In 2-iodo-
N-(3-nitrobenzyl)aniline, C
13H
11IN
2O
2, 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
CCDC references: 193432; 193433
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)].
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.
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).
(I) 2-iodo-
N-(3-Nitrobenzyl)aniline
top
Crystal data top
C13H11IN2O2 | F(000) = 688 |
Mr = 354.14 | Dx = 1.945 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2744 reflections |
a = 11.4056 (3) Å | θ = 3.0–27.5° |
b = 8.7364 (3) Å | µ = 2.64 mm−1 |
c = 12.8357 (5) Å | T = 150 K |
β = 109.0049 (12)° | Plate, yellow |
V = 1209.28 (7) Å3 | 0.10 × 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 tube | 2320 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −14→14 |
Tmin = 0.778, Tmax = 0.879 | k = −11→11 |
9597 measured reflections | l = −13→16 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.053 | H-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 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
Crystal data top
C13H11IN2O2 | V = 1209.28 (7) Å3 |
Mr = 354.14 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.4056 (3) Å | µ = 2.64 mm−1 |
b = 8.7364 (3) Å | T = 150 K |
c = 12.8357 (5) Å | 0.10 × 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 = 0.879 | Rint = 0.040 |
9597 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.77 e Å−3 |
2744 reflections | Δρmin = −0.71 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
N1 | 0.7374 (2) | 0.7365 (2) | 0.38064 (18) | 0.0166 (5) | |
C1 | 0.6495 (2) | 0.6280 (3) | 0.3288 (2) | 0.0130 (5) | |
C2 | 0.6207 (2) | 0.5946 (3) | 0.2161 (2) | 0.0136 (5) | |
I2 | 0.711807 (14) | 0.712576 (17) | 0.121937 (13) | 0.01622 (8) | |
C3 | 0.5338 (2) | 0.4850 (3) | 0.1652 (2) | 0.0148 (5) | |
C4 | 0.4712 (2) | 0.4055 (3) | 0.2243 (2) | 0.0169 (6) | |
C5 | 0.4995 (2) | 0.4344 (3) | 0.3356 (2) | 0.0172 (6) | |
C6 | 0.5875 (2) | 0.5435 (3) | 0.3871 (2) | 0.0151 (5) | |
C17 | 0.7430 (3) | 0.8005 (3) | 0.4859 (2) | 0.0178 (6) | |
C11 | 0.8153 (2) | 0.7072 (3) | 0.5856 (2) | 0.0139 (6) | |
C12 | 0.8044 (2) | 0.7450 (3) | 0.6866 (2) | 0.0136 (5) | |
C13 | 0.8743 (2) | 0.6655 (3) | 0.7793 (2) | 0.0145 (5) | |
N13 | 0.8625 (2) | 0.7088 (2) | 0.88553 (19) | 0.0176 (5) | |
O131 | 0.79317 (16) | 0.8139 (2) | 0.88930 (15) | 0.0220 (5) | |
O132 | 0.92388 (19) | 0.6373 (2) | 0.96755 (15) | 0.0317 (5) | |
C14 | 0.9539 (2) | 0.5483 (3) | 0.7750 (2) | 0.0164 (6) | |
C15 | 0.9635 (2) | 0.5119 (3) | 0.6738 (2) | 0.0173 (6) | |
C16 | 0.8947 (2) | 0.5901 (3) | 0.5800 (2) | 0.0165 (6) | |
H1 | 0.7910 | 0.7672 | 0.3489 | 0.020* | |
H3 | 0.5166 | 0.4639 | 0.0891 | 0.018* | |
H4 | 0.4098 | 0.3321 | 0.1887 | 0.020* | |
H5 | 0.4583 | 0.3790 | 0.3772 | 0.021* | |
H6 | 0.6061 | 0.5612 | 0.4639 | 0.018* | |
H17A | 0.6572 | 0.8133 | 0.4872 | 0.021* | |
H17B | 0.7807 | 0.9036 | 0.4924 | 0.021* | |
H2 | 0.7497 | 0.8243 | 0.6923 | 0.016* | |
H14 | 1.0004 | 0.4947 | 0.8397 | 0.020* | |
H15 | 1.0178 | 0.4323 | 0.6683 | 0.021* | |
H16 | 0.9020 | 0.5629 | 0.5107 | 0.020* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0183 (12) | 0.0219 (11) | 0.0107 (12) | −0.0057 (10) | 0.0061 (9) | −0.0019 (9) |
C1 | 0.0140 (12) | 0.0115 (12) | 0.0125 (13) | 0.0036 (11) | 0.0028 (10) | 0.0018 (10) |
C2 | 0.0152 (12) | 0.0131 (12) | 0.0134 (13) | 0.0026 (10) | 0.0059 (10) | 0.0035 (10) |
I2 | 0.01897 (12) | 0.01827 (12) | 0.01286 (12) | −0.00237 (7) | 0.00714 (8) | 0.00039 (6) |
C3 | 0.0163 (12) | 0.0167 (13) | 0.0083 (13) | 0.0022 (11) | 0.0000 (10) | −0.0007 (10) |
C4 | 0.0115 (12) | 0.0161 (13) | 0.0203 (15) | 0.0011 (11) | 0.0011 (11) | −0.0021 (11) |
C5 | 0.0177 (13) | 0.0152 (12) | 0.0214 (15) | 0.0019 (11) | 0.0099 (11) | 0.0033 (11) |
C6 | 0.0165 (12) | 0.0194 (13) | 0.0097 (13) | 0.0039 (11) | 0.0050 (10) | 0.0024 (11) |
C17 | 0.0238 (14) | 0.0162 (13) | 0.0112 (14) | −0.0004 (11) | 0.0027 (12) | −0.0019 (10) |
C11 | 0.0136 (13) | 0.0120 (13) | 0.0146 (14) | −0.0035 (10) | 0.0025 (11) | −0.0006 (10) |
C12 | 0.0130 (13) | 0.0134 (12) | 0.0149 (14) | −0.0033 (10) | 0.0053 (11) | −0.0026 (11) |
C13 | 0.0139 (13) | 0.0176 (12) | 0.0124 (14) | −0.0051 (11) | 0.0048 (11) | −0.0013 (11) |
N13 | 0.0160 (11) | 0.0241 (12) | 0.0127 (12) | −0.0043 (10) | 0.0047 (10) | −0.0013 (9) |
O131 | 0.0207 (11) | 0.0271 (10) | 0.0185 (11) | 0.0041 (8) | 0.0067 (9) | −0.0053 (8) |
O132 | 0.0430 (12) | 0.0397 (12) | 0.0130 (10) | 0.0140 (11) | 0.0100 (9) | 0.0092 (9) |
C14 | 0.0158 (13) | 0.0168 (13) | 0.0146 (14) | −0.0022 (11) | 0.0023 (11) | 0.0028 (11) |
C15 | 0.0162 (12) | 0.0149 (13) | 0.0212 (15) | 0.0015 (11) | 0.0068 (11) | −0.0018 (11) |
C16 | 0.0192 (13) | 0.0185 (13) | 0.0125 (14) | −0.0046 (11) | 0.0060 (11) | −0.0040 (10) |
Geometric parameters (Å, º) top
N1—C1 | 1.383 (3) | C17—H17A | 0.9900 |
N1—C17 | 1.444 (3) | C17—H17B | 0.9900 |
N1—H1 | 0.8800 | C11—C12 | 1.382 (4) |
C1—C6 | 1.397 (3) | C11—C16 | 1.383 (3) |
C1—C2 | 1.406 (3) | C12—C13 | 1.385 (3) |
C2—C3 | 1.380 (3) | C12—H2 | 0.9500 |
C2—I2 | 2.102 (2) | C13—C14 | 1.382 (3) |
C3—C4 | 1.384 (4) | C13—N13 | 1.463 (3) |
C3—H3 | 0.9500 | N13—O131 | 1.223 (3) |
C4—C5 | 1.382 (4) | N13—O132 | 1.228 (3) |
C4—H4 | 0.9500 | C14—C15 | 1.375 (4) |
C5—C6 | 1.386 (3) | C14—H14 | 0.9500 |
C5—H5 | 0.9500 | C15—C16 | 1.385 (3) |
C6—H6 | 0.9500 | C15—H15 | 0.9500 |
C17—C11 | 1.515 (3) | C16—H16 | 0.9500 |
| | | |
C1—N1—C17 | 121.3 (2) | N1—C17—H17B | 108.4 |
C1—N1—H1 | 119.3 | C11—C17—H17B | 108.4 |
C17—N1—H1 | 119.3 | H17A—C17—H17B | 107.5 |
N1—C1—C6 | 121.2 (2) | C12—C11—C16 | 119.1 (2) |
N1—C1—C2 | 121.8 (2) | C12—C11—C17 | 118.2 (2) |
C6—C1—C2 | 116.9 (2) | C16—C11—C17 | 122.6 (2) |
C3—C2—C1 | 121.4 (2) | C11—C12—C13 | 118.9 (2) |
C3—C2—I2 | 118.82 (18) | C11—C12—H2 | 120.5 |
C1—C2—I2 | 119.75 (17) | C13—C12—H2 | 120.5 |
C2—C3—C4 | 120.5 (2) | C14—C13—C12 | 122.6 (2) |
C2—C3—H3 | 119.7 | C14—C13—N13 | 119.4 (2) |
C4—C3—H3 | 119.7 | C12—C13—N13 | 118.0 (2) |
C5—C4—C3 | 119.1 (2) | O131—N13—O132 | 122.9 (2) |
C5—C4—H4 | 120.4 | O131—N13—C13 | 119.2 (2) |
C3—C4—H4 | 120.4 | O132—N13—C13 | 117.9 (2) |
C4—C5—C6 | 120.5 (2) | C15—C14—C13 | 117.7 (2) |
C4—C5—H5 | 119.8 | C15—C14—H14 | 121.2 |
C6—C5—H5 | 119.8 | C13—C14—H14 | 121.2 |
C5—C6—C1 | 121.5 (2) | C14—C15—C16 | 120.7 (2) |
C5—C6—H6 | 119.3 | C14—C15—H15 | 119.6 |
C1—C6—H6 | 119.3 | C16—C15—H15 | 119.6 |
N1—C17—C11 | 115.3 (2) | C11—C16—C15 | 121.0 (2) |
N1—C17—H17A | 108.4 | C11—C16—H16 | 119.5 |
C11—C17—H17A | 108.4 | C15—C16—H16 | 119.5 |
| | | |
C2—C1—N1—C17 | 162.8 (2) | C12—C13—N13—O132 | 179.4 (2) |
C1—N1—C17—C11 | 84.4 (3) | C14—C13—N13—O131 | 179.1 (2) |
N1—C17—C11—C12 | −167.5 (2) | C14—C13—N13—O132 | −0.6 (3) |
C12—C13—N13—O131 | −0.9 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O131i | 0.95 | 2.55 | 3.468 (3) | 164 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
(II) 3-iodo-
N-(3-Nitrobenzyl)aniline
top
Crystal data top
C13H11IN2O2 | F(000) = 1376 |
Mr = 354.14 | Dx = 1.834 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3186 reflections |
a = 7.9024 (5) Å | θ = 1.4–29.0° |
b = 28.7265 (15) Å | µ = 2.49 mm−1 |
c = 11.3019 (6) Å | T = 120 K |
V = 2565.6 (3) Å3 | Lath, orange |
Z = 8 | 0.35 × 0.15 × 0.10 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3186 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2487 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 28.5°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→10 |
Tmin = 0.632, Tmax = 0.775 | k = −37→37 |
16085 measured reflections | l = −15→15 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-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 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −1.26 e Å−3 |
Crystal data top
C13H11IN2O2 | V = 2565.6 (3) Å3 |
Mr = 354.14 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.9024 (5) Å | µ = 2.49 mm−1 |
b = 28.7265 (15) Å | T = 120 K |
c = 11.3019 (6) Å | 0.35 × 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 = 0.775 | Rint = 0.019 |
16085 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.21 | Δρmax = 0.49 e Å−3 |
3186 reflections | Δρmin = −1.26 e Å−3 |
163 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.2440 (3) | 0.35278 (8) | 0.55834 (17) | 0.0177 (4) | |
N1 | 0.3957 (3) | 0.37589 (7) | 0.57762 (15) | 0.0210 (4) | |
C2 | 0.2252 (3) | 0.32010 (7) | 0.46661 (19) | 0.0174 (4) | |
C3 | 0.0710 (3) | 0.29732 (8) | 0.45373 (19) | 0.0183 (4) | |
I3 | 0.04055 (2) | 0.249097 (4) | 0.315030 (14) | 0.02199 (8) | |
C4 | −0.0658 (3) | 0.30543 (8) | 0.5284 (2) | 0.0228 (5) | |
C5 | −0.0449 (3) | 0.33769 (9) | 0.6187 (2) | 0.0238 (5) | |
C6 | 0.1063 (3) | 0.36102 (8) | 0.63407 (19) | 0.0225 (5) | |
C11 | 0.4734 (3) | 0.40475 (8) | 0.3760 (2) | 0.0190 (5) | |
C12 | 0.3905 (3) | 0.44716 (7) | 0.38475 (19) | 0.0195 (5) | |
C13 | 0.3455 (3) | 0.47019 (8) | 0.2813 (2) | 0.0202 (5) | |
N13 | 0.2565 (3) | 0.51451 (8) | 0.28992 (18) | 0.0260 (5) | |
O131 | 0.1950 (3) | 0.53116 (6) | 0.19910 (15) | 0.0363 (5) | |
O132 | 0.2435 (3) | 0.53339 (6) | 0.38672 (16) | 0.0435 (5) | |
C14 | 0.3807 (3) | 0.45262 (8) | 0.1692 (2) | 0.0237 (5) | |
C15 | 0.4641 (3) | 0.41029 (9) | 0.1622 (2) | 0.0262 (5) | |
C16 | 0.5097 (3) | 0.38687 (8) | 0.2645 (2) | 0.0234 (5) | |
C17 | 0.5257 (3) | 0.37839 (8) | 0.4873 (2) | 0.0211 (5) | |
H1 | 0.4134 | 0.3894 | 0.6464 | 0.025* | |
H2 | 0.3163 | 0.3137 | 0.4143 | 0.021* | |
H4 | −0.1700 | 0.2894 | 0.5179 | 0.027* | |
H5 | −0.1364 | 0.3439 | 0.6709 | 0.029* | |
H6 | 0.1173 | 0.3829 | 0.6966 | 0.027* | |
H12 | 0.3650 | 0.4602 | 0.4599 | 0.023* | |
H14 | 0.3487 | 0.4691 | 0.0999 | 0.028* | |
H15 | 0.4900 | 0.3973 | 0.0871 | 0.031* | |
H16 | 0.5671 | 0.3579 | 0.2584 | 0.028* | |
H17A | 0.5583 | 0.3463 | 0.4647 | 0.025* | |
H17B | 0.6269 | 0.3936 | 0.5214 | 0.025* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0213 (11) | 0.0171 (10) | 0.0147 (10) | 0.0033 (9) | −0.0041 (9) | 0.0034 (8) |
N1 | 0.0261 (11) | 0.0223 (10) | 0.0145 (9) | −0.0014 (9) | −0.0050 (8) | −0.0017 (7) |
C2 | 0.0178 (11) | 0.0191 (10) | 0.0153 (10) | 0.0020 (9) | 0.0001 (9) | 0.0021 (8) |
C3 | 0.0204 (11) | 0.0180 (11) | 0.0165 (10) | 0.0031 (9) | −0.0014 (9) | 0.0014 (8) |
I3 | 0.01802 (12) | 0.02279 (12) | 0.02518 (13) | −0.00249 (6) | −0.00290 (5) | −0.00465 (5) |
C4 | 0.0181 (11) | 0.0250 (12) | 0.0252 (12) | 0.0012 (9) | 0.0013 (10) | 0.0061 (10) |
C5 | 0.0255 (13) | 0.0285 (13) | 0.0173 (11) | 0.0075 (10) | 0.0060 (9) | 0.0046 (9) |
C6 | 0.0307 (13) | 0.0222 (11) | 0.0144 (10) | 0.0064 (10) | −0.0009 (10) | 0.0017 (8) |
C11 | 0.0175 (11) | 0.0190 (11) | 0.0206 (11) | −0.0050 (9) | −0.0010 (9) | −0.0012 (8) |
C12 | 0.0225 (12) | 0.0189 (11) | 0.0170 (11) | −0.0036 (9) | 0.0005 (9) | −0.0022 (8) |
C13 | 0.0247 (12) | 0.0167 (11) | 0.0192 (11) | −0.0038 (9) | −0.0002 (10) | −0.0018 (8) |
N13 | 0.0353 (13) | 0.0200 (9) | 0.0228 (10) | −0.0017 (8) | −0.0010 (9) | 0.0034 (8) |
O131 | 0.0543 (13) | 0.0272 (10) | 0.0273 (10) | 0.0065 (9) | −0.0071 (9) | 0.0086 (7) |
O132 | 0.0754 (16) | 0.0288 (10) | 0.0262 (10) | 0.0177 (10) | −0.0014 (10) | −0.0046 (8) |
C14 | 0.0281 (13) | 0.0266 (12) | 0.0163 (11) | −0.0074 (10) | −0.0002 (10) | 0.0026 (9) |
C15 | 0.0279 (14) | 0.0321 (13) | 0.0186 (11) | −0.0021 (10) | 0.0039 (10) | −0.0083 (10) |
C16 | 0.0226 (11) | 0.0204 (12) | 0.0271 (13) | −0.0016 (10) | 0.0029 (10) | −0.0056 (9) |
C17 | 0.0191 (11) | 0.0201 (11) | 0.0240 (12) | −0.0008 (9) | −0.0042 (9) | −0.0012 (9) |
Geometric parameters (Å, º) top
C1—N1 | 1.388 (3) | C11—C16 | 1.390 (3) |
C1—C6 | 1.404 (3) | C11—C17 | 1.525 (3) |
C1—C2 | 1.406 (3) | C12—C13 | 1.389 (3) |
N1—C17 | 1.450 (3) | C12—H12 | 0.9500 |
N1—H1 | 0.8800 | C13—C14 | 1.392 (3) |
C2—C3 | 1.391 (3) | C13—N13 | 1.458 (3) |
C2—H2 | 0.9500 | N13—O132 | 1.225 (3) |
C3—C4 | 1.391 (3) | N13—O131 | 1.232 (3) |
C3—I3 | 2.106 (2) | C14—C15 | 1.385 (3) |
C4—C5 | 1.388 (3) | C14—H14 | 0.9500 |
C4—H4 | 0.9500 | C15—C16 | 1.385 (3) |
C5—C6 | 1.381 (3) | C15—H15 | 0.9500 |
C5—H5 | 0.9500 | C16—H16 | 0.9500 |
C6—H6 | 0.9500 | C17—H17A | 0.9900 |
C11—C12 | 1.387 (3) | C17—H17B | 0.9900 |
| | | |
N1—C1—C6 | 119.53 (19) | C11—C12—C13 | 118.6 (2) |
N1—C1—C2 | 121.8 (2) | C11—C12—H12 | 120.7 |
C6—C1—C2 | 118.7 (2) | C13—C12—H12 | 120.7 |
C1—N1—C17 | 121.67 (17) | C12—C13—C14 | 122.8 (2) |
C1—N1—H1 | 119.2 | C12—C13—N13 | 118.9 (2) |
C17—N1—H1 | 119.2 | C14—C13—N13 | 118.3 (2) |
C3—C2—C1 | 118.9 (2) | O132—N13—O131 | 122.6 (2) |
C3—C2—H2 | 120.5 | O132—N13—C13 | 119.1 (2) |
C1—C2—H2 | 120.5 | O131—N13—C13 | 118.3 (2) |
C4—C3—C2 | 122.6 (2) | C15—C14—C13 | 117.7 (2) |
C4—C3—I3 | 118.23 (17) | C15—C14—H14 | 121.1 |
C2—C3—I3 | 119.18 (16) | C13—C14—H14 | 121.1 |
C5—C4—C3 | 117.7 (2) | C14—C15—C16 | 120.2 (2) |
C5—C4—H4 | 121.1 | C14—C15—H15 | 119.9 |
C3—C4—H4 | 121.1 | C16—C15—H15 | 119.9 |
C6—C5—C4 | 121.3 (2) | C15—C16—C11 | 121.5 (2) |
C6—C5—H5 | 119.3 | C15—C16—H16 | 119.2 |
C4—C5—H5 | 119.3 | C11—C16—H16 | 119.2 |
C5—C6—C1 | 120.8 (2) | N1—C17—C11 | 114.41 (18) |
C5—C6—H6 | 119.6 | N1—C17—H17A | 108.7 |
C1—C6—H6 | 119.6 | C11—C17—H17A | 108.7 |
C12—C11—C16 | 119.1 (2) | N1—C17—H17B | 108.7 |
C12—C11—C17 | 120.4 (2) | C11—C17—H17B | 108.7 |
C16—C11—C17 | 120.5 (2) | H17A—C17—H17B | 107.6 |
| | | |
C6—C1—N1—C17 | −163.72 (19) | C17—C11—C12—C13 | 179.8 (2) |
C2—C1—N1—C17 | 18.2 (3) | C11—C12—C13—C14 | −0.3 (3) |
C1—N1—C17—C11 | 63.7 (3) | C11—C12—C13—N13 | 179.2 (2) |
N1—C17—C11—C12 | 45.5 (3) | C12—C13—N13—O132 | 9.7 (3) |
N1—C1—C2—C3 | 178.49 (19) | C14—C13—N13—O132 | −170.8 (2) |
C6—C1—C2—C3 | 0.3 (3) | C12—C13—N13—O131 | −169.3 (2) |
C1—C2—C3—C4 | −0.2 (3) | C14—C13—N13—O131 | 10.3 (3) |
C1—C2—C3—I3 | 179.07 (15) | C12—C13—C14—C15 | 0.1 (4) |
C2—C3—C4—C5 | 0.1 (3) | N13—C13—C14—C15 | −179.4 (2) |
I3—C3—C4—C5 | −179.26 (17) | C13—C14—C15—C16 | 0.0 (4) |
C3—C4—C5—C6 | 0.0 (3) | C14—C15—C16—C11 | 0.2 (4) |
C4—C5—C6—C1 | 0.1 (3) | C12—C11—C16—C15 | −0.4 (3) |
N1—C1—C6—C5 | −178.5 (2) | C17—C11—C16—C15 | −179.7 (2) |
C2—C1—C6—C5 | −0.3 (3) | C16—C11—C17—N1 | −135.1 (2) |
C16—C11—C12—C13 | 0.4 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O131i | 0.88 | 2.51 | 3.087 (3) | 124 |
C14—H14···O132ii | 0.95 | 2.52 | 3.364 (3) | 148 |
C15—H15···Cg1iii | 0.95 | 2.57 | 3.438 (3) | 151 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) x+1/2, y, −z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C13H11IN2O2 | C13H11IN2O2 |
Mr | 354.14 | 354.14 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pbca |
Temperature (K) | 150 | 120 |
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), 90 | 90, 90, 90 |
V (Å3) | 1209.28 (7) | 2565.6 (3) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.64 | 2.49 |
Crystal size (mm) | 0.10 × 0.10 × 0.05 | 0.35 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.778, 0.879 | 0.632, 0.775 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9597, 2744, 2320 | 16085, 3186, 2487 |
Rint | 0.040 | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 | 0.671 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.053, 1.06 | 0.023, 0.083, 1.21 |
No. of reflections | 2744 | 3186 |
No. of parameters | 163 | 163 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −0.71 | 0.49, −1.26 |
Selected torsion angles (º) for (I) topC2—C1—N1—C17 | 162.8 (2) | N1—C17—C11—C12 | −167.5 (2) |
C1—N1—C17—C11 | 84.4 (3) | C12—C13—N13—O131 | −0.9 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O131i | 0.95 | 2.55 | 3.468 (3) | 164 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Selected torsion angles (º) for (II) topC2—C1—N1—C17 | 18.2 (3) | N1—C17—C11—C12 | 45.5 (3) |
C1—N1—C17—C11 | 63.7 (3) | C12—C13—N13—O131 | −169.3 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O131i | 0.88 | 2.51 | 3.087 (3) | 124 |
C14—H14···O132ii | 0.95 | 2.52 | 3.364 (3) | 148 |
C15—H15···Cg1iii | 0.95 | 2.57 | 3.438 (3) | 151 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) x+1/2, y, −z+1/2. |
We have recently reported (Glidewell et al., 2002) the molecular and supramolecular structures of eight isomeric nitrobenzylidene-iodoanilines, O2NC6H4CH═NC6H4I, 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.