

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103025654/gg1198sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270103025654/gg1198Isup2.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270103025654/gg1198IIsup3.hkl |
CCDC references: 231051; 231052
To prepare compound (I), 5-nitrosalicaldehyde (10 mmol) was dissolved in warm methanol (30 ml) and a solution of K[ICl2] in methanol (2 M, 10 ml) was added with stirring. After a few hours, the reaction mixture was diluted with water (100 ml) and compound (I) was collected by filtration, washed with water and crystallized from aqueous ethanol (yield 83%, m. p. 432–433 K). To prepare compound (II), a solution of K[ICl2] in methanol (2 M, 25 ml) was added to a methanolic solution (50 ml) of 2-nitrophenol (20 mmol) and the mixture was gently warmed. Water (100 ml) was added to the reaction mixture and 2,4-diiodo-6-nitrophenol was precipitated out, collected by filtration and washed with water. This material was dissolved in acetone (50 ml) and to this solution was added K2CO3 (30 mmol) followed by an excess of Me2SO4 (10 ml). The resulting mixture was stirred at room temperature for 3 d, after which time the reaction mixture was concentrated by evaporation of the volatiles. The addition of water (100 ml) precipitated compound (II), which was collected by filtration and crystallized from aqueous ethanol (yield 93%, m. p. 385–386 K).
Crystals of (I) and (II) are monoclinic. For (I), the space group P21/c was uniquely assigned from the systematic absences, while for (II), the systematic absences permitted Cc and C2/c as possible space groups; C2/c was selected, and confirmed by the subsequent structure analysis. It was apparent at an early stage that the molecules of (II) were disordered over two sets of sites such that all atoms, except one nitro group and one I atom, were common to both orientations. When the site-occupancy factors for these disordered substituents were refined they gave values of 0.48 (3) and 0.52 (3), and hence they were both thereafter fixed at 0.50. When full anisotropic refinement was attempted for (II), the behaviour of the disordered nitro groups was erratic and not satisfactory. Accordingly, the atoms in these substituents were constrained to have the same anisotropic displacement parameters and the refinement then behaved satisfactorily. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.93 (aromatic and CHO) and 0.96 Å (methyl), and O—H distances of 0.82 Å.
For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; 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).
C7H4INO4 | F(000) = 552 |
Mr = 293.01 | Dx = 2.348 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1901 reflections |
a = 8.2556 (3) Å | θ = 3.0–27.5° |
b = 15.3414 (8) Å | µ = 3.84 mm−1 |
c = 7.2521 (4) Å | T = 120 K |
β = 115.496 (3)° | Lath, colourless |
V = 829.05 (7) Å3 | 0.36 × 0.05 × 0.02 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 1901 independent reflections |
Radiation source: rotating anode | 1482 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −10→10 |
Tmin = 0.339, Tmax = 0.927 | k = −19→19 |
8251 measured reflections | l = −9→9 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0348P)2] where P = (Fo2 + 2Fc2)/3 |
1901 reflections | (Δ/σ)max = 0.001 |
119 parameters | Δρmax = 1.13 e Å−3 |
0 restraints | Δρmin = −1.08 e Å−3 |
C7H4INO4 | V = 829.05 (7) Å3 |
Mr = 293.01 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.2556 (3) Å | µ = 3.84 mm−1 |
b = 15.3414 (8) Å | T = 120 K |
c = 7.2521 (4) Å | 0.36 × 0.05 × 0.02 mm |
β = 115.496 (3)° |
Nonius KappaCCD diffractometer | 1901 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 1482 reflections with I > 2σ(I) |
Tmin = 0.339, Tmax = 0.927 | Rint = 0.065 |
8251 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.13 e Å−3 |
1901 reflections | Δρmin = −1.08 e Å−3 |
119 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2059 (6) | 0.1453 (2) | 0.1802 (6) | 0.0135 (8) | |
N1 | 0.3257 (5) | 0.0711 (2) | 0.2125 (5) | 0.0170 (8) | |
O11 | 0.4865 (4) | 0.08468 (18) | 0.2696 (5) | 0.0236 (7) | |
O12 | 0.2593 (4) | −0.00229 (19) | 0.1838 (5) | 0.0252 (8) | |
C2 | 0.0318 (6) | 0.1324 (3) | 0.1491 (6) | 0.0174 (9) | |
C3 | −0.0769 (6) | 0.2043 (3) | 0.1281 (6) | 0.0160 (9) | |
C4 | −0.0087 (6) | 0.2900 (3) | 0.1386 (6) | 0.0159 (9) | |
C5 | 0.1703 (6) | 0.3002 (2) | 0.1698 (6) | 0.0157 (9) | |
I5 | 0.28173 (4) | 0.424544 (16) | 0.19310 (4) | 0.02033 (12) | |
C6 | 0.2773 (6) | 0.2286 (3) | 0.1902 (5) | 0.0153 (8) | |
C31 | −0.2675 (6) | 0.1906 (3) | 0.1045 (6) | 0.0168 (9) | |
O31 | −0.3591 (4) | 0.2513 (2) | 0.1010 (5) | 0.0277 (7) | |
O41 | −0.1079 (4) | 0.36054 (18) | 0.1176 (5) | 0.0231 (7) | |
H2 | −0.0129 | 0.0762 | 0.1421 | 0.021* | |
H31 | −0.3130 | 0.1344 | 0.0927 | 0.020* | |
H41 | −0.2028 | 0.3466 | 0.1202 | 0.035* | |
H6 | 0.3957 | 0.2357 | 0.2106 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.017 (2) | 0.0113 (19) | 0.0123 (19) | 0.0047 (17) | 0.0061 (17) | −0.0005 (15) |
N1 | 0.023 (2) | 0.0131 (19) | 0.0169 (17) | −0.0002 (16) | 0.0102 (16) | −0.0027 (14) |
O11 | 0.0198 (19) | 0.0181 (17) | 0.0352 (18) | 0.0013 (13) | 0.0140 (15) | −0.0013 (13) |
O12 | 0.031 (2) | 0.0124 (16) | 0.0347 (19) | −0.0029 (13) | 0.0168 (17) | −0.0038 (13) |
C2 | 0.021 (3) | 0.015 (2) | 0.016 (2) | −0.0040 (18) | 0.0067 (18) | −0.0019 (16) |
C3 | 0.017 (2) | 0.016 (2) | 0.0151 (19) | 0.0010 (17) | 0.0073 (18) | 0.0005 (16) |
C4 | 0.022 (2) | 0.016 (2) | 0.0116 (18) | 0.0022 (18) | 0.0093 (17) | 0.0009 (16) |
C5 | 0.022 (3) | 0.013 (2) | 0.0143 (19) | −0.0019 (17) | 0.0095 (18) | −0.0016 (15) |
I5 | 0.0290 (2) | 0.01252 (17) | 0.02228 (17) | −0.00365 (12) | 0.01369 (13) | −0.00179 (12) |
C6 | 0.021 (2) | 0.015 (2) | 0.0128 (18) | −0.0016 (18) | 0.0094 (17) | −0.0011 (16) |
C31 | 0.030 (3) | 0.008 (2) | 0.0111 (19) | 0.0020 (19) | 0.0073 (18) | 0.0020 (16) |
O31 | 0.0204 (18) | 0.0314 (19) | 0.0332 (18) | 0.0028 (15) | 0.0133 (15) | 0.0099 (14) |
O41 | 0.0223 (19) | 0.0158 (15) | 0.0377 (18) | 0.0059 (13) | 0.0189 (16) | 0.0042 (13) |
C1—C2 | 1.370 (6) | C2—H2 | 0.93 |
C2—C3 | 1.389 (6) | C3—C31 | 1.522 (6) |
C3—C4 | 1.419 (5) | C31—O31 | 1.193 (5) |
C4—C5 | 1.404 (6) | C31—H31 | 0.93 |
C5—C6 | 1.376 (6) | C4—O41 | 1.327 (5) |
C6—C1 | 1.396 (6) | O41—H41 | 0.82 |
C1—N1 | 1.459 (5) | C5—I5 | 2.093 (4) |
N1—O11 | 1.226 (5) | C6—H6 | 0.93 |
N1—O12 | 1.231 (4) | ||
C2—C1—C6 | 122.0 (4) | O31—C31—H31 | 119.7 |
C2—C1—N1 | 120.3 (4) | C3—C31—H31 | 119.7 |
C6—C1—N1 | 117.6 (4) | O41—C4—C5 | 118.9 (4) |
O11—N1—O12 | 123.4 (4) | O41—C4—C3 | 122.6 (4) |
O11—N1—C1 | 118.9 (3) | C5—C4—C3 | 118.6 (4) |
O12—N1—C1 | 117.7 (4) | C4—O41—H41 | 109.5 |
C1—C2—C3 | 119.1 (4) | C6—C5—C4 | 120.7 (4) |
C1—C2—H2 | 120.4 | C6—C5—I5 | 118.6 (3) |
C3—C2—H2 | 120.4 | C4—C5—I5 | 120.7 (3) |
C2—C3—C4 | 120.4 (4) | C5—C6—C1 | 119.2 (4) |
C2—C3—C31 | 119.4 (4) | C5—C6—H6 | 120.4 |
C4—C3—C31 | 120.1 (4) | C1—C6—H6 | 120.4 |
O31—C31—C3 | 120.7 (4) | ||
C2—C1—N1—O11 | −169.4 (4) | C31—C3—C4—O41 | −3.7 (6) |
C6—C1—N1—O11 | 8.2 (5) | C2—C3—C4—C5 | 0.2 (6) |
C2—C1—N1—O12 | 9.5 (5) | C31—C3—C4—C5 | 177.1 (3) |
C6—C1—N1—O12 | −173.0 (3) | O41—C4—C5—C6 | −179.4 (3) |
C6—C1—C2—C3 | −0.4 (6) | C3—C4—C5—C6 | −0.1 (6) |
N1—C1—C2—C3 | 177.0 (3) | O41—C4—C5—I5 | 2.1 (5) |
C1—C2—C3—C4 | 0.1 (6) | C3—C4—C5—I5 | −178.7 (3) |
C1—C2—C3—C31 | −176.9 (4) | C4—C5—C6—C1 | −0.2 (6) |
C2—C3—C31—O31 | 174.6 (4) | I5—C5—C6—C1 | 178.4 (3) |
C4—C3—C31—O31 | −2.4 (6) | C2—C1—C6—C5 | 0.4 (6) |
C2—C3—C4—O41 | 179.4 (4) | N1—C1—C6—C5 | −177.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···O31 | 0.82 | 1.92 | 2.629 (5) | 145 |
C6—H6···O31i | 0.93 | 2.48 | 3.351 (6) | 155 |
Symmetry code: (i) x+1, y, z. |
C7H5I2NO3 | F(000) = 1472 |
Mr = 404.92 | Dx = 2.609 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3712 reflections |
a = 32.999 (2) Å | θ = 2.5–32.6° |
b = 4.2305 (3) Å | µ = 6.08 mm−1 |
c = 14.8328 (11) Å | T = 120 K |
β = 95.225 (2)° | Needle, colourless |
V = 2062.1 (2) Å3 | 0.34 × 0.04 × 0.04 mm |
Z = 8 |
Nonius KappaCCD diffractometer | 3712 independent reflections |
Radiation source: rotating anode | 1520 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ scans, and ω scans with κ offsets | θmax = 32.6°, θmin = 2.5° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −49→33 |
Tmin = 0.232, Tmax = 0.793 | k = −6→6 |
10606 measured reflections | l = −22→22 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0721P)2] where P = (Fo2 + 2Fc2)/3 |
3712 reflections | (Δ/σ)max < 0.001 |
126 parameters | Δρmax = 1.07 e Å−3 |
10 restraints | Δρmin = −1.29 e Å−3 |
C7H5I2NO3 | V = 2062.1 (2) Å3 |
Mr = 404.92 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 32.999 (2) Å | µ = 6.08 mm−1 |
b = 4.2305 (3) Å | T = 120 K |
c = 14.8328 (11) Å | 0.34 × 0.04 × 0.04 mm |
β = 95.225 (2)° |
Nonius KappaCCD diffractometer | 3712 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 1520 reflections with I > 2σ(I) |
Tmin = 0.232, Tmax = 0.793 | Rint = 0.044 |
10606 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 10 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 0.89 | Δρmax = 1.07 e Å−3 |
3712 reflections | Δρmin = −1.29 e Å−3 |
126 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.1408 (2) | 0.3638 (13) | 0.5217 (3) | 0.0539 (15) | |
I1 | 0.14846 (4) | 0.5738 (3) | 0.64326 (6) | 0.0692 (3) | 0.50 |
N1 | 0.1473 (4) | 0.525 (4) | 0.6090 (6) | 0.113 (2) | 0.50 |
O11 | 0.1770 (3) | 0.691 (3) | 0.6295 (7) | 0.113 (2) | 0.50 |
O12 | 0.1220 (3) | 0.486 (4) | 0.6629 (8) | 0.113 (2) | 0.50 |
C2 | 0.10114 (19) | 0.3350 (13) | 0.4756 (4) | 0.0488 (14) | |
O21 | 0.06871 (13) | 0.4760 (11) | 0.5092 (3) | 0.0616 (12) | |
C21 | 0.0465 (2) | 0.2755 (19) | 0.5662 (5) | 0.077 (2) | |
C3 | 0.09815 (15) | 0.1894 (15) | 0.3909 (4) | 0.0518 (15) | |
N3 | 0.0590 (2) | 0.162 (4) | 0.3371 (6) | 0.113 (2) | 0.50 |
O31 | 0.0584 (3) | 0.149 (4) | 0.2548 (7) | 0.113 (2) | 0.50 |
O32 | 0.0272 (3) | 0.140 (4) | 0.3726 (7) | 0.113 (2) | 0.50 |
I3 | 0.04405 (3) | 0.1563 (3) | 0.31796 (6) | 0.0732 (3) | 0.50 |
C4 | 0.1321 (2) | 0.0604 (15) | 0.3566 (4) | 0.0590 (17) | |
C5 | 0.17055 (19) | 0.0899 (15) | 0.4032 (4) | 0.0540 (15) | |
I5 | 0.221995 (15) | −0.09284 (11) | 0.34922 (4) | 0.0749 (2) | |
C6 | 0.1749 (2) | 0.2420 (16) | 0.4848 (4) | 0.0574 (16) | |
H21A | 0.0316 | 0.1199 | 0.5296 | 0.115* | |
H21B | 0.0279 | 0.4016 | 0.5971 | 0.115* | |
H21C | 0.0653 | 0.1718 | 0.6098 | 0.115* | |
H4 | 0.1292 | −0.0474 | 0.3017 | 0.071* | |
H6 | 0.2006 | 0.2642 | 0.5157 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.070 (4) | 0.047 (4) | 0.045 (3) | 0.002 (3) | 0.007 (3) | 0.010 (3) |
I1 | 0.0891 (7) | 0.0674 (6) | 0.0507 (5) | 0.0001 (6) | 0.0045 (5) | −0.0066 (4) |
N1 | 0.085 (4) | 0.157 (6) | 0.095 (4) | −0.006 (4) | 0.000 (4) | −0.030 (4) |
O11 | 0.085 (4) | 0.157 (6) | 0.095 (4) | −0.006 (4) | 0.000 (4) | −0.030 (4) |
O12 | 0.085 (4) | 0.157 (6) | 0.095 (4) | −0.006 (4) | 0.000 (4) | −0.030 (4) |
C2 | 0.056 (4) | 0.048 (3) | 0.044 (3) | 0.006 (3) | 0.015 (3) | 0.007 (3) |
O21 | 0.060 (3) | 0.065 (3) | 0.063 (3) | 0.015 (2) | 0.021 (2) | 0.004 (2) |
C21 | 0.067 (5) | 0.093 (5) | 0.074 (5) | 0.002 (4) | 0.033 (4) | 0.004 (4) |
C3 | 0.048 (3) | 0.060 (4) | 0.048 (3) | −0.002 (3) | 0.007 (3) | 0.000 (3) |
N3 | 0.085 (4) | 0.157 (6) | 0.095 (4) | −0.006 (4) | 0.000 (4) | −0.030 (4) |
O31 | 0.085 (4) | 0.157 (6) | 0.095 (4) | −0.006 (4) | 0.000 (4) | −0.030 (4) |
O32 | 0.085 (4) | 0.157 (6) | 0.095 (4) | −0.006 (4) | 0.000 (4) | −0.030 (4) |
I3 | 0.0548 (6) | 0.1124 (9) | 0.0518 (5) | 0.0057 (6) | 0.0013 (4) | −0.0050 (5) |
C4 | 0.070 (4) | 0.057 (4) | 0.053 (4) | 0.002 (3) | 0.025 (3) | −0.003 (3) |
C5 | 0.053 (4) | 0.051 (4) | 0.062 (4) | 0.000 (3) | 0.027 (3) | 0.013 (3) |
I5 | 0.0687 (3) | 0.0625 (3) | 0.0993 (4) | 0.0104 (2) | 0.0396 (3) | 0.0057 (3) |
C6 | 0.054 (4) | 0.061 (4) | 0.059 (4) | 0.002 (3) | 0.013 (3) | 0.001 (3) |
C1—C6 | 1.394 (9) | C21—H21C | 0.96 |
C1—C2 | 1.427 (9) | C3—C4 | 1.383 (8) |
C1—N1 | 1.4603 (10) | C3—N3 | 1.4608 (10) |
C1—I1 | 2.005 (5) | C3—I3 | 2.007 (5) |
N1—O12 | 1.2203 (10) | N3—O31 | 1.2202 (10) |
N1—O11 | 1.2205 (10) | N3—O32 | 1.2204 (10) |
C2—O21 | 1.359 (7) | C4—C5 | 1.395 (10) |
C2—C3 | 1.394 (8) | C4—H4 | 0.93 |
O21—C21 | 1.443 (8) | C5—C6 | 1.368 (9) |
C21—H21A | 0.96 | C5—I5 | 2.090 (6) |
C21—H21B | 0.96 | C6—H6 | 0.93 |
C6—C1—C2 | 121.3 (5) | C4—C3—C2 | 120.8 (5) |
C6—C1—N1 | 117.5 (8) | C4—C3—N3 | 118.2 (7) |
C2—C1—N1 | 121.3 (7) | C2—C3—N3 | 120.9 (7) |
C6—C1—I1 | 118.5 (5) | C4—C3—I3 | 118.9 (4) |
C2—C1—I1 | 120.3 (4) | C2—C3—I3 | 120.2 (4) |
O12—N1—O11 | 119.61 (15) | O31—N3—O32 | 119.57 (15) |
O12—N1—C1 | 117.7 (9) | O31—N3—C3 | 118.8 (8) |
O11—N1—C1 | 122.7 (9) | O32—N3—C3 | 121.5 (8) |
O21—C2—C3 | 122.1 (5) | C3—C4—C5 | 120.9 (6) |
O21—C2—C1 | 120.4 (5) | C3—C4—H4 | 119.6 |
C3—C2—C1 | 117.2 (5) | C5—C4—H4 | 119.6 |
C2—O21—C21 | 114.5 (5) | C6—C5—C4 | 119.9 (6) |
O21—C21—H21A | 109.5 | C6—C5—I5 | 119.3 (5) |
O21—C21—H21B | 109.5 | C4—C5—I5 | 120.8 (5) |
H21A—C21—H21B | 109.5 | C5—C6—C1 | 119.8 (6) |
O21—C21—H21C | 109.5 | C5—C6—H6 | 120.1 |
H21A—C21—H21C | 109.5 | C1—C6—H6 | 120.1 |
H21B—C21—H21C | 109.5 | ||
C6—C1—N1—O12 | −142.1 (13) | O21—C2—C3—I3 | −4.3 (8) |
C2—C1—N1—O12 | 38.5 (18) | C1—C2—C3—I3 | −177.0 (4) |
I1—C1—N1—O12 | −21 (19) | C4—C3—N3—O31 | −28.8 (19) |
C6—C1—N1—O11 | 37.2 (19) | C2—C3—N3—O31 | 152.6 (13) |
C2—C1—N1—O11 | −142.2 (14) | I3—C3—N3—O31 | 138 (54) |
I1—C1—N1—O11 | 158 (21) | C4—C3—N3—O32 | 148.1 (14) |
C6—C1—C2—O21 | −174.9 (5) | C2—C3—N3—O32 | −30 (2) |
N1—C1—C2—O21 | 4.5 (11) | I3—C3—N3—O32 | −45 (52) |
I1—C1—C2—O21 | 6.4 (7) | C2—C3—C4—C5 | −4.0 (10) |
C6—C1—C2—C3 | −2.1 (8) | N3—C3—C4—C5 | 177.4 (9) |
N1—C1—C2—C3 | 177.3 (9) | I3—C3—C4—C5 | 177.2 (5) |
I1—C1—C2—C3 | 179.3 (4) | C3—C4—C5—C6 | 1.4 (9) |
C3—C2—O21—C21 | 93.7 (7) | C3—C4—C5—I5 | −178.1 (5) |
C1—C2—O21—C21 | −93.8 (7) | C4—C5—C6—C1 | 0.8 (9) |
O21—C2—C3—C4 | 177.0 (6) | I5—C5—C6—C1 | −179.7 (4) |
C1—C2—C3—C4 | 4.2 (9) | C2—C1—C6—C5 | −0.4 (9) |
O21—C2—C3—N3 | −4.5 (11) | N1—C1—C6—C5 | −179.8 (9) |
C1—C2—C3—N3 | −177.2 (9) | I1—C1—C6—C5 | 178.2 (5) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C7H4INO4 | C7H5I2NO3 |
Mr | 293.01 | 404.92 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 8.2556 (3), 15.3414 (8), 7.2521 (4) | 32.999 (2), 4.2305 (3), 14.8328 (11) |
β (°) | 115.496 (3) | 95.225 (2) |
V (Å3) | 829.05 (7) | 2062.1 (2) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 3.84 | 6.08 |
Crystal size (mm) | 0.36 × 0.05 × 0.02 | 0.34 × 0.04 × 0.04 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.339, 0.927 | 0.232, 0.793 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8251, 1901, 1482 | 10606, 3712, 1520 |
Rint | 0.065 | 0.044 |
(sin θ/λ)max (Å−1) | 0.650 | 0.758 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.074, 1.03 | 0.053, 0.154, 0.89 |
No. of reflections | 1901 | 3712 |
No. of parameters | 119 | 126 |
No. of restraints | 0 | 10 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.13, −1.08 | 1.07, −1.29 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O41—H41···O31 | 0.82 | 1.92 | 2.629 (5) | 145 |
C6—H6···O31i | 0.93 | 2.48 | 3.351 (6) | 155 |
Symmetry code: (i) x+1, y, z. |
We have recently reported the supramolecular aggregation of a wide range of different types of iodo-nitro aromatic compounds (McWilliam et al., 2001; Garden, da Cunha et al., 2002; Garden, Fontes et al., 2002; Kelly et al., 2002; Glidewell, Howie et al., 2002; Glidewell, Low et al., 2002; Glidewell et al., 2003), in which the patterns of supramolecular aggregation depend on the interplay of a wide range of weak intermolecular forces, including hard and soft (Desiraju & Steiner, 1999) hydrogen bonds of various types, iodo···nitro interactions and aromatic π–π stacking interactions. Here, we report the molecular and supramolecular structures of two further examples of such compounds, 2-hydroxy-3-iodo-5-nitrobenzaldehyde, (I), and 2,4-diiodo-6-nitroanisole, (II), the latter being isomeric with 2,6-diiodo-4-nitroanisole, (III) (Garden, da Cunha et al., 2002). \sch
In compound (I) [Fig. 1, where the crystallographic atom-numbering scheme differs from the conventional chemical numbering scheme, in order that both (I) and (II) have a nitro group at position 1 and an iodo substituent at position 5], there is an intramolecular O—H···O hydrogen bond, forming an S(6) motif (Bernstein et al., 1995). There are three distinct types of intermolecular interactions linking the molecules of (I). A soft hydrogen bond and an iodo···nitro interaction each form a chain motif. Thus, aromatic atom C6 in the molecule at (x, y, z) acts as hydrogen-bond donor to the aldehydic atom O31 in the molecule at (1 + x, y, z), so generating by translation a C(7) chain running parallel to the [100] direction (Fig. 2). At the same time, atom I5 in the molecule at (x, y, z) forms a short two-centre iodo···nitro interaction with nitro atom O11 in the molecule at (1 − x, 1/2 + y, 1/2 − z), with I···O 3.054 (3) Å, C—I···O 167.8 (2)° and I···O—N 116.0 (2)°, so producing a C(6) chain (Starbuck et al., 1999) running parallel to the [010] direction and generated by the 21 screw axis along (1/2, y, 1/4). The combination of the [100] and [010] chains generates an elegant sheet parallel to (001), in the form of a (4,4) net (Batten & Robson, 1998) containing equal numbers of S(6) and R54(22) rings (Fig. 2).
Two sheets of this type pass through each unit cell of (I), lying in the domains 0.09 < z < 0.41 and 0.59 < z < 0.91, and adjacent sheets are weakly linked by the third type of intermolecular interaction, an aromatic π–π stacking interaction. The aryl ring in the molecule at (x, y, z), which lies in the 0.09 < z < 0.41 sheet, and those in the molecules at (x, 1/2 − y, 1/2 + z) and (x, 1/2 − y, z − 1/2), which lie in the domains 0.59 < z < 0.91 and −0.41 < z < −0.09, respectively, are nearly parallel, with an interplanar angle between rings in adjacent sheets of only ca 1.3°. The centroid separations are both 3.767 (3) Å and the interplanar separations are ca 3.46 Å, corresponding to centroid offsets of ca 1.49 Å (Fig. 3).
In the disordered structure of (II) (Fig. 4, where again the crystallographic atom-numbering scheme differs from the conventional chemical numbering scheme, see above), in contrast with (I), there are neither C—H···O hydrogen bonds nor aromatic π–π stacking interactions. The only direction-specific intermolecular interaction is a two-centre iodo···nitro interaction involving the fully occupied I5 site and the half-occupied O1 site in the molecules at (x, y, z) and (1/2 − x, 1/2 − y, 1 − z), with I···O 3.339 (13) Å, C—I···O 148.5 (2)° and I···O—N 135.3 (13)°. If the O11 sites in both of these molecules were fully occupied, the resulting dimer would contain an R22(14) motif (Fig. 5). However, each such pair of molecules may, in fact, contain two, one or zero I···O interactions, depending upon the local occupancy of the O11 sites, with an average value of one. There are four of these dimeric aggregates in each unit cell of (II), but there are no direction-specific interactions between them. In the isomeric compound, (III), the fully ordered molecules are linked into isolated chains by a single two-centre iodo···nitro interaction (Garden, da Cunha et al., 2002). The intramolecular distances and angles in (I) and (II) present no unusual features.