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In 2-iodo-N-(3-nitro­benzyl)­aniline, C13H11IN2O2, the mol­ecules are linked into a three-dimensional structure by a combination of C—H...O hydrogen bonds, iodo–nitro interactions and aromatic π–π-stacking interactions, but N—H...O and C—H...π(arene) hydrogen bonds are absent. In the isomeric 3-iodo-N-(3-nitro­benzyl)­aniline, a two-dimensional array is generated by a combination of N—H...O, C—H...O and C—H...π(arene) hydrogen bonds, but iodo–nitro interactions and aromatic π–π-stacking interactions are both absent.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010201140X/gg1122sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010201140X/gg1122Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010201140X/gg1122IIsup3.hkl
Contains datablock II

CCDC references: 193432; 193433

Comment top

We have recently reported (Glidewell et al., 2002) the molecular and supramolecular structures of eight isomeric nitrobenzylidene-iodoanilines, O2NC6H4CHNC6H4I, all of which manifest different combinations of C—H···O hydrogen bonds, iodo···nitro interactions, and aromatic π···π stacking interactions, giving supramolecular structures in zero, one, two or three dimensions. Here, we report the structures of two representative iodo-N-(nitrobenzyl)anilines, compounds (I) and (II), of general formula O2NC6H4CH2NHC6H4I, in which N—H···O hydrogen bonds can occur, in addition to all of the interactions noted above. \sch

The bond lengths and inter-bond angles in (I) and (II) show no unusual features, but the molecular conformations are markedly different. If the C1—N1—C17 fragment is taken as a reference plane, it is clear from the torsion angles (Tables 1 and 3; Figs. 1 and 4) that the location of the I and nitro substituents is entirely different in (I) and (II). Since the overall conformations are dependent on largely unhindered rotations about single bonds in the C1—N1—C17—C11 unit, it is likely that the observed conformations are determined primarily by direction-specific intermolecular interactions of various types, the manifestation of which differs significantly between the two structures.

In the supramolecular structure of compound (I) (Fig. 1), there are, surprisingly, no N—H···O hydrogen bonds. Instead, the structure is determined by a combination of weak C—H···O hydrogen bonds, iodo···nitro interactions and aromatic π···π stacking interactions. Atom C4 in the iodinated ring of the molecule at (x, y, z) acts as a hydrogen-bond donor to atom O131 in the molecule at (1 - x, 1 - y, 1 - z) (Table 2), so generating a cyclic centrosymmetric motif (Fig. 2). Atom I2 in the molecule at (x, y, z) forms a weak two-centre iodo···nitro interaction with atom O131ii, with I···Oii 3.517 (2) Å, C—I···Oii 158.12 (7)° and I···Oii—Nii 101.4 (2)° [symmetry code: (ii) x, y, z - 1]. The combination of these two interactions generates a molecular ladder, or a chain of edge-fused rings, running parallel to the [001] direction, with hydrogen-bonded R22(24) rings centred at (1/2,1/2,1/2+n) (n = zero or integer), and R42(12) rings containing both hydrogen bonds and I···O interactions (Bernstein et al., 1995; Starbuck et al., 1999) centred at (1/2,1/2,n) (n = zero or integer) (Fig. 2).

Two of these molecular ladders pass through each unit cell, and each ladder is linked to its four immediate neighbours by means of aromatic π···π stacking interactions, so linking all of the ladders into a single three-dimensional continuum. The nitrated ring of the molecule at (x, y, z) forms a π···π stacking interaction with the iodinated ring of the molecule at (1/2 + x, 3/2 - y, 1/2 + z) (Fig. 3), where the interplanar angle is 5.3°, the centroid separation is 3.696 (2) Å and the interplanar spacing is ca 3.42 Å, corresponding to a centroid offset of ca 1.40 Å (Fig. 3). The molecules at (x, y, z) and (1/2 + x, 3/2 - y, 1/2 + z) form part of the ladders along (1/2, 1/2, z) and (1, 1, z), respectively. Propagation of the π···π stacking interaction by the n-glide plane links the ladder along (1/2,1/2,z) to that at (0,1,z), while the action of the centres of inversion links the (1/2,1/2,z) ladder to those along (0,0,z) and (1,0,z) also. Hence, each ladder is linked to four others, forming a continuously linked bundle.

The structure of compound (II) (Fig. 4), by contrast with that of (I), is dominated by hydrogen bonds (Table 4), while iodo···nitro interactions and aromatic π···π stacking interactions are both absent. The amino atom N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom O131 in the molecule at (1/2 - x, 1 - y, 1/2 + z) and, at the same time, atom C14 at (x, y, z) acts as a hydrogen-bond donor to atom O132 at (1/2 - x, 1 - y, z - 1/2). Propagation of these two hydrogen bonds thus produces a C(5) C(8)[R22(13)] chain of rings (Bernstein et al., 1995), running parallel to the [001] direction and generated by the 21 screw axis along (1/4,1/2,z) (Fig. 5).

Four [001] chains run through each unit cell of (II) and they are linked into sheets, parallel to (010), by means of a single C—H···π(arene) hydrogen bond. Atom C15 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the iodinated ring C1—C6 (centroid Cg1, Table 4) of the molecule at (1/2 + x, y, 1/2 - z), and propagation of this interaction produces a chain running parallel to the [100] direction, generated by the a-glide plane at z = 1/4 (Fig. 6). The combination of the [100] and [001] chains generates the (010) sheet.

In view of the differences between compounds (I) and (II), in terms both of the overall supramolecular structures and of the types of weak intermolecular interaction involved, it is of interest to compare these structures with those of the analogues, (III) and (IV), from the structures of which N—H···O hydrogen bonds are precluded (Glidewell et al., 2002). In compound (III), the molecules are linked into simple chains by C—H···O hydrogen bonds. Unlike (I), there are no iodo···nitro interactions in (III) and, indeed, such interactions are absent from all isomers of (III) having the I substituent in the 2-position. In the structure of (IV), a combination of C—H···O hydrogen bonds and iodo···nitro interactions generates molecular ladders, which are themselves linked into sheets by aromatic π···π stacking interactions. As noted above, in the saturated analogue, (II), there are neither iodo···nitro interactions nor aromatic π···π stacking interactions. Thus, both (I) and (II) exhibit very marked differences in supramolecular aggregation from their analogues, (III) and (IV), respectively. These differences were not predicted, and they are not readily explicable.

Experimental top

Samples of (I) and (II) were prepared by reduction of the corresponding benzylidine-anilines, (III) and (IV), respectively, using a fivefold molar excess of Na[BH4] in refluxing methanol during 1 h. After work-up, crystals of (I) and (II) suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in ethanol [m.p. 361–363 K for (I), 352–353 K for (II)].

Refinement top

For compounds (I) and (II), the space groups P21/n and Pbca, respectively, were uniquely assigned from the systematic absences. H atoms were treated as riding atoms, with C—H distances of 0.95 Å (aromatic) and 0.99 Å (CH2), and N—H distances of 0.88 Å.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997) for (I); SMART (Bruker, 1998) for (II). Cell refinement: DENZO-SMN (Otwinowski & Minor, 1997) for (I); SAINT (Bruker, 2000) for (II). Data reduction: DENZO-SMN for (I); SAINT (Bruker, 2000) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing formation of a molecular ladder along [001]. The atoms marked with an asterisk (*), hash (#), dollar sign (add), ampersand (add) or at sign (@) are at the symmetry positions (x, y, 1 + z), (x, y, z - 1), (1 - x, 1 - y, -z), (1 - x, 1 - y, 1 - z) and (1 - x, 1 - y, 2 - z), respectively.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the aromatic π···π stacking interaction between rings of different types. For the sake of clarity, the unit-cell box has been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1/2 + x, 3/2 - y, 1/2 + z).
[Figure 4] Fig. 4. A view of the molecule of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 5] Fig. 5. Part of the crystal structure of (II), showing formation of a chain of rings along [001]. The atoms marked with an asterisk (*), hash (#) or dollar sign (add) are at the symmetry positions (1/2 - x, 1 - y, 1/2 + z), (1/2 - x, 1 - y, z - 1/2) and (x, y, 1 + z), respectively.
[Figure 6] Fig. 6. A stereoview of part of the crystal structure of (II), showing formation by the C—H···π(arene) hydrogen bond of a chain along [100].
(I) 2-iodo-N-(3-Nitrobenzyl)aniline top
Crystal data top
C13H11IN2O2F(000) = 688
Mr = 354.14Dx = 1.945 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2744 reflections
a = 11.4056 (3) Åθ = 3.0–27.5°
b = 8.7364 (3) ŵ = 2.64 mm1
c = 12.8357 (5) ÅT = 150 K
β = 109.0049 (12)°Plate, yellow
V = 1209.28 (7) Å30.10 × 0.10 × 0.05 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
2744 independent reflections
Radiation source: fine-focus sealed X-ray tube2320 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 1414
Tmin = 0.778, Tmax = 0.879k = 1111
9597 measured reflectionsl = 1316
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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2)P)2 + 0.2916P]
where P = (Fo2 + 2Fc2)/3
2744 reflections(Δ/σ)max = 0.002
163 parametersΔρmax = 0.77 e Å3
0 restraintsΔρmin = 0.71 e Å3
Crystal data top
C13H11IN2O2V = 1209.28 (7) Å3
Mr = 354.14Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.4056 (3) ŵ = 2.64 mm1
b = 8.7364 (3) ÅT = 150 K
c = 12.8357 (5) Å0.10 × 0.10 × 0.05 mm
β = 109.0049 (12)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
2744 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
2320 reflections with I > 2σ(I)
Tmin = 0.778, Tmax = 0.879Rint = 0.040
9597 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.053H-atom parameters constrained
S = 1.06Δρmax = 0.77 e Å3
2744 reflectionsΔρmin = 0.71 e Å3
163 parameters
Special details top

Experimental. The program DENZOo-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G. C. & Holmes, K. C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code word was used.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.7374 (2)0.7365 (2)0.38064 (18)0.0166 (5)
C10.6495 (2)0.6280 (3)0.3288 (2)0.0130 (5)
C20.6207 (2)0.5946 (3)0.2161 (2)0.0136 (5)
I20.711807 (14)0.712576 (17)0.121937 (13)0.01622 (8)
C30.5338 (2)0.4850 (3)0.1652 (2)0.0148 (5)
C40.4712 (2)0.4055 (3)0.2243 (2)0.0169 (6)
C50.4995 (2)0.4344 (3)0.3356 (2)0.0172 (6)
C60.5875 (2)0.5435 (3)0.3871 (2)0.0151 (5)
C170.7430 (3)0.8005 (3)0.4859 (2)0.0178 (6)
C110.8153 (2)0.7072 (3)0.5856 (2)0.0139 (6)
C120.8044 (2)0.7450 (3)0.6866 (2)0.0136 (5)
C130.8743 (2)0.6655 (3)0.7793 (2)0.0145 (5)
N130.8625 (2)0.7088 (2)0.88553 (19)0.0176 (5)
O1310.79317 (16)0.8139 (2)0.88930 (15)0.0220 (5)
O1320.92388 (19)0.6373 (2)0.96755 (15)0.0317 (5)
C140.9539 (2)0.5483 (3)0.7750 (2)0.0164 (6)
C150.9635 (2)0.5119 (3)0.6738 (2)0.0173 (6)
C160.8947 (2)0.5901 (3)0.5800 (2)0.0165 (6)
H10.79100.76720.34890.020*
H30.51660.46390.08910.018*
H40.40980.33210.18870.020*
H50.45830.37900.37720.021*
H60.60610.56120.46390.018*
H17A0.65720.81330.48720.021*
H17B0.78070.90360.49240.021*
H20.74970.82430.69230.016*
H141.00040.49470.83970.020*
H151.01780.43230.66830.021*
H160.90200.56290.51070.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0183 (12)0.0219 (11)0.0107 (12)0.0057 (10)0.0061 (9)0.0019 (9)
C10.0140 (12)0.0115 (12)0.0125 (13)0.0036 (11)0.0028 (10)0.0018 (10)
C20.0152 (12)0.0131 (12)0.0134 (13)0.0026 (10)0.0059 (10)0.0035 (10)
I20.01897 (12)0.01827 (12)0.01286 (12)0.00237 (7)0.00714 (8)0.00039 (6)
C30.0163 (12)0.0167 (13)0.0083 (13)0.0022 (11)0.0000 (10)0.0007 (10)
C40.0115 (12)0.0161 (13)0.0203 (15)0.0011 (11)0.0011 (11)0.0021 (11)
C50.0177 (13)0.0152 (12)0.0214 (15)0.0019 (11)0.0099 (11)0.0033 (11)
C60.0165 (12)0.0194 (13)0.0097 (13)0.0039 (11)0.0050 (10)0.0024 (11)
C170.0238 (14)0.0162 (13)0.0112 (14)0.0004 (11)0.0027 (12)0.0019 (10)
C110.0136 (13)0.0120 (13)0.0146 (14)0.0035 (10)0.0025 (11)0.0006 (10)
C120.0130 (13)0.0134 (12)0.0149 (14)0.0033 (10)0.0053 (11)0.0026 (11)
C130.0139 (13)0.0176 (12)0.0124 (14)0.0051 (11)0.0048 (11)0.0013 (11)
N130.0160 (11)0.0241 (12)0.0127 (12)0.0043 (10)0.0047 (10)0.0013 (9)
O1310.0207 (11)0.0271 (10)0.0185 (11)0.0041 (8)0.0067 (9)0.0053 (8)
O1320.0430 (12)0.0397 (12)0.0130 (10)0.0140 (11)0.0100 (9)0.0092 (9)
C140.0158 (13)0.0168 (13)0.0146 (14)0.0022 (11)0.0023 (11)0.0028 (11)
C150.0162 (12)0.0149 (13)0.0212 (15)0.0015 (11)0.0068 (11)0.0018 (11)
C160.0192 (13)0.0185 (13)0.0125 (14)0.0046 (11)0.0060 (11)0.0040 (10)
Geometric parameters (Å, º) top
N1—C11.383 (3)C17—H17A0.9900
N1—C171.444 (3)C17—H17B0.9900
N1—H10.8800C11—C121.382 (4)
C1—C61.397 (3)C11—C161.383 (3)
C1—C21.406 (3)C12—C131.385 (3)
C2—C31.380 (3)C12—H20.9500
C2—I22.102 (2)C13—C141.382 (3)
C3—C41.384 (4)C13—N131.463 (3)
C3—H30.9500N13—O1311.223 (3)
C4—C51.382 (4)N13—O1321.228 (3)
C4—H40.9500C14—C151.375 (4)
C5—C61.386 (3)C14—H140.9500
C5—H50.9500C15—C161.385 (3)
C6—H60.9500C15—H150.9500
C17—C111.515 (3)C16—H160.9500
C1—N1—C17121.3 (2)N1—C17—H17B108.4
C1—N1—H1119.3C11—C17—H17B108.4
C17—N1—H1119.3H17A—C17—H17B107.5
N1—C1—C6121.2 (2)C12—C11—C16119.1 (2)
N1—C1—C2121.8 (2)C12—C11—C17118.2 (2)
C6—C1—C2116.9 (2)C16—C11—C17122.6 (2)
C3—C2—C1121.4 (2)C11—C12—C13118.9 (2)
C3—C2—I2118.82 (18)C11—C12—H2120.5
C1—C2—I2119.75 (17)C13—C12—H2120.5
C2—C3—C4120.5 (2)C14—C13—C12122.6 (2)
C2—C3—H3119.7C14—C13—N13119.4 (2)
C4—C3—H3119.7C12—C13—N13118.0 (2)
C5—C4—C3119.1 (2)O131—N13—O132122.9 (2)
C5—C4—H4120.4O131—N13—C13119.2 (2)
C3—C4—H4120.4O132—N13—C13117.9 (2)
C4—C5—C6120.5 (2)C15—C14—C13117.7 (2)
C4—C5—H5119.8C15—C14—H14121.2
C6—C5—H5119.8C13—C14—H14121.2
C5—C6—C1121.5 (2)C14—C15—C16120.7 (2)
C5—C6—H6119.3C14—C15—H15119.6
C1—C6—H6119.3C16—C15—H15119.6
N1—C17—C11115.3 (2)C11—C16—C15121.0 (2)
N1—C17—H17A108.4C11—C16—H16119.5
C11—C17—H17A108.4C15—C16—H16119.5
C2—C1—N1—C17162.8 (2)C12—C13—N13—O132179.4 (2)
C1—N1—C17—C1184.4 (3)C14—C13—N13—O131179.1 (2)
N1—C17—C11—C12167.5 (2)C14—C13—N13—O1320.6 (3)
C12—C13—N13—O1310.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O131i0.952.553.468 (3)164
Symmetry code: (i) x+1, y+1, z+1.
(II) 3-iodo-N-(3-Nitrobenzyl)aniline top
Crystal data top
C13H11IN2O2F(000) = 1376
Mr = 354.14Dx = 1.834 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3186 reflections
a = 7.9024 (5) Åθ = 1.4–29.0°
b = 28.7265 (15) ŵ = 2.49 mm1
c = 11.3019 (6) ÅT = 120 K
V = 2565.6 (3) Å3Lath, orange
Z = 80.35 × 0.15 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3186 independent reflections
Radiation source: fine-focus sealed X-ray tube2487 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ϕ and ω scansθmax = 28.5°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.632, Tmax = 0.775k = 3737
16085 measured reflectionsl = 1515
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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.21 w = 1/[σ2(Fo2) + (0.0447P)2 + 0.5158P]
where P = (Fo2 + 2Fc2)/3
3186 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 1.26 e Å3
Crystal data top
C13H11IN2O2V = 2565.6 (3) Å3
Mr = 354.14Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.9024 (5) ŵ = 2.49 mm1
b = 28.7265 (15) ÅT = 120 K
c = 11.3019 (6) Å0.35 × 0.15 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3186 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2487 reflections with I > 2σ(I)
Tmin = 0.632, Tmax = 0.775Rint = 0.019
16085 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.21Δρmax = 0.49 e Å3
3186 reflectionsΔρmin = 1.26 e Å3
163 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2440 (3)0.35278 (8)0.55834 (17)0.0177 (4)
N10.3957 (3)0.37589 (7)0.57762 (15)0.0210 (4)
C20.2252 (3)0.32010 (7)0.46661 (19)0.0174 (4)
C30.0710 (3)0.29732 (8)0.45373 (19)0.0183 (4)
I30.04055 (2)0.249097 (4)0.315030 (14)0.02199 (8)
C40.0658 (3)0.30543 (8)0.5284 (2)0.0228 (5)
C50.0449 (3)0.33769 (9)0.6187 (2)0.0238 (5)
C60.1063 (3)0.36102 (8)0.63407 (19)0.0225 (5)
C110.4734 (3)0.40475 (8)0.3760 (2)0.0190 (5)
C120.3905 (3)0.44716 (7)0.38475 (19)0.0195 (5)
C130.3455 (3)0.47019 (8)0.2813 (2)0.0202 (5)
N130.2565 (3)0.51451 (8)0.28992 (18)0.0260 (5)
O1310.1950 (3)0.53116 (6)0.19910 (15)0.0363 (5)
O1320.2435 (3)0.53339 (6)0.38672 (16)0.0435 (5)
C140.3807 (3)0.45262 (8)0.1692 (2)0.0237 (5)
C150.4641 (3)0.41029 (9)0.1622 (2)0.0262 (5)
C160.5097 (3)0.38687 (8)0.2645 (2)0.0234 (5)
C170.5257 (3)0.37839 (8)0.4873 (2)0.0211 (5)
H10.41340.38940.64640.025*
H20.31630.31370.41430.021*
H40.17000.28940.51790.027*
H50.13640.34390.67090.029*
H60.11730.38290.69660.027*
H120.36500.46020.45990.023*
H140.34870.46910.09990.028*
H150.49000.39730.08710.031*
H160.56710.35790.25840.028*
H17A0.55830.34630.46470.025*
H17B0.62690.39360.52140.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0213 (11)0.0171 (10)0.0147 (10)0.0033 (9)0.0041 (9)0.0034 (8)
N10.0261 (11)0.0223 (10)0.0145 (9)0.0014 (9)0.0050 (8)0.0017 (7)
C20.0178 (11)0.0191 (10)0.0153 (10)0.0020 (9)0.0001 (9)0.0021 (8)
C30.0204 (11)0.0180 (11)0.0165 (10)0.0031 (9)0.0014 (9)0.0014 (8)
I30.01802 (12)0.02279 (12)0.02518 (13)0.00249 (6)0.00290 (5)0.00465 (5)
C40.0181 (11)0.0250 (12)0.0252 (12)0.0012 (9)0.0013 (10)0.0061 (10)
C50.0255 (13)0.0285 (13)0.0173 (11)0.0075 (10)0.0060 (9)0.0046 (9)
C60.0307 (13)0.0222 (11)0.0144 (10)0.0064 (10)0.0009 (10)0.0017 (8)
C110.0175 (11)0.0190 (11)0.0206 (11)0.0050 (9)0.0010 (9)0.0012 (8)
C120.0225 (12)0.0189 (11)0.0170 (11)0.0036 (9)0.0005 (9)0.0022 (8)
C130.0247 (12)0.0167 (11)0.0192 (11)0.0038 (9)0.0002 (10)0.0018 (8)
N130.0353 (13)0.0200 (9)0.0228 (10)0.0017 (8)0.0010 (9)0.0034 (8)
O1310.0543 (13)0.0272 (10)0.0273 (10)0.0065 (9)0.0071 (9)0.0086 (7)
O1320.0754 (16)0.0288 (10)0.0262 (10)0.0177 (10)0.0014 (10)0.0046 (8)
C140.0281 (13)0.0266 (12)0.0163 (11)0.0074 (10)0.0002 (10)0.0026 (9)
C150.0279 (14)0.0321 (13)0.0186 (11)0.0021 (10)0.0039 (10)0.0083 (10)
C160.0226 (11)0.0204 (12)0.0271 (13)0.0016 (10)0.0029 (10)0.0056 (9)
C170.0191 (11)0.0201 (11)0.0240 (12)0.0008 (9)0.0042 (9)0.0012 (9)
Geometric parameters (Å, º) top
C1—N11.388 (3)C11—C161.390 (3)
C1—C61.404 (3)C11—C171.525 (3)
C1—C21.406 (3)C12—C131.389 (3)
N1—C171.450 (3)C12—H120.9500
N1—H10.8800C13—C141.392 (3)
C2—C31.391 (3)C13—N131.458 (3)
C2—H20.9500N13—O1321.225 (3)
C3—C41.391 (3)N13—O1311.232 (3)
C3—I32.106 (2)C14—C151.385 (3)
C4—C51.388 (3)C14—H140.9500
C4—H40.9500C15—C161.385 (3)
C5—C61.381 (3)C15—H150.9500
C5—H50.9500C16—H160.9500
C6—H60.9500C17—H17A0.9900
C11—C121.387 (3)C17—H17B0.9900
N1—C1—C6119.53 (19)C11—C12—C13118.6 (2)
N1—C1—C2121.8 (2)C11—C12—H12120.7
C6—C1—C2118.7 (2)C13—C12—H12120.7
C1—N1—C17121.67 (17)C12—C13—C14122.8 (2)
C1—N1—H1119.2C12—C13—N13118.9 (2)
C17—N1—H1119.2C14—C13—N13118.3 (2)
C3—C2—C1118.9 (2)O132—N13—O131122.6 (2)
C3—C2—H2120.5O132—N13—C13119.1 (2)
C1—C2—H2120.5O131—N13—C13118.3 (2)
C4—C3—C2122.6 (2)C15—C14—C13117.7 (2)
C4—C3—I3118.23 (17)C15—C14—H14121.1
C2—C3—I3119.18 (16)C13—C14—H14121.1
C5—C4—C3117.7 (2)C14—C15—C16120.2 (2)
C5—C4—H4121.1C14—C15—H15119.9
C3—C4—H4121.1C16—C15—H15119.9
C6—C5—C4121.3 (2)C15—C16—C11121.5 (2)
C6—C5—H5119.3C15—C16—H16119.2
C4—C5—H5119.3C11—C16—H16119.2
C5—C6—C1120.8 (2)N1—C17—C11114.41 (18)
C5—C6—H6119.6N1—C17—H17A108.7
C1—C6—H6119.6C11—C17—H17A108.7
C12—C11—C16119.1 (2)N1—C17—H17B108.7
C12—C11—C17120.4 (2)C11—C17—H17B108.7
C16—C11—C17120.5 (2)H17A—C17—H17B107.6
C6—C1—N1—C17163.72 (19)C17—C11—C12—C13179.8 (2)
C2—C1—N1—C1718.2 (3)C11—C12—C13—C140.3 (3)
C1—N1—C17—C1163.7 (3)C11—C12—C13—N13179.2 (2)
N1—C17—C11—C1245.5 (3)C12—C13—N13—O1329.7 (3)
N1—C1—C2—C3178.49 (19)C14—C13—N13—O132170.8 (2)
C6—C1—C2—C30.3 (3)C12—C13—N13—O131169.3 (2)
C1—C2—C3—C40.2 (3)C14—C13—N13—O13110.3 (3)
C1—C2—C3—I3179.07 (15)C12—C13—C14—C150.1 (4)
C2—C3—C4—C50.1 (3)N13—C13—C14—C15179.4 (2)
I3—C3—C4—C5179.26 (17)C13—C14—C15—C160.0 (4)
C3—C4—C5—C60.0 (3)C14—C15—C16—C110.2 (4)
C4—C5—C6—C10.1 (3)C12—C11—C16—C150.4 (3)
N1—C1—C6—C5178.5 (2)C17—C11—C16—C15179.7 (2)
C2—C1—C6—C50.3 (3)C16—C11—C17—N1135.1 (2)
C16—C11—C12—C130.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O131i0.882.513.087 (3)124
C14—H14···O132ii0.952.523.364 (3)148
C15—H15···Cg1iii0.952.573.438 (3)151
Symmetry codes: (i) x+1/2, y+1, z+1/2; (ii) x+1/2, y+1, z1/2; (iii) x+1/2, y, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC13H11IN2O2C13H11IN2O2
Mr354.14354.14
Crystal system, space groupMonoclinic, P21/nOrthorhombic, Pbca
Temperature (K)150120
a, b, c (Å)11.4056 (3), 8.7364 (3), 12.8357 (5)7.9024 (5), 28.7265 (15), 11.3019 (6)
α, β, γ (°)90, 109.0049 (12), 9090, 90, 90
V3)1209.28 (7)2565.6 (3)
Z48
Radiation typeMo KαMo Kα
µ (mm1)2.642.49
Crystal size (mm)0.10 × 0.10 × 0.050.35 × 0.15 × 0.10
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Multi-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.778, 0.8790.632, 0.775
No. of measured, independent and
observed [I > 2σ(I)] reflections
9597, 2744, 2320 16085, 3186, 2487
Rint0.0400.019
(sin θ/λ)max1)0.6490.671
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.053, 1.06 0.023, 0.083, 1.21
No. of reflections27443186
No. of parameters163163
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.77, 0.710.49, 1.26

Computer programs: KappaCCD Server Software (Nonius, 1997), SMART (Bruker, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SAINT (Bruker, 2000), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected torsion angles (º) for (I) top
C2—C1—N1—C17162.8 (2)N1—C17—C11—C12167.5 (2)
C1—N1—C17—C1184.4 (3)C12—C13—N13—O1310.9 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O131i0.952.553.468 (3)164
Symmetry code: (i) x+1, y+1, z+1.
Selected torsion angles (º) for (II) top
C2—C1—N1—C1718.2 (3)N1—C17—C11—C1245.5 (3)
C1—N1—C17—C1163.7 (3)C12—C13—N13—O131169.3 (2)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O131i0.882.513.087 (3)124
C14—H14···O132ii0.952.523.364 (3)148
C15—H15···Cg1iii0.952.573.438 (3)151
Symmetry codes: (i) x+1/2, y+1, z+1/2; (ii) x+1/2, y+1, z1/2; (iii) x+1/2, y, z+1/2.
 

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