.
(I,I-B) 4-iodobenzaldehyde azine top
Crystal data top
C14H10I2N2F(000) = 428
Mr = 460.04Dx = 2.173 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.4303 (17) ÅCell parameters from 2860 reflections
b = 5.6453 (12) Åθ = 2.5–25.5°
c = 15.248 (3) ŵ = 4.46 mm1
β = 104.346 (3)°T = 174 K
V = 703.0 (3) Å3Needle, pale yellow
Z = 20.30 × 0.06 × 0.03 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1600 independent reflections
Radiation source: fine-focus sealed tube1189 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
h = 1010
Tmin = 0.54, Tmax = 0.87k = 77
7699 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.028P)2]
where P = (Fo2 + 2Fc2)/3
1600 reflections(Δ/σ)max = 0.001
83 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.61 e Å3
Crystal data top
C14H10I2N2V = 703.0 (3) Å3
Mr = 460.04Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.4303 (17) ŵ = 4.46 mm1
b = 5.6453 (12) ÅT = 174 K
c = 15.248 (3) Å0.30 × 0.06 × 0.03 mm
β = 104.346 (3)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1600 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
1189 reflections with I > 2σ(I)
Tmin = 0.54, Tmax = 0.87Rint = 0.052
7699 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.02Δρmax = 0.48 e Å3
1600 reflectionsΔρmin = 0.61 e Å3
83 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I11.14291 (3)1.16954 (5)0.306393 (19)0.03499 (13)
N10.5738 (4)0.5302 (7)0.4884 (2)0.0301 (8)
C10.9511 (5)1.0231 (7)0.3531 (3)0.0251 (9)
C20.8041 (5)1.1403 (7)0.3377 (3)0.0289 (9)
C30.6780 (5)1.0432 (7)0.3695 (3)0.0274 (9)
C40.6982 (5)0.8283 (7)0.4157 (3)0.0263 (9)
C50.8486 (5)0.7121 (7)0.4307 (3)0.0286 (9)
C60.9762 (5)0.8064 (7)0.4003 (3)0.0299 (10)
C70.5607 (5)0.7274 (7)0.4465 (3)0.0285 (10)
H20.78901.28620.30570.035*
H30.57641.12440.35960.033*
H50.86330.56560.46230.034*
H61.07860.72710.41090.036*
H70.45980.81090.43480.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.02812 (17)0.0440 (2)0.03479 (19)0.00089 (15)0.01144 (12)0.00570 (16)
N10.0252 (18)0.030 (2)0.036 (2)0.0060 (16)0.0102 (16)0.0003 (17)
C10.027 (2)0.024 (2)0.026 (2)0.0049 (18)0.0097 (18)0.0032 (18)
C20.034 (2)0.026 (2)0.026 (2)0.001 (2)0.0059 (18)0.0007 (18)
C30.022 (2)0.029 (2)0.031 (2)0.0006 (18)0.0066 (18)0.0029 (19)
C40.029 (2)0.026 (2)0.023 (2)0.001 (2)0.0056 (17)0.0042 (19)
C50.030 (2)0.024 (2)0.029 (2)0.0019 (18)0.0032 (18)0.0056 (18)
C60.027 (2)0.033 (2)0.029 (2)0.006 (2)0.0056 (18)0.005 (2)
C70.027 (2)0.030 (2)0.028 (2)0.0017 (18)0.0059 (19)0.0073 (19)
Geometric parameters (Å, º) top
I1—C12.091 (4)C6—C11.409 (5)
C4—C31.392 (6)C6—H60.9500
C4—C51.395 (5)C1—C21.373 (5)
C4—C71.468 (6)C2—C31.386 (5)
N1—C71.275 (5)C2—H20.9500
N1—N1i1.418 (6)C3—H30.9500
C5—C61.380 (6)C7—H70.9500
C5—H50.9500
C3—C4—C5119.0 (4)C2—C1—I1119.5 (3)
C3—C4—C7119.5 (4)C6—C1—I1119.1 (3)
C5—C4—C7121.5 (4)C1—C2—C3119.2 (4)
C7—N1—N1i111.3 (4)C1—C2—H2120.4
C6—C5—C4121.1 (4)C3—C2—H2120.4
C6—C5—H5119.5C2—C3—C4120.9 (4)
C4—C5—H5119.5C2—C3—H3119.6
C5—C6—C1118.4 (4)C4—C3—H3119.6
C5—C6—H6120.8N1—C7—C4121.4 (4)
C1—C6—H6120.8N1—C7—H7119.3
C2—C1—C6121.3 (4)C4—C7—H7119.3
C3—C4—C5—C60.2 (6)C1—C2—C3—C40.6 (6)
C7—C4—C5—C6179.0 (4)C5—C4—C3—C20.7 (6)
C4—C5—C6—C10.3 (6)C7—C4—C3—C2178.5 (4)
C5—C6—C1—C20.4 (6)N1i—N1—C7—C4179.7 (4)
C5—C6—C1—I1180.0 (3)C3—C4—C7—N1179.5 (4)
C6—C1—C2—C30.1 (6)C5—C4—C7—N10.3 (6)
I1—C1—C2—C3179.5 (3)
Symmetry code: (i) x+1, y+1, z+1.
(I,I-C) 4-iodobenzaldehyde azine top
Crystal data top
C14H10I2N2F(000) = 428
Mr = 460.04Dx = 2.188 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.2077 (17) ÅCell parameters from 3960 reflections
b = 4.1543 (10) Åθ = 2.8–27.5°
c = 23.317 (6) ŵ = 4.49 mm1
β = 90.314 (4)°T = 174 K
V = 698.2 (3) Å3Needle, pale yellow
Z = 20.45 × 0.10 × 0.04 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1601 independent reflections
Radiation source: fine-focus sealed tube1290 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
h = 99
Tmin = 0.24, Tmax = 0.84k = 55
7115 measured reflectionsl = 3030
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.064P)2 + 3.31P]
where P = (Fo2 + 2Fc2)/3
1601 reflections(Δ/σ)max = 0.001
82 parametersΔρmax = 3.00 e Å3
0 restraintsΔρmin = 1.34 e Å3
Crystal data top
C14H10I2N2V = 698.2 (3) Å3
Mr = 460.04Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.2077 (17) ŵ = 4.49 mm1
b = 4.1543 (10) ÅT = 174 K
c = 23.317 (6) Å0.45 × 0.10 × 0.04 mm
β = 90.314 (4)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1601 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
1290 reflections with I > 2σ(I)
Tmin = 0.24, Tmax = 0.84Rint = 0.085
7115 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.122H-atom parameters constrained
S = 1.05Δρmax = 3.00 e Å3
1601 reflectionsΔρmin = 1.34 e Å3
82 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.36110 (6)0.86627 (12)0.308402 (18)0.02813 (19)
C10.1234 (9)0.7210 (17)0.3534 (3)0.0217 (13)
N10.4138 (8)0.5574 (16)0.4905 (2)0.0305 (14)
C20.0112 (9)0.5424 (17)0.3250 (3)0.0245 (14)
H20.00650.48050.28610.029*
C30.1724 (9)0.4558 (19)0.3545 (3)0.0270 (14)
H30.26490.33350.33550.032*
C40.1998 (9)0.5447 (18)0.4110 (3)0.0259 (14)
C50.0624 (10)0.7242 (19)0.4393 (3)0.0288 (15)
H50.08030.78670.47810.035*
C60.0992 (10)0.8102 (18)0.4105 (3)0.0291 (16)
H60.19280.92940.42960.035*
C70.3726 (10)0.4583 (19)0.4403 (3)0.0284 (15)
H70.45790.32210.42110.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0228 (3)0.0252 (3)0.0363 (3)0.00290 (19)0.00815 (17)0.00015 (18)
C10.016 (3)0.018 (3)0.031 (3)0.000 (3)0.007 (2)0.003 (2)
N10.026 (3)0.034 (4)0.032 (3)0.004 (3)0.005 (2)0.000 (3)
C20.025 (3)0.019 (3)0.030 (3)0.003 (3)0.004 (2)0.003 (3)
C30.019 (3)0.032 (4)0.030 (3)0.003 (3)0.002 (2)0.001 (3)
C40.020 (3)0.028 (4)0.030 (3)0.004 (3)0.003 (2)0.001 (3)
C50.028 (4)0.029 (4)0.030 (3)0.005 (3)0.002 (3)0.003 (3)
C60.028 (3)0.032 (4)0.028 (3)0.010 (3)0.002 (3)0.001 (3)
C70.022 (3)0.027 (4)0.036 (4)0.003 (3)0.002 (3)0.003 (3)
Geometric parameters (Å, º) top
I1—C12.094 (6)C3—H30.9500
C1—C61.391 (9)C4—C51.406 (10)
C1—C21.392 (10)C4—C71.463 (9)
N1—C71.274 (9)C5—C61.388 (10)
N1—N1i1.400 (12)C5—H50.9500
C2—C31.395 (9)C6—H60.9500
C2—H20.9500C7—H70.9500
C3—C41.381 (9)
C6—C1—C2120.9 (6)C3—C4—C7119.8 (6)
C6—C1—I1120.0 (5)C5—C4—C7120.7 (6)
C2—C1—I1119.0 (5)C6—C5—C4120.1 (6)
C7—N1—N1i112.4 (7)C6—C5—H5120.0
C1—C2—C3118.8 (6)C4—C5—H5120.0
C1—C2—H2120.6C5—C6—C1119.6 (6)
C3—C2—H2120.6C5—C6—H6120.2
C4—C3—C2121.1 (6)C1—C6—H6120.2
C4—C3—H3119.5N1—C7—C4122.9 (7)
C2—C3—H3119.5N1—C7—H7118.5
C3—C4—C5119.5 (6)C4—C7—H7118.5
C6—C1—C2—C30.5 (10)C4—C5—C6—C10.7 (11)
I1—C1—C2—C3177.8 (5)C2—C1—C6—C50.9 (11)
C1—C2—C3—C40.1 (11)I1—C1—C6—C5177.3 (6)
C2—C3—C4—C50.3 (11)N1i—N1—C7—C4180.0 (7)
C2—C3—C4—C7178.2 (7)C3—C4—C7—N1173.4 (7)
C3—C4—C5—C60.1 (11)C5—C4—C7—N15.1 (11)
C7—C4—C5—C6178.6 (7)
Symmetry code: (i) x+1, y+1, z+1.
(I,Cl) 1-(4-Chlorobenzylidene)-2-(4-iodobenzylidene)diazane top
Crystal data top
C14H10ClIN2F(000) = 356
Mr = 368.59Dx = 1.808 Mg m3
Monoclinic, PcMo Kα radiation, λ = 0.71073 Å
a = 11.499 (2) ÅCell parameters from 3282 reflections
b = 4.0006 (7) Åθ = 2.8–27.5°
c = 14.717 (3) ŵ = 2.55 mm1
β = 90.900 (3)°T = 174 K
V = 676.9 (2) Å3Plate, yellow
Z = 20.20 × 0.20 × 0.05 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
3089 independent reflections
Radiation source: fine-focus sealed tube2308 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ω scansθmax = 28.2°, θmin = 1.8°
Absorption correction: multi-scan
SADABS; Sheldrick, 2003; Blessing, 1995
h = 1515
Tmin = 0.42, Tmax = 0.88k = 55
7262 measured reflectionsl = 1918
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.072 w = 1/[σ2(Fo2) + (0.017P)2 + 0.681P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.02
3089 reflectionsΔρmax = 0.50 e Å3
164 parametersΔρmin = 0.33 e Å3
109 restraintsAbsolute structure: Flack (1983), 1476 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.17 (7)
Crystal data top
C14H10ClIN2V = 676.9 (2) Å3
Mr = 368.59Z = 2
Monoclinic, PcMo Kα radiation
a = 11.499 (2) ŵ = 2.55 mm1
b = 4.0006 (7) ÅT = 174 K
c = 14.717 (3) Å0.20 × 0.20 × 0.05 mm
β = 90.900 (3)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
3089 independent reflections
Absorption correction: multi-scan
SADABS; Sheldrick, 2003; Blessing, 1995
2308 reflections with I > 2σ(I)
Tmin = 0.42, Tmax = 0.88Rint = 0.032
7262 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.072Δρmax = 0.50 e Å3
S = 1.05Δρmin = 0.33 e Å3
3089 reflectionsAbsolute structure: Flack (1983), 1476 Friedel pairs
164 parametersAbsolute structure parameter: 0.17 (7)
109 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.2105 (10)0.678 (4)0.2032 (6)0.0338 (13)0.5858 (17)
C20.1493 (7)0.807 (5)0.2760 (8)0.0378 (14)0.5858 (17)
H20.06870.85630.27000.045*0.5858 (17)
C30.2079 (8)0.862 (5)0.3569 (7)0.0385 (13)0.5858 (17)
H30.16780.96210.40600.046*0.5858 (17)
C40.3247 (8)0.775 (5)0.3685 (6)0.0350 (8)0.5858 (17)
C50.3808 (9)0.618 (4)0.2962 (7)0.0353 (13)0.5858 (17)
H50.45820.53880.30440.042*0.5858 (17)
C60.3250 (10)0.575 (4)0.2134 (6)0.0361 (12)0.5858 (17)
H60.36460.47710.16390.043*0.5858 (17)
C70.3862 (12)0.857 (6)0.4527 (8)0.0365 (12)0.5858 (17)
H70.35201.00740.49450.044*0.5858 (17)
N10.486 (2)0.728 (8)0.4713 (15)0.041 (2)0.5858 (17)
I10.1235 (4)0.5523 (8)0.0819 (3)0.0389 (2)0.5858 (17)
C110.8013 (12)0.858 (7)0.8289 (7)0.0338 (13)0.5858 (17)
C120.8598 (12)0.697 (7)0.7595 (10)0.0378 (14)0.5858 (17)
H120.93770.62350.76820.045*0.5858 (17)
C130.8026 (12)0.647 (8)0.6777 (11)0.0385 (13)0.5858 (17)
H130.84180.53620.63000.046*0.5858 (17)
C140.6883 (11)0.755 (7)0.6634 (8)0.0350 (8)0.5858 (17)
C150.6333 (13)0.927 (8)0.7338 (9)0.0353 (13)0.5858 (17)
H150.55581.00370.72520.042*0.5858 (17)
C160.6904 (16)0.985 (9)0.8154 (10)0.0361 (12)0.5858 (17)
H160.65401.11090.86170.043*0.5858 (17)
C170.6301 (17)0.695 (12)0.5765 (12)0.0365 (12)0.5858 (17)
H170.67100.58740.52910.044*0.5858 (17)
N20.5236 (17)0.785 (9)0.5630 (12)0.041 (2)0.5858 (17)
Cl10.8762 (8)0.904 (2)0.9323 (5)0.0389 (2)0.5858 (17)
C1A0.2116 (14)0.610 (6)0.1946 (10)0.0338 (13)0.4142 (17)
C2A0.1596 (12)0.820 (7)0.2575 (12)0.0378 (14)0.4142 (17)
H2A0.08580.91760.24490.045*0.4142 (17)
C3A0.2173 (12)0.883 (7)0.3384 (11)0.0385 (13)0.4142 (17)
H3A0.18251.02560.38180.046*0.4142 (17)
C4A0.3259 (12)0.742 (7)0.3581 (9)0.0350 (8)0.4142 (17)
C5A0.3787 (12)0.548 (6)0.2910 (10)0.0353 (13)0.4142 (17)
H5A0.45320.45290.30260.042*0.4142 (17)
C6A0.3237 (14)0.492 (6)0.2084 (9)0.0361 (12)0.4142 (17)
H6A0.36210.37390.16160.043*0.4142 (17)
C7A0.3816 (18)0.799 (9)0.4460 (11)0.0365 (12)0.4142 (17)
H7A0.34310.92900.49040.044*0.4142 (17)
N1A0.483 (3)0.675 (12)0.465 (2)0.041 (2)0.4142 (17)
Cl1A0.1289 (14)0.585 (4)0.0944 (7)0.0389 (2)0.4142 (17)
C11A0.8080 (17)0.860 (10)0.8115 (10)0.0338 (13)0.4142 (17)
C12A0.8602 (16)0.668 (10)0.7448 (14)0.0378 (14)0.4142 (17)
H12A0.93550.57590.75460.045*0.4142 (17)
C13A0.8003 (16)0.613 (11)0.6644 (15)0.0385 (13)0.4142 (17)
H13A0.83690.49260.61710.046*0.4142 (17)
C14A0.6872 (14)0.732 (11)0.6507 (11)0.0350 (8)0.4142 (17)
C15A0.6333 (17)0.897 (11)0.7228 (12)0.0353 (13)0.4142 (17)
H15A0.55450.96580.71640.042*0.4142 (17)
C16A0.693 (2)0.962 (12)0.8027 (15)0.0361 (12)0.4142 (17)
H16A0.65651.07580.85110.043*0.4142 (17)
C17A0.628 (3)0.682 (17)0.5638 (18)0.0365 (12)0.4142 (17)
H17A0.66420.55160.51820.044*0.4142 (17)
N2A0.527 (3)0.812 (13)0.5477 (18)0.041 (2)0.4142 (17)
I1A0.8899 (4)0.9487 (8)0.9374 (3)0.0389 (2)0.4142 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0354 (17)0.023 (3)0.043 (2)0.0047 (17)0.0129 (18)0.002 (3)
C20.0353 (17)0.033 (3)0.046 (4)0.0018 (16)0.018 (2)0.003 (3)
C30.0428 (18)0.033 (3)0.041 (3)0.0040 (17)0.0230 (19)0.000 (3)
C40.0390 (16)0.024 (3)0.042 (2)0.0001 (13)0.0165 (15)0.001 (2)
C50.0330 (14)0.024 (4)0.049 (2)0.0001 (16)0.0131 (15)0.002 (2)
C60.0422 (17)0.020 (4)0.047 (2)0.0018 (18)0.0201 (17)0.005 (2)
C70.0396 (17)0.029 (4)0.042 (3)0.001 (2)0.0205 (18)0.003 (3)
N10.0423 (17)0.041 (5)0.039 (3)0.001 (3)0.0161 (19)0.001 (4)
I10.0397 (4)0.0424 (6)0.0346 (4)0.0062 (3)0.0009 (3)0.0015 (3)
C110.0354 (17)0.023 (3)0.043 (2)0.0047 (17)0.0129 (18)0.002 (3)
C120.0353 (17)0.033 (3)0.046 (4)0.0018 (16)0.018 (2)0.003 (3)
C130.0428 (18)0.033 (3)0.041 (3)0.0040 (17)0.0230 (19)0.000 (3)
C140.0390 (16)0.024 (3)0.042 (2)0.0001 (13)0.0165 (15)0.001 (2)
C150.0330 (14)0.024 (4)0.049 (2)0.0001 (16)0.0131 (15)0.002 (2)
C160.0422 (17)0.020 (4)0.047 (2)0.0018 (18)0.0201 (17)0.005 (2)
C170.0396 (17)0.029 (4)0.042 (3)0.001 (2)0.0205 (18)0.003 (3)
N20.0423 (17)0.041 (5)0.039 (3)0.001 (3)0.0161 (19)0.001 (4)
Cl10.0397 (4)0.0424 (6)0.0346 (4)0.0062 (3)0.0009 (3)0.0015 (3)
C1A0.0354 (17)0.023 (3)0.043 (2)0.0047 (17)0.0129 (18)0.002 (3)
C2A0.0353 (17)0.033 (3)0.046 (4)0.0018 (16)0.018 (2)0.003 (3)
C3A0.0428 (18)0.033 (3)0.041 (3)0.0040 (17)0.0230 (19)0.000 (3)
C4A0.0390 (16)0.024 (3)0.042 (2)0.0001 (13)0.0165 (15)0.001 (2)
C5A0.0330 (14)0.024 (4)0.049 (2)0.0001 (16)0.0131 (15)0.002 (2)
C6A0.0422 (17)0.020 (4)0.047 (2)0.0018 (18)0.0201 (17)0.005 (2)
C7A0.0396 (17)0.029 (4)0.042 (3)0.001 (2)0.0205 (18)0.003 (3)
N1A0.0423 (17)0.041 (5)0.039 (3)0.001 (3)0.0161 (19)0.001 (4)
Cl1A0.0397 (4)0.0424 (6)0.0346 (4)0.0062 (3)0.0009 (3)0.0015 (3)
C11A0.0354 (17)0.023 (3)0.043 (2)0.0047 (17)0.0129 (18)0.002 (3)
C12A0.0353 (17)0.033 (3)0.046 (4)0.0018 (16)0.018 (2)0.003 (3)
C13A0.0428 (18)0.033 (3)0.041 (3)0.0040 (17)0.0230 (19)0.000 (3)
C14A0.0390 (16)0.024 (3)0.042 (2)0.0001 (13)0.0165 (15)0.001 (2)
C15A0.0330 (14)0.024 (4)0.049 (2)0.0001 (16)0.0131 (15)0.002 (2)
C16A0.0422 (17)0.020 (4)0.047 (2)0.0018 (18)0.0201 (17)0.005 (2)
C17A0.0396 (17)0.029 (4)0.042 (3)0.001 (2)0.0205 (18)0.003 (3)
N2A0.0423 (17)0.041 (5)0.039 (3)0.001 (3)0.0161 (19)0.001 (4)
I1A0.0397 (4)0.0424 (6)0.0346 (4)0.0062 (3)0.0009 (3)0.0015 (3)
Geometric parameters (Å, º) top
C1—C61.384 (4)C1A—C6A1.385 (4)
C1—C21.390 (4)C1A—C2A1.391 (4)
C1—I12.0946 (10)C1A—Cl1A1.7458 (10)
C2—C31.377 (4)C2A—C3A1.377 (4)
C2—H20.9500C2A—H2A0.9500
C3—C41.396 (4)C3A—C4A1.396 (4)
C3—H30.9500C3A—H3A0.9500
C4—C51.403 (4)C4A—C5A1.403 (4)
C4—C71.453 (4)C4A—C7A1.453 (4)
C5—C61.379 (4)C5A—C6A1.379 (4)
C5—H50.9500C5A—H5A0.9500
C6—H60.9500C6A—H6A0.9500
C7—N11.289 (4)C7A—N1A1.289 (4)
C7—H70.9500C7A—H7A0.9500
N1—N21.427 (11)N1A—N2A1.427 (11)
C11—C161.384 (4)C11A—C16A1.385 (4)
C11—C121.390 (4)C11A—C12A1.391 (4)
C11—Cl11.7461 (10)C11A—I1A2.0951 (11)
C12—C131.377 (4)C12A—C13A1.377 (4)
C12—H120.9500C12A—H12A0.9500
C13—C141.396 (4)C13A—C14A1.396 (4)
C13—H130.9500C13A—H13A0.9500
C14—C151.403 (4)C14A—C15A1.403 (4)
C14—C171.453 (4)C14A—C17A1.453 (4)
C15—C161.379 (4)C15A—C16A1.379 (4)
C15—H150.9500C15A—H15A0.9500
C16—H160.9500C16A—H16A0.9500
C17—N21.289 (4)C17A—N2A1.289 (4)
C17—H170.9500C17A—H17A0.9500
C6—C1—C2121.3 (3)C6A—C1A—C2A121.2 (3)
C6—C1—I1117.5 (6)C6A—C1A—Cl1A126.6 (11)
C2—C1—I1120.3 (7)C2A—C1A—Cl1A111.3 (11)
C3—C2—C1118.7 (3)C3A—C2A—C1A118.6 (3)
C3—C2—H2120.7C3A—C2A—H2A120.7
C1—C2—H2120.7C1A—C2A—H2A120.7
C2—C3—C4121.5 (3)C2A—C3A—C4A121.5 (3)
C2—C3—H3119.3C2A—C3A—H3A119.2
C4—C3—H3119.3C4A—C3A—H3A119.2
C3—C4—C5118.2 (3)C3A—C4A—C5A118.2 (3)
C3—C4—C7120.1 (3)C3A—C4A—C7A120.1 (3)
C5—C4—C7121.6 (3)C5A—C4A—C7A121.6 (3)
C6—C5—C4120.8 (3)C6A—C5A—C4A120.8 (3)
C6—C5—H5119.6C6A—C5A—H5A119.6
C4—C5—H5119.6C4A—C5A—H5A119.6
C5—C6—C1119.2 (3)C5A—C6A—C1A119.1 (3)
C5—C6—H6120.4C5A—C6A—H6A120.5
C1—C6—H6120.4C1A—C6A—H6A120.5
N1—C7—C4120.9 (3)N1A—C7A—C4A120.8 (3)
N1—C7—H7119.6N1A—C7A—H7A119.6
C4—C7—H7119.6C4A—C7A—H7A119.6
C7—N1—N2113.0 (10)C7A—N1A—N2A110.2 (11)
C16—C11—C12121.3 (3)C16A—C11A—C12A121.2 (3)
C16—C11—Cl1121.8 (8)C16A—C11A—I1A116.5 (10)
C12—C11—Cl1116.8 (8)C12A—C11A—I1A121.6 (11)
C13—C12—C11118.7 (3)C13A—C12A—C11A118.6 (3)
C13—C12—H12120.7C13A—C12A—H12A120.7
C11—C12—H12120.7C11A—C12A—H12A120.7
C12—C13—C14121.5 (3)C12A—C13A—C14A121.5 (3)
C12—C13—H13119.2C12A—C13A—H13A119.3
C14—C13—H13119.2C14A—C13A—H13A119.3
C13—C14—C15118.2 (3)C13A—C14A—C15A118.2 (3)
C13—C14—C17120.1 (3)C13A—C14A—C17A120.1 (3)
C15—C14—C17121.6 (3)C15A—C14A—C17A121.6 (3)
C16—C15—C14120.9 (3)C16A—C15A—C14A120.9 (3)
C16—C15—H15119.6C16A—C15A—H15A119.6
C14—C15—H15119.6C14A—C15A—H15A119.6
C15—C16—C11119.2 (3)C15A—C16A—C11A119.1 (3)
C15—C16—H16120.4C15A—C16A—H16A120.4
C11—C16—H16120.4C11A—C16A—H16A120.4
N2—C17—C14120.8 (3)N2A—C17A—C14A120.9 (3)
N2—C17—H17119.6N2A—C17A—H17A119.6
C14—C17—H17119.6C14A—C17A—H17A119.6
C17—N2—N1111.7 (11)C17A—N2A—N1A108.2 (12)

Experimental details

(I,I-A)(I,I-B)(I,I-C)(I,Cl)
Crystal data
Chemical formulaC14H10I2N2C14H10I2N2C14H10I2N2C14H10ClIN2
Mr460.04460.04460.04368.59
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/nMonoclinic, P21/cMonoclinic, Pc
Temperature (K)174174174174
a, b, c (Å)11.854 (2), 7.7308 (13), 7.6827 (13)8.4303 (17), 5.6453 (12), 15.248 (3)7.2077 (17), 4.1543 (10), 23.317 (6)11.499 (2), 4.0006 (7), 14.717 (3)
β (°) 92.407 (3) 104.346 (3) 90.314 (4) 90.900 (3)
V3)703.5 (2)703.0 (3)698.2 (3)676.9 (2)
Z2222
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)4.454.464.492.55
Crystal size (mm)0.45 × 0.35 × 0.060.30 × 0.06 × 0.030.45 × 0.10 × 0.040.20 × 0.20 × 0.05
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Bruker SMART 1K CCD area-detector
diffractometer
Bruker SMART 1K CCD area-detector
diffractometer
Bruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
Multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
Multi-scan
(SADABS; Sheldrick, 2003; Blessing, 1995)
Multi-scan
SADABS; Sheldrick, 2003; Blessing, 1995
Tmin, Tmax0.32, 0.770.54, 0.870.24, 0.840.42, 0.88
No. of measured, independent and
observed [I > 2σ(I)] reflections
7773, 1602, 1442 7699, 1600, 1189 7115, 1601, 1290 7262, 3089, 2308
Rint0.0310.0520.0850.032
(sin θ/λ)max1)0.6490.6490.6500.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.022, 0.054, 1.11 0.031, 0.061, 1.02 0.047, 0.122, 1.05 0.038, 0.072, 1.05
No. of reflections1602160016013089
No. of parameters838382164
No. of restraints000109
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.86, 0.550.48, 0.613.00, 1.340.50, 0.33
Absolute structure???Flack (1983), 1476 Friedel pairs
Absolute structure parameter???0.17 (7)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.

Table 1. Distances and angles (Å, °) in the X···X contacts in (X,X) and (X,X)*a
For comparison, the van der Waals contact distances (Bondi, 1964; Rowland &amp; Taylor, 1996) are Cl···Cl = 3.50 Å; Br···Br = 3.70 Å; I···I = 3.96 Å.
top
Compoundtemp(K)XX'C-X···X'X···X'X···X'-Cref.
(Cl,Cl)173Cl1Cl1i74.1 (1)3.887 (1)105.9 (1)b
(Cl,Cl)173Cl1Cl173.8 (1)3.892 (1)105.9 (1)c
(Cl,Cl)294Cl1Cl174.1 (1)3.958 (1)106.2 (1)d
(Br,Br)173Br1Br1ii127.1 (1)3.812 (2)152.6 (1)b
173Br1Br1iii74.2 (1)3.977 (1)105.8 (1)b
(Br,Br)294Br1Br1126.3 (3)3.861 (4)153.4 (3)e
294Br1Br173.3 (3)4.051 (4)106.7 (3)e
(I,I-A)173I1I1iv147.0 (2)3.781 (1)147.0 (2)f
(I,I-B)173I1I1v109.9 (3)3.965 (2)154.5 (3)f
(I,I-C)173I1I1vi127.1 (5)3.960 (4)154.9 (5)f
173I1I1iii73.2 (5)4.154 (1)106.8 (5)f
(Cl,Cl)*294Cl1Cl2163.4 (2)3.340 (1)163.6 (2)g
(Br,Br)*294Br1Br2168.8 (2)3.560 (1)97.0 (2)g
(I,I)*173I1I1'155.3 (3)4.122 (1)101.8 (3)h
(a) The (X,X)* structures are for analogous compounds where the azine H atoms have been replaced by methyl groups. (b) Ojala et al. (2007a). (c) Glaser et al. (2006). (d) Zheng et al. (2005). (e) Marignan et al. (1972). (f) This work. (g) Chen et al. (1994). (h) Lewis et al. (1999). Symmetry codes: (i) 1+x, y, z; (ii) 3/2-x, -1/2+y, 3/2-z; (iii) x, -1+y, z; (iv) -x, 1-y, -1-z;(v) 3/2-x, -1/2+y, 1/2-z; (vi) -1-x, -1/2+y, 1/2-z.
Table 3. π contacts: inter-ring distances (Å) and ring overlaps (%) top
compounddistance(Å)overlap(%)ref.
(Cl,Cl)3.459 (4)17.8 (2)a
(Br,Br)3.479 (6)12.8 (2)a
(I,I-A)no_overlapb
(I,I-B)3.584 (8)12.7 (2)b
(I,I-C)3.522 (3)5.7 (2)b
(a) Ojala et al. (2007a). (b) This work.
Table 4. Cell constants (Å, °, Å3) for all (X,X) and (X,Y) structures at 173 K. top
CompoundabcβVreference
(Cl,Cl)3.887 (1)6.990 (1)22.980 (2)90.77 (1)624.3 (1)a
(Br,Cl)6.995 (1)3.945 (1)22.971 (4)92.72 (1)633.1 (2)b
(Br,Br)7.027 (1)3.977 (1)23.141 (3)91.72 (1)646.5 (1)a
(I,Cl)11.499 (2)4.001 (1)14.717 (3)90.90 (1)676.9 (2)c
(I,Br)11.513 (5)4.044 (2)14.719 (4)90.34 (2)685.3 (3)b
(I,I-A)11.854 (2)7.731 (1)7.683 (1)92.41 (1)703.5 (2)c
(I,I-B)8.430 (2)5.645 (1)15.248 (3)104.35 (1)703.0 (3)c
(I,I-C)7.208 (2)4.154 (1)23.317 (6)90.31 (1)698.2 (3)c
(a) Ojala et al. (2007a). (b) Ojala et al. (2007b). (c) This work.
Table 2. Comparison of N-N distances (Å) between (X,X) and (X-X)* top
Xdist._in_(X,X)referencedist._in_(X,X)*reference
H1.418 (3)a1.403 (3)b
1.412 (10)c1.396 (2)d
Cl1.412 (2)e1.398 (3)b
1.414 (3)f
1.409 (2))g
Br1.450 (22)h1.383 (6)b
1.411 (4)g
I1.411 (4)i1.396 (6)j
1.418 (6)i
1.400 (12)i
(a) Mom & de With (1978). (b) Chen et al. (1994). (c) Burke-Laing & Laing (1976). (d) Bolte & Ton (2003). (e) Glaser et al. (2006 (f) Zheng et al. (2005). (g) Ojala et al. (2007a). (h) Marignan et al. (1972).This work. (j) Lewis et al. (1999).
 

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