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organic compounds
N-(2-Hydroxy-3-iodo-5-nitrobenzylidene)-3-nitroaniline: conformational isomers linked into complex sheets by five C—H⋯O hydrogen bonds and a two-centre iodo–nitro interaction
aDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, bInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk
The title compound, C13H8IN3O5, crystallizes with Z′ = 2 in the P21/n. The two independent molecules, which are both almost planar, are conformational isomers. The molecules are linked into complex sheets by a combination of five independent C—H⋯O hydrogen bonds and an almost linear two-centre iodo–nitro interaction.
Comment
We have recently reported the supramolecular structures of N-(2-iodobenzylidene)-3-nitroaniline, 2-IC6H4CH=NC6H4NO2-3′ (Wardell et al., 2002), and the various isomeric N-(nitrobenzylidene)iodoanilines, O2NC6H4CH=NC6H4I (Glidewell et al., 2002
), several of which crystallize in two polymorphic forms (Ferguson et al., 2005
). We have now continued our studies in this area with the title compound, (I)
, an imine containing an additional nitro group as well as a hard hydrogen-bonding donor group.
Compound (I) crystallizes with Z′ = 2 in the P21/n (Fig. 1
). In each of the independent molecules there is an intramolecular O—H⋯N hydrogen bond, forming an S(6) motif (Bernstein et al., 1995
), and these interactions undoubtedly influence the molecular conformations. Both molecules are nearly planar. The overall conformation in each is defined by five torsion angles (Table 1
), and it is striking that in molecule A the two nitro groups are on the same edge of the molecule, whereas in molecule B these substituents are on opposite edges (Fig. 1
). The two molecules are thus conformational isomers, and this alone suffices to preclude any possible additional symmetry.
Within the molecules, the bond distances show some interesting patterns (Table 1), consequent upon the mutually
![Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19. [Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]](../../../../../../logos/arrows/c_arr.gif)
![[link]](../../../../../../logos/arrows/c_arr.gif)
Within the selected and Table 2
), and this bimolecular aggregate can be regarded as the basic building block within the supramolecular structure. Three further C—H⋯O hydrogen bonds and a two-centre iodo–nitro interaction then link these aggregates into complex sheets, the formation of which can be readily analysed in terms of one-dimensional substructures.
In the principal B at (x, y, z) acts as hydrogen-bond donor to atom O14B at (−x, −y, 1 − z), so generating by inversion a centrosymmetric R22(10) motif centred at (0, 0, ). At the same time, atom I3B at (x, y, z) forms a two-centre interaction with atom O13A at (−x, 1 − y, 1 − z), with dimensions I⋯O = 3.173 (4) Å and C—I⋯O = 175.6 (2)°, so generating by inversion an R44(28) (Starbuck et al., 1999
) motif centred at (0,
,
). Propagation by inversion of these two interactions then generates a chain running parallel to the [010] direction containing R22(10) rings centred at (0, n,
) (n = zero or integer) and R44(28) rings centred at (0, n +
,
) (n = zero or integer), together with two types of S(6) ring and an R22(14) ring (Fig. 2
).
Two further C—H⋯O hydrogen bonds link the [010] chains into sheets. The type A molecules (Fig. 1) at (x, y, z) and (−x, −y, 1 − z) form part of the chain along (0, y,
) (Fig. 2
). The C14A atoms at (x, y, z) and (−x, −y, 1 − z), act as hydrogen-bond donors to, respectively, atoms O51A at (
− x,
+ y,
− z) and (−
+ x, −
− y,
+ z), which themselves lie in the [010] chains along (
, y, 0) and (
, y, 1), respectively. Hence, the propagation of this hydrogen bond by the 21 screw axes along [3(2m + 1)/4, y, (1 − 2m)/4] (m = zero or integer) links the [010] chains into a (103) sheet. The formation of this sheet is reinforced by the final C—H⋯O hydrogen bond, in which atom C16A at (x, y, z) acts as hydrogen-bond donor to atom O13B at (
+ x,
− y, −
+ z), so forming a C22(18)C22(18)[R22(14)] chain of rings running parallel to the [30
] direction and generated by the n-glide plane at y =
(Fig. 3
).
There are no direction-specific interactions between adjacent sheets. In particular, C—H⋯π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent from the structure of (I).
![]() | Figure 1 The two independent molecules of compound (I) ![]() |
![]() | Figure 2 A stereoview of part of the crystal structure of compound (I) ![]() |
![]() | Figure 3 A stereoview of part of the crystal structure of compound (I) ![]() ![]() |
Experimental
A solution of 3-nitroaniline (1.38 g, 10 mmol) and 2-hydroxy-3-iodo-5-nitrobenzaldehyde (0.55 g, 10 mmol) (Garden et al., 2004) in methanol (30 ml) was heated under reflux for 45 min. The mixture was then cooled and the solvent was removed under reduced pressure. Crystallization from ethanol of the resulting solid product gave crystals of (I)
suitable for single-crystal X-ray diffraction.
Crystal data
|
Refinement
|
|
|
The P21/n was uniquely assigned from the All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.93 Å, O—H = 0.82 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).
Data collection: SMART (Bruker, 1998); cell SAINT (Bruker, 2000
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997
); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997
); molecular graphics: PLATON (Spek, 2003
); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999
).
Supporting information
10.1107/S0108270106020373/sk3030sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270106020373/sk3030Isup2.hkl
A solution of 3-nitroaniline (1.38 g, 10 mmol) and 2-hydroxy-3-iodo-5-nitrobenzaldehyde (0.55 g, 10 mmol) (Garden et al., 2004) in methanol (30 ml) was heated under reflux for 45 min. The mixture was then cooled and the solvent was removed under reduced pressure. Crystallization from ethanol of the resulting solid product gave crystals of (I) suitable for single-crystal X-ray diffraction.
The
P21/n was uniquely assigned from the All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.93 Å and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).Data collection: SMART (Bruker, 1998); cell
SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).C13H8IN3O5 | F(000) = 1600 |
Mr = 413.12 | Dx = 1.948 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 10158 reflections |
a = 9.2957 (4) Å | θ = 2.0–32.5° |
b = 27.5905 (13) Å | µ = 2.30 mm−1 |
c = 11.0084 (5) Å | T = 291 K |
β = 93.830 (2)° | Plate, colourless |
V = 2817.1 (2) Å3 | 0.30 × 0.22 × 0.05 mm |
Z = 8 |
Bruker SMART 1000 CCD area-detector diffractometer | 10158 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 4201 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
ϕ/ω scans | θmax = 32.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −12→14 |
Tmin = 0.545, Tmax = 0.893 | k = −41→40 |
29048 measured reflections | l = −14→16 |
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) = 0.093 | H-atom parameters constrained |
S = 0.87 | w = 1/[σ2(Fo2) + (0.0298P)2] where P = (Fo2 + 2Fc2)/3 |
10158 reflections | (Δ/σ)max = 0.001 |
399 parameters | Δρmax = 0.72 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
C13H8IN3O5 | V = 2817.1 (2) Å3 |
Mr = 413.12 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.2957 (4) Å | µ = 2.30 mm−1 |
b = 27.5905 (13) Å | T = 291 K |
c = 11.0084 (5) Å | 0.30 × 0.22 × 0.05 mm |
β = 93.830 (2)° |
Bruker SMART 1000 CCD area-detector diffractometer | 10158 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 4201 reflections with I > 2σ(I) |
Tmin = 0.545, Tmax = 0.893 | Rint = 0.068 |
29048 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.72 e Å−3 |
10158 reflections | Δρmin = −0.51 e Å−3 |
399 parameters |
x | y | z | Uiso*/Ueq | ||
C1A | 0.7396 (4) | 0.32517 (14) | 0.2209 (4) | 0.0415 (10) | |
C2A | 0.8625 (4) | 0.30384 (15) | 0.1745 (4) | 0.0421 (10) | |
C3A | 0.8740 (4) | 0.25305 (14) | 0.1702 (4) | 0.0409 (10) | |
C4A | 0.7664 (4) | 0.22415 (14) | 0.2109 (4) | 0.0437 (10) | |
C5A | 0.6448 (4) | 0.24585 (14) | 0.2533 (4) | 0.0417 (10) | |
C6A | 0.6301 (4) | 0.29554 (15) | 0.2596 (4) | 0.0424 (10) | |
O2A | 0.9685 (3) | 0.33075 (10) | 0.1356 (3) | 0.0554 (8) | |
I3A | 1.06008 (3) | 0.222130 (10) | 0.10789 (3) | 0.05289 (10) | |
N5A | 0.5291 (4) | 0.21515 (14) | 0.2923 (3) | 0.0538 (10) | |
O51A | 0.5482 (3) | 0.17160 (12) | 0.2999 (4) | 0.0795 (11) | |
O52A | 0.4151 (3) | 0.23460 (11) | 0.3152 (3) | 0.0687 (10) | |
C7A | 0.7259 (4) | 0.37732 (14) | 0.2311 (4) | 0.0473 (11) | |
N1A | 0.8246 (3) | 0.40571 (12) | 0.1978 (3) | 0.0481 (9) | |
C11A | 0.8200 (4) | 0.45685 (14) | 0.2106 (4) | 0.0451 (10) | |
C12A | 0.7079 (4) | 0.48208 (14) | 0.2607 (4) | 0.0495 (11) | |
C13A | 0.7214 (4) | 0.53096 (14) | 0.2715 (4) | 0.0514 (11) | |
C14A | 0.8390 (5) | 0.55672 (16) | 0.2374 (5) | 0.0655 (14) | |
C15A | 0.9482 (5) | 0.53111 (17) | 0.1880 (5) | 0.0767 (16) | |
C16A | 0.9380 (5) | 0.48180 (17) | 0.1743 (5) | 0.0642 (14) | |
N13A | 0.6041 (4) | 0.55855 (14) | 0.3252 (4) | 0.0645 (11) | |
O13A | 0.4970 (4) | 0.53663 (12) | 0.3453 (4) | 0.1098 (16) | |
O14A | 0.6206 (4) | 0.60154 (12) | 0.3412 (4) | 0.0835 (12) | |
C1B | 0.0925 (4) | 0.30637 (14) | 0.4377 (4) | 0.0389 (9) | |
C2B | −0.0316 (4) | 0.32694 (15) | 0.4857 (4) | 0.0430 (10) | |
C3B | −0.0414 (4) | 0.37800 (15) | 0.4930 (4) | 0.0446 (10) | |
C4B | 0.0665 (4) | 0.40661 (15) | 0.4539 (4) | 0.0495 (11) | |
C5B | 0.1856 (4) | 0.38511 (15) | 0.4065 (4) | 0.0471 (11) | |
C6B | 0.2002 (4) | 0.33623 (15) | 0.3984 (4) | 0.0480 (11) | |
O2B | −0.1357 (3) | 0.29980 (10) | 0.5232 (3) | 0.0551 (8) | |
I3B | −0.22515 (3) | 0.408833 (11) | 0.56081 (3) | 0.06011 (11) | |
N5B | 0.3001 (4) | 0.41635 (15) | 0.3659 (4) | 0.0703 (12) | |
O51B | 0.2877 (4) | 0.45952 (13) | 0.3771 (5) | 0.128 (2) | |
O52B | 0.4033 (3) | 0.39706 (12) | 0.3204 (4) | 0.0836 (12) | |
C7B | 0.1070 (4) | 0.25474 (15) | 0.4298 (4) | 0.0446 (10) | |
N1B | 0.0085 (3) | 0.22593 (12) | 0.4636 (3) | 0.0430 (8) | |
C11B | 0.0187 (4) | 0.17463 (14) | 0.4586 (4) | 0.0440 (10) | |
C12B | −0.0938 (4) | 0.14925 (15) | 0.5043 (4) | 0.0475 (11) | |
C13B | −0.0864 (4) | 0.09943 (15) | 0.5059 (4) | 0.0507 (11) | |
C14B | 0.0262 (5) | 0.07417 (16) | 0.4619 (4) | 0.0574 (12) | |
C15B | 0.1353 (5) | 0.10006 (16) | 0.4145 (4) | 0.0585 (13) | |
C16B | 0.1336 (4) | 0.14985 (16) | 0.4124 (4) | 0.0514 (11) | |
N13B | −0.2059 (4) | 0.07247 (15) | 0.5560 (4) | 0.0675 (12) | |
O13B | −0.3092 (4) | 0.09588 (12) | 0.5844 (4) | 0.0943 (13) | |
O14B | −0.1970 (4) | 0.02889 (12) | 0.5645 (4) | 0.0867 (12) | |
H4A | 0.7751 | 0.1906 | 0.2099 | 0.052* | |
H6A | 0.5479 | 0.3091 | 0.2893 | 0.051* | |
H2A | 0.9468 | 0.3595 | 0.1396 | 0.083* | |
H7A | 0.6439 | 0.3904 | 0.2625 | 0.057* | |
H12A | 0.6270 | 0.4660 | 0.2858 | 0.059* | |
H14A | 0.8445 | 0.5902 | 0.2473 | 0.079* | |
H15A | 1.0292 | 0.5473 | 0.1639 | 0.092* | |
H16A | 1.0119 | 0.4650 | 0.1399 | 0.077* | |
H4B | 0.0601 | 0.4402 | 0.4590 | 0.059* | |
H6B | 0.2817 | 0.3229 | 0.3669 | 0.058* | |
H2B | −0.1174 | 0.2712 | 0.5111 | 0.083* | |
H7B | 0.1897 | 0.2418 | 0.3995 | 0.054* | |
H12B | −0.1725 | 0.1654 | 0.5333 | 0.057* | |
H14B | 0.0285 | 0.0405 | 0.4641 | 0.069* | |
H15B | 0.2119 | 0.0836 | 0.3833 | 0.070* | |
H16B | 0.2086 | 0.1669 | 0.3803 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.031 (2) | 0.045 (2) | 0.049 (3) | 0.0070 (18) | 0.0061 (19) | −0.003 (2) |
C2A | 0.031 (2) | 0.050 (3) | 0.046 (3) | 0.0040 (19) | 0.0074 (19) | −0.002 (2) |
C3A | 0.027 (2) | 0.046 (2) | 0.050 (3) | 0.0050 (18) | 0.0087 (19) | 0.000 (2) |
C4A | 0.041 (2) | 0.046 (2) | 0.045 (3) | 0.008 (2) | 0.0071 (19) | −0.002 (2) |
C5A | 0.032 (2) | 0.047 (2) | 0.047 (3) | −0.0023 (18) | 0.0067 (19) | −0.001 (2) |
C6A | 0.029 (2) | 0.055 (3) | 0.044 (3) | 0.0048 (18) | 0.0054 (19) | −0.007 (2) |
O2A | 0.0409 (16) | 0.0458 (16) | 0.082 (2) | 0.0023 (14) | 0.0223 (16) | 0.0047 (18) |
I3A | 0.04261 (16) | 0.05769 (18) | 0.0606 (2) | 0.01476 (14) | 0.02029 (14) | 0.00158 (16) |
N5A | 0.041 (2) | 0.063 (3) | 0.059 (2) | −0.0084 (19) | 0.0167 (18) | −0.012 (2) |
O51A | 0.071 (2) | 0.047 (2) | 0.125 (3) | −0.0056 (17) | 0.042 (2) | 0.004 (2) |
O52A | 0.0349 (16) | 0.074 (2) | 0.100 (3) | −0.0055 (15) | 0.0251 (17) | −0.0183 (19) |
C7A | 0.040 (2) | 0.050 (3) | 0.052 (3) | 0.008 (2) | 0.007 (2) | −0.004 (2) |
N1A | 0.038 (2) | 0.045 (2) | 0.062 (2) | 0.0051 (16) | 0.0080 (17) | 0.0005 (19) |
C11A | 0.036 (2) | 0.042 (2) | 0.058 (3) | 0.0056 (19) | 0.009 (2) | −0.002 (2) |
C12A | 0.038 (2) | 0.041 (2) | 0.071 (3) | 0.0013 (19) | 0.015 (2) | 0.005 (2) |
C13A | 0.044 (3) | 0.042 (3) | 0.069 (3) | 0.005 (2) | 0.009 (2) | −0.005 (2) |
C14A | 0.060 (3) | 0.044 (3) | 0.094 (4) | −0.006 (2) | 0.017 (3) | −0.008 (3) |
C15A | 0.051 (3) | 0.060 (3) | 0.123 (5) | −0.015 (2) | 0.029 (3) | −0.008 (3) |
C16A | 0.043 (3) | 0.062 (3) | 0.090 (4) | 0.002 (2) | 0.023 (3) | −0.001 (3) |
N13A | 0.060 (3) | 0.045 (2) | 0.091 (3) | 0.009 (2) | 0.020 (2) | −0.005 (2) |
O13A | 0.082 (3) | 0.055 (2) | 0.202 (5) | 0.0031 (19) | 0.083 (3) | −0.012 (3) |
O14A | 0.084 (3) | 0.047 (2) | 0.120 (3) | 0.0045 (18) | 0.019 (2) | −0.025 (2) |
C1B | 0.028 (2) | 0.047 (2) | 0.042 (3) | −0.0005 (18) | 0.0054 (18) | 0.000 (2) |
C2B | 0.035 (2) | 0.049 (2) | 0.047 (3) | −0.0011 (19) | 0.0110 (19) | 0.001 (2) |
C3B | 0.029 (2) | 0.058 (3) | 0.048 (3) | 0.0003 (19) | 0.0100 (19) | 0.002 (2) |
C4B | 0.044 (2) | 0.046 (2) | 0.060 (3) | −0.001 (2) | 0.015 (2) | −0.004 (2) |
C5B | 0.031 (2) | 0.051 (3) | 0.061 (3) | −0.0104 (19) | 0.018 (2) | −0.002 (2) |
C6B | 0.033 (2) | 0.058 (3) | 0.055 (3) | −0.0046 (19) | 0.014 (2) | −0.005 (2) |
O2B | 0.0374 (16) | 0.0538 (17) | 0.077 (2) | −0.0032 (14) | 0.0260 (15) | 0.0060 (18) |
I3B | 0.04633 (17) | 0.0628 (2) | 0.0742 (2) | 0.00891 (14) | 0.02602 (16) | −0.00050 (17) |
N5B | 0.046 (2) | 0.060 (3) | 0.107 (4) | −0.013 (2) | 0.027 (2) | 0.001 (3) |
O51B | 0.101 (3) | 0.049 (2) | 0.246 (6) | −0.021 (2) | 0.097 (4) | −0.010 (3) |
O52B | 0.0451 (19) | 0.081 (2) | 0.130 (3) | −0.0077 (17) | 0.045 (2) | 0.005 (2) |
C7B | 0.036 (2) | 0.058 (3) | 0.041 (3) | 0.002 (2) | 0.0105 (19) | −0.004 (2) |
N1B | 0.0344 (18) | 0.050 (2) | 0.046 (2) | −0.0031 (16) | 0.0094 (16) | 0.0010 (18) |
C11B | 0.043 (2) | 0.045 (2) | 0.044 (3) | −0.0024 (19) | 0.008 (2) | −0.001 (2) |
C12B | 0.037 (2) | 0.049 (3) | 0.058 (3) | −0.003 (2) | 0.011 (2) | −0.004 (2) |
C13B | 0.044 (2) | 0.052 (3) | 0.057 (3) | −0.004 (2) | 0.014 (2) | −0.002 (2) |
C14B | 0.055 (3) | 0.050 (3) | 0.070 (3) | 0.004 (2) | 0.017 (3) | 0.001 (2) |
C15B | 0.051 (3) | 0.058 (3) | 0.068 (3) | 0.008 (2) | 0.016 (2) | −0.003 (3) |
C16B | 0.040 (2) | 0.057 (3) | 0.059 (3) | 0.002 (2) | 0.019 (2) | 0.002 (2) |
N13B | 0.059 (3) | 0.056 (3) | 0.091 (3) | −0.013 (2) | 0.027 (2) | −0.004 (2) |
O13B | 0.058 (2) | 0.064 (2) | 0.167 (4) | −0.0051 (18) | 0.055 (2) | −0.003 (2) |
O14B | 0.088 (3) | 0.045 (2) | 0.132 (3) | −0.0091 (18) | 0.046 (2) | 0.004 (2) |
C1A—C2A | 1.411 (5) | C1B—C2B | 1.419 (5) |
C2A—C3A | 1.406 (5) | C2B—C3B | 1.414 (5) |
C3A—C4A | 1.377 (5) | C3B—C4B | 1.368 (5) |
C4A—C5A | 1.387 (5) | C4B—C5B | 1.388 (5) |
C5A—C6A | 1.380 (5) | C5B—C6B | 1.359 (5) |
C6A—C1A | 1.394 (5) | C6B—C1B | 1.388 (5) |
C2A—O2A | 1.327 (4) | C2B—O2B | 1.311 (4) |
C5A—N5A | 1.457 (5) | C5B—N5B | 1.463 (5) |
N5A—O51A | 1.217 (4) | N5B—O51B | 1.204 (4) |
N5A—O52A | 1.229 (4) | N5B—O52B | 1.232 (4) |
C13A—N13A | 1.484 (5) | C13B—N13B | 1.475 (5) |
N13A—O13A | 1.198 (5) | N13B—O13B | 1.215 (5) |
N13A—O14A | 1.207 (4) | N13B—O14B | 1.208 (4) |
C1A—C7A | 1.450 (5) | C1B—C7B | 1.434 (5) |
C3A—I3A | 2.086 (3) | C3B—I3B | 2.090 (4) |
C4A—H4A | 0.93 | C4B—H4B | 0.93 |
C6A—H6A | 0.93 | C6B—H6B | 0.93 |
O2A—H2A | 0.82 | O2B—H2B | 0.82 |
C7A—N1A | 1.279 (5) | C7B—N1B | 1.286 (5) |
C7A—H7A | 0.93 | C7B—H7B | 0.93 |
N1A—C11A | 1.419 (5) | N1B—C11B | 1.420 (5) |
C11A—C16A | 1.377 (6) | C11B—C12B | 1.381 (5) |
C11A—C12A | 1.398 (5) | C11B—C16B | 1.393 (5) |
C12A—C13A | 1.359 (5) | C12B—C13B | 1.376 (5) |
C12A—H12A | 0.93 | C12B—H12B | 0.93 |
C13A—C14A | 1.377 (6) | C13B—C14B | 1.372 (5) |
C14A—C15A | 1.378 (6) | C14B—C15B | 1.372 (6) |
C14A—H14A | 0.93 | C14B—H14B | 0.93 |
C15A—C16A | 1.372 (6) | C15B—C16B | 1.374 (6) |
C15A—H15A | 0.93 | C15B—H15B | 0.93 |
C16A—H16A | 0.93 | C16B—H16B | 0.93 |
C6A—C1A—C2A | 119.4 (4) | C6B—C1B—C2B | 120.0 (4) |
C6A—C1A—C7A | 119.2 (3) | C6B—C1B—C7B | 119.9 (3) |
C2A—C1A—C7A | 121.3 (4) | C2B—C1B—C7B | 120.1 (3) |
O2A—C2A—C3A | 119.2 (3) | O2B—C2B—C3B | 120.0 (3) |
O2A—C2A—C1A | 121.3 (4) | O2B—C2B—C1B | 121.6 (4) |
C3A—C2A—C1A | 119.5 (4) | C3B—C2B—C1B | 118.4 (3) |
C4A—C3A—C2A | 120.5 (3) | C4B—C3B—C2B | 120.4 (4) |
C4A—C3A—I3A | 120.4 (3) | C4B—C3B—I3B | 120.8 (3) |
C2A—C3A—I3A | 119.0 (3) | C2B—C3B—I3B | 118.9 (3) |
C3A—C4A—C5A | 119.0 (4) | C3B—C4B—C5B | 119.4 (4) |
C3A—C4A—H4A | 120.5 | C3B—C4B—H4B | 120.3 |
C5A—C4A—H4A | 120.5 | C5B—C4B—H4B | 120.3 |
C6A—C5A—C4A | 122.1 (4) | C6B—C5B—C4B | 122.3 (4) |
C6A—C5A—N5A | 119.0 (3) | C6B—C5B—N5B | 119.1 (4) |
C4A—C5A—N5A | 118.9 (4) | C4B—C5B—N5B | 118.6 (4) |
C5A—C6A—C1A | 119.3 (3) | C5B—C6B—C1B | 119.4 (4) |
C5A—C6A—H6A | 120.3 | C5B—C6B—H6B | 120.3 |
C1A—C6A—H6A | 120.3 | C1B—C6B—H6B | 120.3 |
C2A—O2A—H2A | 109.5 | C2B—O2B—H2B | 109.5 |
O51A—N5A—O52A | 122.8 (4) | O51B—N5B—O52B | 123.5 (4) |
O51A—N5A—C5A | 119.2 (3) | O51B—N5B—C5B | 118.3 (4) |
O52A—N5A—C5A | 118.1 (4) | O52B—N5B—C5B | 118.2 (4) |
N1A—C7A—C1A | 121.1 (4) | N1B—C7B—C1B | 121.7 (4) |
N1A—C7A—H7A | 119.4 | N1B—C7B—H7B | 119.2 |
C1A—C7A—H7A | 119.4 | C1B—C7B—H7B | 119.2 |
C7A—N1A—C11A | 123.6 (3) | C7B—N1B—C11B | 123.6 (3) |
C16A—C11A—C12A | 119.7 (4) | C12B—C11B—C16B | 120.1 (4) |
C16A—C11A—N1A | 116.0 (4) | C12B—C11B—N1B | 115.9 (3) |
C12A—C11A—N1A | 124.2 (4) | C16B—C11B—N1B | 124.0 (4) |
C13A—C12A—C11A | 117.5 (4) | C13B—C12B—C11B | 118.2 (4) |
C13A—C12A—H12A | 121.2 | C13B—C12B—H12B | 120.9 |
C11A—C12A—H12A | 121.2 | C11B—C12B—H12B | 120.9 |
C12A—C13A—C14A | 124.0 (4) | C14B—C13B—C12B | 122.8 (4) |
C12A—C13A—N13A | 118.5 (4) | C14B—C13B—N13B | 119.2 (4) |
C14A—C13A—N13A | 117.5 (4) | C12B—C13B—N13B | 118.0 (4) |
C13A—C14A—C15A | 117.5 (4) | C15B—C14B—C13B | 118.1 (4) |
C13A—C14A—H14A | 121.2 | C15B—C14B—H14B | 121.0 |
C15A—C14A—H14A | 121.2 | C13B—C14B—H14B | 121.0 |
C16A—C15A—C14A | 120.3 (4) | C14B—C15B—C16B | 121.3 (4) |
C16A—C15A—H15A | 119.8 | C14B—C15B—H15B | 119.4 |
C14A—C15A—H15A | 119.8 | C16B—C15B—H15B | 119.4 |
C15A—C16A—C11A | 121.0 (4) | C15B—C16B—C11B | 119.5 (4) |
C15A—C16A—H16A | 119.5 | C15B—C16B—H16B | 120.2 |
C11A—C16A—H16A | 119.5 | C11B—C16B—H16B | 120.2 |
O13A—N13A—O14A | 124.6 (4) | O14B—N13B—O13B | 124.1 (4) |
O13A—N13A—C13A | 117.1 (4) | O14B—N13B—C13B | 118.7 (4) |
O14A—N13A—C13A | 118.2 (4) | O13B—N13B—C13B | 117.1 (4) |
C1A—C7A—N1A—C11A | −177.1 (4) | C1B—C7B—N1B—C11B | −179.4 (4) |
N1A—C7A—C1A—C2A | 0.4 (7) | N1B—C7B—C1B—C2B | 1.1 (6) |
C7A—N1A—C11A—C12A | −0.1 (7) | C7B—N1B—C11B—C12B | 176.9 (4) |
C4A—C5A—N5A—O51A | 8.2 (6) | C4B—C5B—N5B—O51B | 1.2 (7) |
C12A—C13A—N13A—O13A | −7.1 (7) | C12B—C13B—N13B—O13B | 5.5 (7) |
C6A—C1A—C2A—O2A | 179.3 (4) | C6B—C1B—C2B—O2B | 179.7 (4) |
C7A—C1A—C2A—O2A | −1.8 (7) | C7B—C1B—C2B—O2B | −0.3 (6) |
C6A—C1A—C2A—C3A | −1.2 (6) | C6B—C1B—C2B—C3B | −0.5 (6) |
C7A—C1A—C2A—C3A | 177.7 (4) | C7B—C1B—C2B—C3B | 179.4 (4) |
O2A—C2A—C3A—C4A | 179.4 (4) | O2B—C2B—C3B—C4B | −179.9 (4) |
C1A—C2A—C3A—C4A | 0.0 (6) | C1B—C2B—C3B—C4B | 0.4 (7) |
O2A—C2A—C3A—I3A | 1.9 (6) | O2B—C2B—C3B—I3B | −1.2 (6) |
C1A—C2A—C3A—I3A | −177.6 (3) | C1B—C2B—C3B—I3B | 179.0 (3) |
C2A—C3A—C4A—C5A | 1.6 (6) | C2B—C3B—C4B—C5B | 0.2 (7) |
I3A—C3A—C4A—C5A | 179.1 (3) | I3B—C3B—C4B—C5B | −178.4 (3) |
C3A—C4A—C5A—C6A | −2.0 (6) | C3B—C4B—C5B—C6B | −0.7 (7) |
C3A—C4A—C5A—N5A | 177.9 (4) | C3B—C4B—C5B—N5B | −179.6 (4) |
C4A—C5A—C6A—C1A | 0.8 (6) | C4B—C5B—C6B—C1B | 0.6 (7) |
N5A—C5A—C6A—C1A | −179.2 (4) | N5B—C5B—C6B—C1B | 179.5 (4) |
C2A—C1A—C6A—C5A | 0.9 (6) | C2B—C1B—C6B—C5B | 0.1 (7) |
C7A—C1A—C6A—C5A | −178.1 (4) | C7B—C1B—C6B—C5B | −179.9 (4) |
C6A—C5A—N5A—O51A | −171.8 (4) | C6B—C5B—N5B—O51B | −177.7 (5) |
C6A—C5A—N5A—O52A | 8.9 (6) | C6B—C5B—N5B—O52B | 3.2 (7) |
C4A—C5A—N5A—O52A | −171.1 (4) | C4B—C5B—N5B—O52B | −177.8 (4) |
C6A—C1A—C7A—N1A | 179.3 (4) | C6B—C1B—C7B—N1B | −179.0 (4) |
C7A—N1A—C11A—C16A | 177.5 (4) | C7B—N1B—C11B—C16B | −2.5 (7) |
C16A—C11A—C12A—C13A | −0.1 (7) | C16B—C11B—C12B—C13B | 1.8 (7) |
N1A—C11A—C12A—C13A | 177.4 (4) | N1B—C11B—C12B—C13B | −177.5 (4) |
C11A—C12A—C13A—C14A | −0.7 (7) | C11B—C12B—C13B—C14B | −1.3 (7) |
C11A—C12A—C13A—N13A | −179.6 (4) | C11B—C12B—C13B—N13B | 179.3 (4) |
C12A—C13A—C14A—C15A | 0.8 (8) | C12B—C13B—C14B—C15B | −0.1 (7) |
N13A—C13A—C14A—C15A | 179.7 (5) | N13B—C13B—C14B—C15B | 179.3 (4) |
C13A—C14A—C15A—C16A | 0.0 (8) | C13B—C14B—C15B—C16B | 0.9 (7) |
C14A—C15A—C16A—C11A | −0.8 (9) | C14B—C15B—C16B—C11B | −0.3 (7) |
C12A—C11A—C16A—C15A | 0.9 (8) | C12B—C11B—C16B—C15B | −1.1 (7) |
N1A—C11A—C16A—C15A | −176.9 (5) | N1B—C11B—C16B—C15B | 178.2 (4) |
C14A—C13A—N13A—O13A | 173.9 (5) | C14B—C13B—N13B—O14B | 4.8 (7) |
C12A—C13A—N13A—O14A | 175.7 (5) | C12B—C13B—N13B—O14B | −175.8 (5) |
C14A—C13A—N13A—O14A | −3.3 (7) | C14B—C13B—N13B—O13B | −173.9 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2A···N1A | 0.82 | 1.85 | 2.580 (4) | 148 |
O2B—H2B···N1B | 0.82 | 1.81 | 2.549 (4) | 149 |
C7A—H7A···O52B | 0.93 | 2.37 | 3.263 (5) | 160 |
C7B—H7B···O52A | 0.93 | 2.36 | 3.254 (5) | 162 |
C14A—H14A···O51Ai | 0.93 | 2.53 | 3.372 (6) | 151 |
C14B—H14B···O14Bii | 0.93 | 2.51 | 3.279 (6) | 141 |
C16A—H16A···O13Biii | 0.93 | 2.47 | 3.377 (5) | 166 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x, −y, −z+1; (iii) x+3/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H8IN3O5 |
Mr | 413.12 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 291 |
a, b, c (Å) | 9.2957 (4), 27.5905 (13), 11.0084 (5) |
β (°) | 93.830 (2) |
V (Å3) | 2817.1 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.30 |
Crystal size (mm) | 0.30 × 0.22 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.545, 0.893 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29048, 10158, 4201 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.757 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.093, 0.87 |
No. of reflections | 10158 |
No. of parameters | 399 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72, −0.51 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
C1A—C2A | 1.411 (5) | C1B—C2B | 1.419 (5) |
C2A—C3A | 1.406 (5) | C2B—C3B | 1.414 (5) |
C3A—C4A | 1.377 (5) | C3B—C4B | 1.368 (5) |
C4A—C5A | 1.387 (5) | C4B—C5B | 1.388 (5) |
C5A—C6A | 1.380 (5) | C5B—C6B | 1.359 (5) |
C6A—C1A | 1.394 (5) | C6B—C1B | 1.388 (5) |
C2A—O2A | 1.327 (4) | C2B—O2B | 1.311 (4) |
C5A—N5A | 1.457 (5) | C5B—N5B | 1.463 (5) |
N5A—O51A | 1.217 (4) | N5B—O51B | 1.204 (4) |
N5A—O52A | 1.229 (4) | N5B—O52B | 1.232 (4) |
C13A—N13A | 1.484 (5) | C13B—N13B | 1.475 (5) |
N13A—O13A | 1.198 (5) | N13B—O13B | 1.215 (5) |
N13A—O14A | 1.207 (4) | N13B—O14B | 1.208 (4) |
C1A—C7A—N1A—C11A | −177.1 (4) | C1B—C7B—N1B—C11B | −179.4 (4) |
N1A—C7A—C1A—C2A | 0.4 (7) | N1B—C7B—C1B—C2B | 1.1 (6) |
C7A—N1A—C11A—C12A | −0.1 (7) | C7B—N1B—C11B—C12B | 176.9 (4) |
C4A—C5A—N5A—O51A | 8.2 (6) | C4B—C5B—N5B—O51B | 1.2 (7) |
C12A—C13A—N13A—O13A | −7.1 (7) | C12B—C13B—N13B—O13B | 5.5 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2A···N1A | 0.82 | 1.85 | 2.580 (4) | 148 |
O2B—H2B···N1B | 0.82 | 1.81 | 2.549 (4) | 149 |
C7A—H7A···O52B | 0.93 | 2.37 | 3.263 (5) | 160 |
C7B—H7B···O52A | 0.93 | 2.36 | 3.254 (5) | 162 |
C14A—H14A···O51Ai | 0.93 | 2.53 | 3.372 (6) | 151 |
C14B—H14B···O14Bii | 0.93 | 2.51 | 3.279 (6) | 141 |
C16A—H16A···O13Biii | 0.93 | 2.47 | 3.377 (5) | 166 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x, −y, −z+1; (iii) x+3/2, −y+1/2, z−1/2. |
Acknowledgements
The authors thank the University of Aberdeen for funding the purchase of the diffractometer. JLW thanks CNPq and FAPERJ for financial support.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science 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 (1998). SMART. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2000). SADABS (Version 2.03) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Ferguson, G., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005). Acta Cryst. C61, o445–o449. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Garden, S. J., da Cunha, F. R., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2004). Acta Cryst. C60, o12–o14. Web of Science CSD CrossRef IUCr Journals Google Scholar
Glidewell, C., Howie, R. A., Low, J. N., Skakle, J. M. S., Wardell, S. M. S. V. & Wardell, J. L. (2002). Acta Cryst. B58, 864–876. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. 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
Starbuck, J., Norman, N. C. & Orpen, A. G. (1999). New J. Chem. 23, 969–972. Web of Science CrossRef Google Scholar
Wardell, J. L., Wardell, S. M. S. V., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2002). Acta Cryst. C58, o428–o430. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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We have recently reported the supramolecular structures of imines containing iodo and nitro groups, for example N-(2-iodobenzylidene)-3-nitroaniline, 2-IC6H4CH═ NC6H4NO2-3' (Wardell et al., 2002), and the various isomeric N-(nitrobenzylidene)iodoanilines, O2NC6H4CH═NC6H4I (Glidewell et al., 2002), several of which crystallize in two polymorphic forms (Ferguson et al., 2005). We have now continued our studies in this area with the title compound, (I), an imine containing an additional nitro group as well as a hard hydrogen-bonding donor group.
Compound (I) crystallizes with Z' = 2 in space group P21/n (Fig. 1). In each of the independent molecules there is an intramolecular O—H···N hydrogen bond, forming an S(6) motif (Bernstein et al., 1995), and these interactions undoubtedly influence the molecular conformations. Both molecules are nearly planar. The overall conformation in each is defined by five torsion angles (Table 1), and it is striking that in molecule A (Fig. 1) the two nitro groups are on the same edge of the molecule, whereas in molecule B these substituents are on opposite edges. The two molecules are thus conformational isomers, and this alone suffices to preclude any possible additional symmetry.
Within the molecules, the bond distances show some interesting patterns (Table 1), consequent upon the mutually para arrangement in the iodinated rings of the electron-donor hydroxyl substituent and the electron-acceptor nitro group; in the non-iodinated rings, there is no possibility of any conjugative interactions. Thus, the C—O bonds are significantly shorter than is typical in simple phenols (mean value 1.362 Å; Allen et al., 1987). Of the C—N bonds to the nitro groups, the bonds C5A—N5A and C5B—N5B are both somewhat shorter than the mean value for simple aromatic nitro compounds (1.468 Å), whereas the bonds C13A—N13A and C13B—N13B are both considerably longer. The N—O bonds involving atoms N5A and N5B are consistently shorter than those involving atoms N13A and N13B. Finally, there is some evidence of C—C bond fixation within the iodinated rings. These observations, taken together, provide some evidence in favour of the polarized form, (Ia), as a modest contributor to the overall molecular electronic structure.
Within the selected asymmetric unit, the two molecules are linked by two C—H···O hydrogen bonds (Fig. 1, Table 2), and this bimolecular aggregate can be regarded as the basic building block within the supramolecular structure. Three further C—H···O hydrogen bonds and a two-centre iodo···nitro interaction then link these aggregates into complex sheets, the formation of which can be readily analysed in terms of one-dimensional sub-structures.
In the principal sub-structure, atom C14B at (x, y, z) acts as hydrogen-bond donor to atom O14B at (−x, −y, 1 − z), so generating by inversion a centrosymmetric R22(10) motif centred at (0, 0, 1/2). At the same time, atom I3B at (x, y, z) forms a two-centre interaction with atom O13A at (−x, 1 − y, 1 − z), with dimensions I···Oi = 3.173 (4) Å and C—I···Oi = 175.6 (2)° [symmetry code: (i) −x, 1 − y, 1 − z], so generating by inversion an R44(28) (Starbuck et al., 1999) motif centred at (0, 1/2, 1/2). Propagation by inversion of these two interactions then generates a chain running parallel to the [010] direction containing R22(10) rings centred at (0, n, 1/2) (n = zero or integer) and R44(28) rings centred at (0, n + 1/2, 1/2) (n = zero or integer), together with two types of S(6) ring and an R22(14) ring (Fig. 2).
Two further C—H···O hydrogen bonds link the [010] chains into sheets. The type A molecules (Fig. 1) at (x, y, z) and (−x, −y, 1 − z) form part of the chain along (0, y, 1/2) (Fig. 2). The atoms C14A at (x, y, z) and (−x, −y, 1 − z), act as hydrogen-bond donors to, respectively, atoms O51A at (3/2 − x, 1/2 + y, 1/2 − z) and (−3/2 + x, −1/2 − y, 1/2 + z), which themselves lie in the [010] chains along (3/2, y, 0) and (−3/2, y, 1), respectively. Hence, the propagation of this hydrogen bond by the 21screw axes along [3(2m + 1)/4, y, (1 − 2m)/4] (m = zero or integer) links the [010] chains into a (103) sheet. The formation of this sheet is reinforced by the final C—H···O hydrogen bond, in which atom C16A at (x, y, z) acts as hydrogen-bond donor to atom O13B at (3/2 + x, 1/2 − y, −1/2 + z), so forming a C22(18) C22(18)[R22(14)] chain of rings running parallel to the [301] direction and generated by the n-glide plane at y = 1/4 (Fig. 3).
There are no direction-specific interactions between adjacent sheets. In particular, C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent from the structure of (I).