Molecules of 3- and 4-iodobenzaldehyde 2,4-dinitrophenylhydrazone, C
13H
9IN
4O
4, are both effectively planar. In the crystal structure of each compound, molecules are linked by a combination of N-H
O and C-H
O hydrogen bonds into complex chains of rings, containing four and three different ring motifs, respectively; neither compound contains any iodo-nitro interactions. In 3-iodobenzaldehyde 4-nitrophenylhydrazone, C
13H
10IN
3O
2, where the iodinated aryl ring is disordered over two sets of sites, the hydrogen bonds generate a chain of rings, while two independent I
O interactions generate a three-dimensional framework.
Supporting information
CCDC references: 231054; 231055; 231056
For the preparation of each of (I)–(III), a finely powdered mixture of the appropriate iodobenzaldehyde and the appropriate phenylhydrazine (1:1 molar ratio) was gently heated on a hotplate until effervescence ceased. The mixtures were cooled and recrystallized from ethanol.
Crystals of (I)–(III) are all monoclinic, and for each compound, the systematic absences permitted C2/c and Cc as possible space groups. Space group C2/c was chosen for (I) and (II), and Cc was chosen for (III); these selections were all confirmed by the subsequent structural analyses. In (III), the C—H units of the iodinated ring were disordered over two sets of sites, having occupancies of 0.545 (12) (CnA; n = 2, 3, 5, 6) and 0.455 (12) (CnB); the disordered C atoms were all refined isotropically. A data set for (III) collected at 120 (2) K provided no tractable solution, but in the 291 (2) K data set, only ca 42% of the reflection are labelled observed. All H atoms were treated as riding atoms, with C—H distances of 0.95 Å and N—H distances of 0.88 Å for (I) and (II) at 120 (2) K, and C—H distances of 0.93 Å and N—H distances of 0.86 Å for (III) at 291 (2) K. For (III), the correct orientation of the structure relative to the directions of the polar axes was established by means of the Flack (1983) parameter.
For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997). Program(s) used to solve structure: SHELXS86 (Sheldrick, 1986) for (I); SHELXS97 (Sheldrick, 1997) for (II), (III). For all compounds, 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).
(I) 3-Iodobenzaldehyde 2,4-dinitrophenylhydrazone
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Crystal data top
C13H9IN4O4 | F(000) = 1600 |
Mr = 412.14 | Dx = 1.950 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3220 reflections |
a = 30.0604 (9) Å | θ = 3.0–27.5° |
b = 13.5628 (4) Å | µ = 2.31 mm−1 |
c = 7.0263 (2) Å | T = 120 K |
β = 101.390 (2)° | Plate, colourless |
V = 2808.23 (14) Å3 | 0.45 × 0.25 × 0.02 mm |
Z = 8 | |
Data collection top
Nonius KappaCCD diffractometer | 3220 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2545 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −38→38 |
Tmin = 0.424, Tmax = 0.955 | k = −17→15 |
17244 measured reflections | l = −9→9 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0325P)2 + 3.2981P] where P = (Fo2 + 2Fc2)/3 |
3220 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −1.32 e Å−3 |
Crystal data top
C13H9IN4O4 | V = 2808.23 (14) Å3 |
Mr = 412.14 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 30.0604 (9) Å | µ = 2.31 mm−1 |
b = 13.5628 (4) Å | T = 120 K |
c = 7.0263 (2) Å | 0.45 × 0.25 × 0.02 mm |
β = 101.390 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 3220 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 2545 reflections with I > 2σ(I) |
Tmin = 0.424, Tmax = 0.955 | Rint = 0.052 |
17244 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.77 e Å−3 |
3220 reflections | Δρmin = −1.32 e Å−3 |
199 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.35503 (10) | 0.3679 (2) | 0.0683 (4) | 0.0193 (6) | |
C2 | 0.32014 (9) | 0.4107 (2) | −0.0681 (4) | 0.0176 (6) | |
C3 | 0.28676 (10) | 0.3515 (2) | −0.1728 (4) | 0.0203 (6) | |
C4 | 0.28660 (10) | 0.2499 (2) | −0.1444 (4) | 0.0245 (6) | |
C5 | 0.32147 (10) | 0.2077 (2) | −0.0105 (4) | 0.0243 (7) | |
C6 | 0.35547 (9) | 0.2660 (2) | 0.0953 (4) | 0.0202 (6) | |
I3 | 0.235428 (7) | 0.416977 (15) | −0.38017 (3) | 0.02955 (9) | |
C7 | 0.39109 (9) | 0.4280 (2) | 0.1802 (4) | 0.0193 (6) | |
N1 | 0.39107 (8) | 0.52185 (17) | 0.1563 (3) | 0.0185 (5) | |
N2 | 0.42639 (8) | 0.57186 (16) | 0.2699 (3) | 0.0180 (5) | |
C11 | 0.42588 (9) | 0.6719 (2) | 0.2686 (4) | 0.0173 (6) | |
C12 | 0.45939 (9) | 0.7305 (2) | 0.3869 (4) | 0.0183 (6) | |
C13 | 0.45722 (10) | 0.8335 (2) | 0.3849 (4) | 0.0206 (6) | |
C14 | 0.42178 (10) | 0.8776 (2) | 0.2626 (4) | 0.0223 (6) | |
C15 | 0.38841 (10) | 0.8231 (2) | 0.1417 (4) | 0.0225 (6) | |
C16 | 0.39035 (10) | 0.7231 (2) | 0.1454 (4) | 0.0204 (6) | |
N12 | 0.49819 (8) | 0.68813 (17) | 0.5144 (3) | 0.0192 (5) | |
O21 | 0.50056 (7) | 0.59664 (14) | 0.5290 (3) | 0.0295 (5) | |
O22 | 0.52784 (6) | 0.74225 (15) | 0.6024 (3) | 0.0250 (4) | |
N14 | 0.41871 (9) | 0.98532 (19) | 0.2623 (4) | 0.0308 (6) | |
O41 | 0.44907 (8) | 1.03224 (16) | 0.3626 (4) | 0.0410 (6) | |
O42 | 0.38513 (8) | 1.02313 (17) | 0.1593 (4) | 0.0431 (6) | |
H2 | 0.3195 | 0.4800 | −0.0884 | 0.021* | |
H4 | 0.2630 | 0.2102 | −0.2155 | 0.029* | |
H5 | 0.3221 | 0.1383 | 0.0088 | 0.029* | |
H6 | 0.3792 | 0.2364 | 0.1868 | 0.024* | |
H7 | 0.4147 | 0.3977 | 0.2712 | 0.023* | |
H2A | 0.4490 | 0.5395 | 0.3422 | 0.022* | |
H13 | 0.4797 | 0.8717 | 0.4664 | 0.025* | |
H15 | 0.3644 | 0.8557 | 0.0570 | 0.027* | |
H16 | 0.3673 | 0.6864 | 0.0632 | 0.024* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0178 (14) | 0.0209 (15) | 0.0194 (14) | −0.0009 (12) | 0.0045 (11) | −0.0007 (11) |
C2 | 0.0177 (14) | 0.0164 (14) | 0.0182 (14) | −0.0001 (11) | 0.0026 (11) | 0.0004 (11) |
C3 | 0.0171 (14) | 0.0256 (16) | 0.0171 (14) | −0.0014 (12) | 0.0009 (11) | −0.0017 (12) |
C4 | 0.0253 (16) | 0.0211 (15) | 0.0256 (15) | −0.0057 (13) | 0.0018 (12) | −0.0062 (13) |
C5 | 0.0251 (16) | 0.0188 (15) | 0.0296 (17) | −0.0018 (12) | 0.0067 (13) | −0.0003 (12) |
C6 | 0.0191 (14) | 0.0193 (15) | 0.0218 (14) | 0.0008 (12) | 0.0031 (11) | −0.0009 (12) |
I3 | 0.02467 (13) | 0.03447 (14) | 0.02449 (12) | −0.00515 (9) | −0.00737 (8) | 0.00252 (9) |
C7 | 0.0137 (14) | 0.0249 (16) | 0.0184 (14) | 0.0005 (12) | 0.0013 (11) | −0.0016 (12) |
N1 | 0.0150 (12) | 0.0221 (13) | 0.0173 (11) | −0.0015 (10) | 0.0000 (9) | −0.0038 (10) |
N2 | 0.0135 (12) | 0.0187 (13) | 0.0191 (12) | −0.0001 (10) | −0.0036 (9) | −0.0004 (10) |
C11 | 0.0178 (14) | 0.0176 (14) | 0.0165 (13) | −0.0002 (11) | 0.0030 (11) | −0.0015 (11) |
C12 | 0.0156 (14) | 0.0208 (15) | 0.0177 (13) | 0.0008 (11) | 0.0009 (10) | −0.0006 (11) |
C13 | 0.0195 (15) | 0.0209 (15) | 0.0203 (14) | 0.0008 (12) | 0.0016 (11) | −0.0005 (12) |
C14 | 0.0215 (16) | 0.0185 (14) | 0.0253 (15) | 0.0015 (12) | 0.0005 (12) | 0.0002 (12) |
C15 | 0.0170 (15) | 0.0241 (16) | 0.0244 (15) | 0.0058 (12) | −0.0007 (11) | 0.0019 (12) |
C16 | 0.0177 (14) | 0.0221 (16) | 0.0197 (14) | −0.0017 (12) | −0.0004 (11) | −0.0009 (11) |
N12 | 0.0167 (12) | 0.0205 (13) | 0.0187 (12) | 0.0002 (10) | −0.0005 (9) | −0.0013 (10) |
O21 | 0.0294 (12) | 0.0145 (11) | 0.0376 (13) | 0.0030 (9) | −0.0105 (10) | −0.0016 (9) |
O22 | 0.0175 (10) | 0.0239 (11) | 0.0294 (11) | −0.0037 (9) | −0.0060 (8) | −0.0025 (9) |
N14 | 0.0298 (15) | 0.0200 (14) | 0.0397 (16) | 0.0056 (12) | −0.0002 (12) | 0.0027 (12) |
O41 | 0.0392 (15) | 0.0197 (12) | 0.0572 (16) | −0.0043 (11) | −0.0072 (12) | −0.0040 (11) |
O42 | 0.0432 (15) | 0.0247 (13) | 0.0537 (16) | 0.0128 (11) | −0.0091 (12) | 0.0037 (11) |
Geometric parameters (Å, º) top
C1—C6 | 1.394 (4) | N2—H2A | 0.88 |
C1—C2 | 1.400 (4) | C11—C16 | 1.416 (4) |
C1—C7 | 1.457 (4) | C11—C12 | 1.417 (4) |
C2—C3 | 1.378 (4) | C12—C13 | 1.397 (4) |
C2—H2 | 0.95 | C12—N12 | 1.442 (3) |
C3—C4 | 1.393 (4) | C13—C14 | 1.367 (4) |
C3—I3 | 2.099 (3) | C13—H13 | 0.95 |
C4—C5 | 1.386 (4) | C14—C15 | 1.392 (4) |
C4—H4 | 0.95 | C14—N14 | 1.464 (4) |
C5—C6 | 1.387 (4) | C15—C16 | 1.358 (4) |
C5—H5 | 0.95 | C15—H15 | 0.95 |
C6—H6 | 0.95 | C16—H16 | 0.95 |
C7—N1 | 1.284 (4) | N12—O22 | 1.224 (3) |
C7—H7 | 0.95 | N12—O21 | 1.246 (3) |
N1—N2 | 1.375 (3) | N14—O41 | 1.217 (3) |
N2—C11 | 1.357 (3) | N14—O42 | 1.232 (3) |
| | | |
C6—C1—C2 | 119.4 (3) | N2—C11—C16 | 120.0 (2) |
C6—C1—C7 | 119.7 (3) | N2—C11—C12 | 123.5 (2) |
C2—C1—C7 | 121.0 (3) | C16—C11—C12 | 116.5 (2) |
C3—C2—C1 | 119.5 (3) | C13—C12—C11 | 121.9 (2) |
C3—C2—H2 | 120.3 | C13—C12—N12 | 115.8 (2) |
C1—C2—H2 | 120.3 | C11—C12—N12 | 122.3 (2) |
C2—C3—C4 | 121.5 (3) | C14—C13—C12 | 118.2 (3) |
C2—C3—I3 | 118.8 (2) | C14—C13—H13 | 120.9 |
C4—C3—I3 | 119.7 (2) | C12—C13—H13 | 120.9 |
C5—C4—C3 | 118.8 (3) | C13—C14—C15 | 122.0 (3) |
C5—C4—H4 | 120.6 | C13—C14—N14 | 118.6 (3) |
C3—C4—H4 | 120.6 | C15—C14—N14 | 119.4 (2) |
C4—C5—C6 | 120.5 (3) | C16—C15—C14 | 119.7 (3) |
C4—C5—H5 | 119.8 | C16—C15—H15 | 120.1 |
C6—C5—H5 | 119.8 | C14—C15—H15 | 120.1 |
C5—C6—C1 | 120.4 (3) | C15—C16—C11 | 121.7 (3) |
C5—C6—H6 | 119.8 | C15—C16—H16 | 119.2 |
C1—C6—H6 | 119.8 | C11—C16—H16 | 119.2 |
N1—C7—C1 | 120.2 (3) | O22—N12—O21 | 122.1 (2) |
N1—C7—H7 | 119.9 | O22—N12—C12 | 119.6 (2) |
C1—C7—H7 | 119.9 | O21—N12—C12 | 118.3 (2) |
C7—N1—N2 | 115.7 (2) | O41—N14—O42 | 123.8 (3) |
C11—N2—N1 | 118.9 (2) | O41—N14—C14 | 118.8 (2) |
C11—N2—H2A | 120.6 | O42—N14—C14 | 117.4 (2) |
N1—N2—H2A | 120.6 | | |
| | | |
C6—C1—C2—C3 | 0.2 (4) | C16—C11—C12—N12 | −177.9 (2) |
C7—C1—C2—C3 | 179.4 (3) | C11—C12—C13—C14 | −0.8 (4) |
C1—C2—C3—C4 | 0.8 (4) | N12—C12—C13—C14 | 178.2 (2) |
C1—C2—C3—I3 | −178.9 (2) | C12—C13—C14—C15 | −0.1 (4) |
C2—C3—C4—C5 | −1.4 (4) | C12—C13—C14—N14 | 178.8 (3) |
I3—C3—C4—C5 | 178.3 (2) | C13—C14—C15—C16 | 0.8 (5) |
C3—C4—C5—C6 | 1.0 (4) | N14—C14—C15—C16 | −178.1 (3) |
C4—C5—C6—C1 | −0.1 (4) | C14—C15—C16—C11 | −0.6 (5) |
C2—C1—C6—C5 | −0.6 (4) | N2—C11—C16—C15 | 179.3 (3) |
C7—C1—C6—C5 | −179.8 (3) | C12—C11—C16—C15 | −0.4 (4) |
C6—C1—C7—N1 | 179.9 (3) | C13—C12—N12—O22 | −4.5 (4) |
C2—C1—C7—N1 | 0.7 (4) | C11—C12—N12—O22 | 174.6 (2) |
C1—C7—N1—N2 | 179.6 (2) | C13—C12—N12—O21 | 176.4 (3) |
C7—N1—N2—C11 | −172.6 (3) | C11—C12—N12—O21 | −4.5 (4) |
N1—N2—C11—C16 | −2.7 (4) | C13—C14—N14—O41 | 4.1 (4) |
N1—N2—C11—C12 | 176.9 (2) | C15—C14—N14—O41 | −177.0 (3) |
N2—C11—C12—C13 | −178.5 (3) | C13—C14—N14—O42 | −175.9 (3) |
C16—C11—C12—C13 | 1.1 (4) | C15—C14—N14—O42 | 3.1 (4) |
N2—C11—C12—N12 | 2.5 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O21 | 0.88 | 1.98 | 2.607 (3) | 127 |
N2—H2A···O21i | 0.88 | 2.45 | 3.289 (3) | 160 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
(II) 4-Iodobenzaldehyde 2,4-dinitrophenylhydrazone
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Crystal data top
C13H9IN4O4 | F(000) = 1600 |
Mr = 412.14 | Dx = 2.002 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3074 reflections |
a = 32.359 (2) Å | θ = 3.2–27.6° |
b = 4.6293 (3) Å | µ = 2.37 mm−1 |
c = 18.4169 (15) Å | T = 120 K |
β = 97.631 (3)° | Needle, orange |
V = 2734.4 (3) Å3 | 0.45 × 0.04 × 0.02 mm |
Z = 8 | |
Data collection top
Nonius KappaCCD diffractometer | 3074 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.118 |
ϕ scans, and ω scans with κ offsets | θmax = 27.6°, θmin = 3.2° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −41→40 |
Tmin = 0.416, Tmax = 0.954 | k = −5→6 |
12789 measured reflections | l = −23→19 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0235P)2] where P = (Fo2 + 2Fc2)/3 |
3074 reflections | (Δ/σ)max = 0.002 |
199 parameters | Δρmax = 0.82 e Å−3 |
0 restraints | Δρmin = −1.09 e Å−3 |
Crystal data top
C13H9IN4O4 | V = 2734.4 (3) Å3 |
Mr = 412.14 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 32.359 (2) Å | µ = 2.37 mm−1 |
b = 4.6293 (3) Å | T = 120 K |
c = 18.4169 (15) Å | 0.45 × 0.04 × 0.02 mm |
β = 97.631 (3)° | |
Data collection top
Nonius KappaCCD diffractometer | 3074 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 1686 reflections with I > 2σ(I) |
Tmin = 0.416, Tmax = 0.954 | Rint = 0.118 |
12789 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.82 e Å−3 |
3074 reflections | Δρmin = −1.09 e Å−3 |
199 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.64812 (15) | 0.1563 (13) | 0.5656 (3) | 0.0175 (12) | |
C2 | 0.68385 (16) | 0.1696 (13) | 0.5303 (3) | 0.0252 (13) | |
C3 | 0.71950 (16) | 0.0187 (12) | 0.5565 (3) | 0.0244 (14) | |
C4 | 0.71927 (15) | −0.1527 (13) | 0.6195 (3) | 0.0209 (12) | |
I4 | 0.775212 (12) | −0.34687 (10) | 0.66469 (2) | 0.03486 (15) | |
C5 | 0.68422 (16) | −0.1763 (13) | 0.6532 (3) | 0.0204 (12) | |
C6 | 0.64889 (16) | −0.0236 (11) | 0.6271 (3) | 0.0179 (13) | |
C7 | 0.61134 (15) | 0.3253 (13) | 0.5414 (3) | 0.0191 (12) | |
N1 | 0.61077 (13) | 0.4974 (10) | 0.4869 (3) | 0.0191 (11) | |
N2 | 0.57452 (12) | 0.6449 (10) | 0.4666 (2) | 0.0153 (9) | |
C11 | 0.57281 (15) | 0.8431 (13) | 0.4120 (3) | 0.0169 (12) | |
C12 | 0.53684 (15) | 0.9993 (11) | 0.3841 (3) | 0.0136 (12) | |
C13 | 0.53751 (15) | 1.2104 (11) | 0.3306 (3) | 0.0147 (12) | |
C14 | 0.57387 (17) | 1.2603 (11) | 0.3020 (3) | 0.0193 (14) | |
C15 | 0.61022 (15) | 1.1059 (12) | 0.3265 (3) | 0.0214 (14) | |
C16 | 0.60956 (16) | 0.9011 (12) | 0.3802 (3) | 0.0180 (13) | |
N12 | 0.49666 (13) | 0.9529 (10) | 0.4092 (3) | 0.0196 (11) | |
O21 | 0.49351 (11) | 0.7448 (7) | 0.4517 (2) | 0.0213 (10) | |
O22 | 0.46768 (10) | 1.1144 (8) | 0.38838 (19) | 0.0212 (9) | |
N14 | 0.57510 (15) | 1.4769 (10) | 0.2455 (3) | 0.0202 (11) | |
O41 | 0.54354 (11) | 1.6251 (9) | 0.2271 (2) | 0.0241 (9) | |
O42 | 0.60789 (12) | 1.5108 (9) | 0.2191 (2) | 0.0278 (10) | |
H2 | 0.6835 | 0.2845 | 0.4874 | 0.030* | |
H3 | 0.7437 | 0.0304 | 0.5326 | 0.029* | |
H5 | 0.6843 | −0.2982 | 0.6947 | 0.025* | |
H6 | 0.6247 | −0.0402 | 0.6509 | 0.022* | |
H7 | 0.5875 | 0.3086 | 0.5660 | 0.023* | |
H2A | 0.5525 | 0.6118 | 0.4888 | 0.018* | |
H13 | 0.5131 | 1.3185 | 0.3140 | 0.018* | |
H15 | 0.6352 | 1.1424 | 0.3060 | 0.026* | |
H16 | 0.6343 | 0.7958 | 0.3965 | 0.022* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.015 (3) | 0.021 (3) | 0.017 (3) | −0.001 (3) | 0.001 (2) | −0.002 (3) |
C2 | 0.025 (3) | 0.032 (3) | 0.021 (3) | 0.000 (3) | 0.010 (3) | 0.006 (3) |
C3 | 0.017 (3) | 0.030 (4) | 0.026 (4) | 0.003 (3) | 0.004 (3) | 0.003 (3) |
C4 | 0.020 (3) | 0.018 (3) | 0.024 (3) | 0.004 (3) | 0.000 (2) | 0.004 (3) |
I4 | 0.0238 (2) | 0.0470 (3) | 0.0338 (3) | 0.0126 (2) | 0.00383 (16) | 0.0104 (3) |
C5 | 0.025 (3) | 0.020 (3) | 0.015 (3) | 0.000 (3) | −0.002 (2) | 0.002 (3) |
C6 | 0.018 (3) | 0.020 (3) | 0.017 (3) | 0.004 (2) | 0.005 (2) | 0.001 (2) |
C7 | 0.018 (3) | 0.017 (3) | 0.023 (3) | −0.005 (3) | 0.004 (2) | −0.001 (3) |
N1 | 0.020 (2) | 0.016 (3) | 0.022 (3) | 0.004 (2) | 0.004 (2) | −0.001 (2) |
N2 | 0.016 (2) | 0.016 (2) | 0.013 (3) | 0.000 (2) | 0.0012 (19) | −0.001 (2) |
C11 | 0.021 (3) | 0.020 (3) | 0.010 (3) | −0.001 (3) | 0.003 (2) | −0.001 (3) |
C12 | 0.014 (3) | 0.019 (3) | 0.009 (3) | −0.001 (2) | 0.004 (2) | −0.005 (2) |
C13 | 0.015 (3) | 0.019 (3) | 0.009 (3) | 0.001 (2) | −0.001 (2) | −0.002 (2) |
C14 | 0.025 (3) | 0.024 (4) | 0.008 (3) | 0.000 (2) | 0.002 (2) | 0.002 (2) |
C15 | 0.012 (3) | 0.031 (4) | 0.021 (3) | −0.002 (3) | 0.005 (2) | −0.003 (3) |
C16 | 0.018 (3) | 0.019 (4) | 0.018 (3) | −0.001 (2) | 0.005 (2) | −0.001 (2) |
N12 | 0.015 (2) | 0.027 (3) | 0.016 (3) | 0.006 (2) | −0.002 (2) | −0.001 (2) |
O21 | 0.021 (2) | 0.027 (3) | 0.016 (2) | −0.0006 (16) | 0.0026 (17) | 0.0091 (17) |
O22 | 0.0184 (19) | 0.027 (2) | 0.017 (2) | 0.0037 (19) | 0.0007 (16) | 0.0011 (18) |
N14 | 0.029 (3) | 0.016 (3) | 0.015 (3) | 0.000 (2) | 0.003 (2) | −0.002 (2) |
O41 | 0.026 (2) | 0.025 (2) | 0.021 (2) | 0.002 (2) | −0.0013 (17) | 0.0024 (19) |
O42 | 0.028 (2) | 0.032 (2) | 0.028 (3) | −0.0054 (19) | 0.018 (2) | 0.0045 (19) |
Geometric parameters (Å, º) top
C1—C2 | 1.402 (7) | N2—H2A | 0.88 |
C1—C6 | 1.402 (7) | C11—C12 | 1.408 (7) |
C1—C7 | 1.445 (7) | C11—C16 | 1.419 (7) |
C2—C3 | 1.380 (7) | C12—C13 | 1.391 (7) |
C2—H2 | 0.95 | C12—N12 | 1.452 (6) |
C3—C4 | 1.405 (8) | C13—C14 | 1.371 (7) |
C3—H3 | 0.95 | C13—H13 | 0.95 |
C4—C5 | 1.368 (7) | C14—C15 | 1.399 (7) |
C4—I4 | 2.092 (5) | C14—N14 | 1.449 (7) |
C5—C6 | 1.375 (7) | C15—C16 | 1.373 (7) |
C5—H5 | 0.95 | C15—H15 | 0.95 |
C6—H6 | 0.95 | C16—H16 | 0.95 |
C7—N1 | 1.280 (7) | N12—O22 | 1.221 (5) |
C7—H7 | 0.95 | N12—O21 | 1.254 (5) |
N1—N2 | 1.365 (6) | N14—O42 | 1.234 (5) |
N2—C11 | 1.357 (7) | N14—O41 | 1.240 (5) |
| | | |
C2—C1—C6 | 118.3 (5) | N2—C11—C12 | 124.6 (5) |
C2—C1—C7 | 121.9 (5) | N2—C11—C16 | 118.7 (5) |
C6—C1—C7 | 119.8 (5) | C12—C11—C16 | 116.7 (5) |
C3—C2—C1 | 121.1 (5) | C13—C12—C11 | 122.0 (5) |
C3—C2—H2 | 119.4 | C13—C12—N12 | 115.4 (4) |
C1—C2—H2 | 119.4 | C11—C12—N12 | 122.7 (5) |
C2—C3—C4 | 118.7 (5) | C14—C13—C12 | 119.1 (5) |
C2—C3—H3 | 120.7 | C14—C13—H13 | 120.5 |
C4—C3—H3 | 120.7 | C12—C13—H13 | 120.5 |
C5—C4—C3 | 121.0 (5) | C13—C14—C15 | 121.2 (5) |
C5—C4—I4 | 120.7 (4) | C13—C14—N14 | 120.0 (5) |
C3—C4—I4 | 118.2 (4) | C15—C14—N14 | 118.9 (5) |
C4—C5—C6 | 120.0 (5) | C16—C15—C14 | 119.5 (5) |
C4—C5—H5 | 120.0 | C16—C15—H15 | 120.3 |
C6—C5—H5 | 120.0 | C14—C15—H15 | 120.3 |
C5—C6—C1 | 120.8 (5) | C15—C16—C11 | 121.5 (5) |
C5—C6—H6 | 119.6 | C15—C16—H16 | 119.3 |
C1—C6—H6 | 119.6 | C11—C16—H16 | 119.3 |
N1—C7—C1 | 120.3 (5) | O22—N12—O21 | 123.0 (4) |
N1—C7—H7 | 119.8 | O22—N12—C12 | 119.5 (5) |
C1—C7—H7 | 119.8 | O21—N12—C12 | 117.6 (4) |
C7—N1—N2 | 116.6 (4) | O42—N14—O41 | 122.8 (5) |
C11—N2—N1 | 119.3 (4) | O42—N14—C14 | 118.5 (5) |
C11—N2—H2A | 120.4 | O41—N14—C14 | 118.6 (5) |
N1—N2—H2A | 120.4 | | |
| | | |
C6—C1—C2—C3 | −2.4 (9) | C16—C11—C12—N12 | 177.2 (5) |
C7—C1—C2—C3 | 176.4 (6) | C11—C12—C13—C14 | 2.6 (8) |
C1—C2—C3—C4 | 0.7 (9) | N12—C12—C13—C14 | −177.7 (5) |
C2—C3—C4—C5 | 1.6 (9) | C12—C13—C14—C15 | −0.9 (8) |
C2—C3—C4—I4 | −174.0 (4) | C12—C13—C14—N14 | 179.3 (5) |
C3—C4—C5—C6 | −2.2 (9) | C13—C14—C15—C16 | −0.2 (8) |
I4—C4—C5—C6 | 173.3 (4) | N14—C14—C15—C16 | 179.7 (5) |
C4—C5—C6—C1 | 0.4 (8) | C14—C15—C16—C11 | −0.4 (8) |
C2—C1—C6—C5 | 1.9 (8) | N2—C11—C16—C15 | −177.8 (5) |
C7—C1—C6—C5 | −177.0 (5) | C12—C11—C16—C15 | 1.9 (8) |
C2—C1—C7—N1 | −1.2 (9) | C13—C12—N12—O22 | −7.1 (7) |
C6—C1—C7—N1 | 177.7 (5) | C11—C12—N12—O22 | 172.7 (5) |
C1—C7—N1—N2 | 178.8 (5) | C13—C12—N12—O21 | 172.7 (4) |
C7—N1—N2—C11 | 176.2 (5) | C11—C12—N12—O21 | −7.5 (7) |
N1—N2—C11—C12 | 177.1 (5) | C13—C14—N14—O42 | −177.7 (5) |
N1—N2—C11—C16 | −3.2 (8) | C15—C14—N14—O42 | 2.4 (7) |
N2—C11—C12—C13 | 176.7 (5) | C13—C14—N14—O41 | 4.1 (7) |
C16—C11—C12—C13 | −3.1 (8) | C15—C14—N14—O41 | −175.8 (5) |
N2—C11—C12—N12 | −3.0 (9) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O21 | 0.88 | 2.04 | 2.640 (5) | 125 |
N2—H2A···O21i | 0.88 | 2.56 | 3.353 (6) | 150 |
C13—H13···O41ii | 0.95 | 2.37 | 3.310 (6) | 175 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2. |
(III) 4-Iodobenzaldehyde 4-nitrophenylhydrazone
top
Crystal data top
C13H10IN3O2 | F(000) = 712 |
Mr = 367.14 | Dx = 1.742 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 4058 reflections |
a = 4.9348 (4) Å | θ = 2.5–32.5° |
b = 27.825 (2) Å | µ = 2.29 mm−1 |
c = 10.3893 (9) Å | T = 291 K |
β = 101.076 (2)° | Plate, orange |
V = 1399.99 (19) Å3 | 0.42 × 0.20 × 0.04 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD diffractometer | 4058 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ scans, and ω scans with κ offsets | θmax = 32.5°, θmin = 2.5° |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | h = −7→7 |
Tmin = 0.447, Tmax = 0.914 | k = −42→35 |
7191 measured reflections | l = −15→10 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0438P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.88 | (Δ/σ)max < 0.001 |
4058 reflections | Δρmax = 0.48 e Å−3 |
169 parameters | Δρmin = −0.44 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 1511 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (3) |
Crystal data top
C13H10IN3O2 | V = 1399.99 (19) Å3 |
Mr = 367.14 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 4.9348 (4) Å | µ = 2.29 mm−1 |
b = 27.825 (2) Å | T = 291 K |
c = 10.3893 (9) Å | 0.42 × 0.20 × 0.04 mm |
β = 101.076 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 4058 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | 1686 reflections with I > 2σ(I) |
Tmin = 0.447, Tmax = 0.914 | Rint = 0.029 |
7191 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.106 | Δρmax = 0.48 e Å−3 |
S = 0.88 | Δρmin = −0.44 e Å−3 |
4058 reflections | Absolute structure: Flack (1983), 1511 Friedel pairs |
169 parameters | Absolute structure parameter: 0.01 (3) |
2 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.4725 (11) | 0.29436 (18) | 0.4907 (6) | 0.0620 (14) | |
C4 | 0.6416 (13) | 0.19899 (17) | 0.5281 (6) | 0.0728 (17) | |
C2A | 0.348 (3) | 0.2628 (3) | 0.5718 (14) | 0.067 (3)* | 0.545 (12) |
C3A | 0.438 (3) | 0.2163 (4) | 0.5869 (14) | 0.073 (3)* | 0.545 (12) |
C5A | 0.770 (3) | 0.2314 (4) | 0.4489 (13) | 0.079 (4)* | 0.545 (12) |
C6A | 0.684 (3) | 0.2770 (4) | 0.4340 (12) | 0.069 (3)* | 0.545 (12) |
C2B | 0.478 (3) | 0.2718 (5) | 0.6084 (16) | 0.062 (4)* | 0.455 (12) |
C3B | 0.561 (3) | 0.2239 (4) | 0.6350 (15) | 0.061 (4)* | 0.455 (12) |
C5B | 0.625 (3) | 0.2195 (5) | 0.4120 (16) | 0.071 (4)* | 0.455 (12) |
C6B | 0.550 (3) | 0.2678 (4) | 0.3924 (14) | 0.059 (4)* | 0.455 (12) |
I4 | 0.77441 (15) | 0.128099 (11) | 0.56208 (11) | 0.1064 (2) | |
C7 | 0.3867 (12) | 0.3444 (2) | 0.4713 (6) | 0.0688 (15) | |
N1 | 0.2262 (11) | 0.36303 (13) | 0.5428 (7) | 0.0643 (16) | |
N2 | 0.1661 (9) | 0.41057 (16) | 0.5248 (5) | 0.0668 (13) | |
C11 | 0.0103 (10) | 0.43269 (17) | 0.6021 (6) | 0.0548 (12) | |
C12 | −0.1177 (11) | 0.40660 (18) | 0.6895 (6) | 0.0607 (13) | |
C13 | −0.2788 (11) | 0.43068 (17) | 0.7623 (5) | 0.0611 (14) | |
C14 | −0.3117 (10) | 0.47934 (17) | 0.7529 (5) | 0.0521 (12) | |
C15 | −0.1792 (10) | 0.50596 (17) | 0.6690 (6) | 0.0567 (13) | |
C16 | −0.0238 (11) | 0.48263 (19) | 0.5941 (6) | 0.0607 (13) | |
N14 | −0.4857 (9) | 0.50331 (17) | 0.8303 (5) | 0.0649 (13) | |
O41 | −0.6034 (9) | 0.47921 (16) | 0.9003 (4) | 0.0768 (11) | |
O42 | −0.5066 (9) | 0.54726 (14) | 0.8223 (5) | 0.0814 (11) | |
H2A | 0.2092 | 0.2738 | 0.6135 | 0.080* | 0.545 (12) |
H3A | 0.3562 | 0.1957 | 0.6390 | 0.088* | 0.545 (12) |
H5A | 0.9116 | 0.2206 | 0.4086 | 0.095* | 0.545 (12) |
H6A | 0.7698 | 0.2976 | 0.3839 | 0.082* | 0.545 (12) |
H2B | 0.4223 | 0.2893 | 0.6750 | 0.075* | 0.455 (12) |
H3B | 0.5642 | 0.2096 | 0.7161 | 0.073* | 0.455 (12) |
H5B | 0.6645 | 0.2015 | 0.3424 | 0.085* | 0.455 (12) |
H6B | 0.5529 | 0.2821 | 0.3117 | 0.071* | 0.455 (12) |
H7 | 0.4472 | 0.3628 | 0.4078 | 0.083* | |
H2 | 0.2261 | 0.4265 | 0.4651 | 0.080* | |
H12 | −0.0938 | 0.3735 | 0.6979 | 0.073* | |
H13 | −0.3671 | 0.4135 | 0.8191 | 0.073* | |
H15 | −0.1972 | 0.5392 | 0.6645 | 0.068* | |
H16 | 0.0612 | 0.5001 | 0.5366 | 0.073* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.071 (3) | 0.052 (3) | 0.066 (4) | 0.004 (3) | 0.022 (3) | −0.005 (2) |
C4 | 0.087 (4) | 0.049 (3) | 0.082 (5) | 0.011 (3) | 0.015 (3) | −0.002 (3) |
I4 | 0.1229 (3) | 0.0594 (2) | 0.1328 (4) | 0.0207 (3) | 0.0147 (3) | −0.0009 (3) |
C7 | 0.080 (4) | 0.065 (3) | 0.065 (4) | 0.010 (3) | 0.024 (3) | 0.008 (3) |
N1 | 0.064 (4) | 0.052 (2) | 0.078 (4) | 0.006 (2) | 0.017 (4) | 0.000 (3) |
N2 | 0.071 (3) | 0.060 (2) | 0.075 (4) | 0.009 (2) | 0.030 (3) | 0.005 (2) |
C11 | 0.051 (3) | 0.052 (3) | 0.059 (3) | 0.003 (2) | 0.006 (3) | 0.004 (2) |
C12 | 0.068 (3) | 0.043 (2) | 0.072 (4) | 0.004 (2) | 0.017 (3) | 0.001 (2) |
C13 | 0.064 (3) | 0.056 (3) | 0.067 (4) | −0.001 (2) | 0.022 (3) | 0.006 (3) |
C14 | 0.045 (3) | 0.054 (3) | 0.056 (3) | 0.003 (2) | 0.007 (2) | −0.004 (2) |
C15 | 0.056 (3) | 0.045 (2) | 0.068 (4) | 0.006 (2) | 0.009 (3) | 0.004 (2) |
C16 | 0.063 (3) | 0.060 (3) | 0.062 (4) | 0.002 (2) | 0.019 (3) | 0.008 (3) |
N14 | 0.058 (3) | 0.068 (3) | 0.063 (3) | 0.003 (2) | −0.001 (3) | −0.011 (3) |
O41 | 0.076 (3) | 0.079 (3) | 0.082 (3) | −0.003 (2) | 0.033 (2) | −0.004 (2) |
O42 | 0.096 (3) | 0.061 (2) | 0.092 (3) | 0.013 (2) | 0.028 (2) | −0.006 (2) |
Geometric parameters (Å, º) top
C1—C2B | 1.370 (15) | C5B—H5B | 0.93 |
C1—C6B | 1.375 (14) | C6B—H6B | 0.93 |
C1—C6A | 1.382 (13) | C7—N1 | 1.294 (9) |
C1—C2A | 1.434 (13) | C7—H7 | 0.93 |
C1—C7 | 1.457 (7) | N1—N2 | 1.361 (6) |
C4—C5B | 1.323 (15) | N2—C11 | 1.361 (7) |
C4—C3A | 1.362 (15) | N2—H2 | 0.86 |
C4—C3B | 1.428 (15) | C11—C16 | 1.400 (7) |
C4—C5A | 1.447 (15) | C11—C12 | 1.404 (8) |
C4—I4 | 2.087 (5) | C12—C13 | 1.373 (8) |
C2A—C3A | 1.367 (14) | C12—H12 | 0.93 |
C2A—H2A | 0.93 | C13—C14 | 1.365 (7) |
C3A—H3A | 0.93 | C13—H13 | 0.93 |
C5A—C6A | 1.337 (14) | C14—C15 | 1.398 (8) |
C5A—H5A | 0.93 | C14—N14 | 1.447 (7) |
C6A—H6A | 0.93 | C15—C16 | 1.358 (8) |
C2B—C3B | 1.407 (16) | C15—H15 | 0.93 |
C2B—H2B | 0.93 | C16—H16 | 0.93 |
C3B—H3B | 0.93 | N14—O41 | 1.216 (6) |
C5B—C6B | 1.399 (17) | N14—O42 | 1.229 (5) |
| | | |
C2B—C1—C6B | 117.2 (9) | C4—C5B—C6B | 121.0 (13) |
C2B—C1—C6A | 109.5 (8) | C4—C5B—H5B | 119.5 |
C6B—C1—C2A | 108.6 (8) | C6B—C5B—H5B | 119.5 |
C6A—C1—C2A | 118.7 (7) | C1—C6B—C5B | 120.9 (12) |
C2B—C1—C7 | 121.0 (7) | C1—C6B—H6B | 119.6 |
C6B—C1—C7 | 121.8 (7) | C5B—C6B—H6B | 119.6 |
C6A—C1—C7 | 119.9 (7) | N1—C7—C1 | 119.8 (5) |
C2A—C1—C7 | 121.3 (6) | N1—C7—H7 | 120.1 |
C5B—C4—C3A | 109.6 (9) | C1—C7—H7 | 120.1 |
C5B—C4—C3B | 121.5 (8) | C7—N1—N2 | 116.9 (6) |
C3A—C4—C5A | 118.5 (8) | N1—N2—C11 | 119.4 (5) |
C3B—C4—C5A | 110.9 (8) | N1—N2—H2 | 120.3 |
C5B—C4—I4 | 121.5 (7) | C11—N2—H2 | 120.3 |
C3A—C4—I4 | 119.6 (7) | N2—C11—C16 | 119.3 (5) |
C3B—C4—I4 | 116.9 (6) | N2—C11—C12 | 121.5 (4) |
C5A—C4—I4 | 121.8 (6) | C16—C11—C12 | 119.2 (5) |
C3A—C2A—C1 | 118.8 (10) | C13—C12—C11 | 118.9 (5) |
C3A—C2A—H2A | 120.6 | C13—C12—H12 | 120.5 |
C1—C2A—H2A | 120.6 | C11—C12—H12 | 120.5 |
C4—C3A—C2A | 122.3 (12) | C14—C13—C12 | 121.2 (5) |
C4—C3A—H3A | 118.9 | C14—C13—H13 | 119.4 |
C2A—C3A—H3A | 118.9 | C12—C13—H13 | 119.4 |
C6A—C5A—C4 | 119.5 (12) | C13—C14—C15 | 120.4 (5) |
C6A—C5A—H5A | 120.3 | C13—C14—N14 | 119.5 (5) |
C4—C5A—H5A | 120.3 | C15—C14—N14 | 120.0 (5) |
C5A—C6A—C1 | 122.2 (11) | C16—C15—C14 | 119.1 (5) |
C5A—C6A—H6A | 118.9 | C16—C15—H15 | 120.4 |
C1—C6A—H6A | 118.9 | C14—C15—H15 | 120.4 |
C1—C2B—C3B | 124.3 (13) | C15—C16—C11 | 121.0 (5) |
C1—C2B—H2B | 117.8 | C15—C16—H16 | 119.5 |
C3B—C2B—H2B | 117.8 | C11—C16—H16 | 119.5 |
C2B—C3B—C4 | 115.0 (11) | O41—N14—O42 | 123.1 (5) |
C2B—C3B—H3B | 122.5 | O41—N14—C14 | 118.7 (5) |
C4—C3B—H3B | 122.5 | O42—N14—C14 | 118.2 (5) |
| | | |
C2B—C1—C2A—C3A | −81.0 (18) | C5A—C4—C5B—C6B | −75.3 (18) |
C6B—C1—C2A—C3A | 31.4 (14) | I4—C4—C5B—C6B | −176.6 (10) |
C6A—C1—C2A—C3A | −2.0 (16) | C2B—C1—C6B—C5B | 1.3 (17) |
C7—C1—C2A—C3A | −179.8 (9) | C6A—C1—C6B—C5B | 84.9 (18) |
C5B—C4—C3A—C2A | −34.9 (16) | C2A—C1—C6B—C5B | −29.7 (15) |
C3B—C4—C3A—C2A | 84.2 (18) | C7—C1—C6B—C5B | −178.4 (10) |
C5A—C4—C3A—C2A | 1.0 (17) | C4—C5B—C6B—C1 | −5 (2) |
I4—C4—C3A—C2A | 177.8 (9) | C6B—C1—C7—N1 | 155.2 (9) |
C1—C2A—C3A—C4 | 0.4 (18) | C6A—C1—C7—N1 | −167.3 (8) |
C5B—C4—C5A—C6A | 82.1 (18) | C2A—C1—C7—N1 | 10.4 (11) |
C3A—C4—C5A—C6A | −0.8 (17) | C2B—C1—C7—N1 | −24.5 (11) |
C3B—C4—C5A—C6A | −33.7 (15) | C1—C7—N1—N2 | 176.5 (5) |
I4—C4—C5A—C6A | −177.6 (9) | C7—N1—N2—C11 | −176.5 (5) |
C4—C5A—C6A—C1 | −0.9 (19) | N1—N2—C11—C16 | 172.5 (5) |
C2B—C1—C6A—C5A | 33.4 (15) | N1—N2—C11—C12 | −7.7 (8) |
C6B—C1—C6A—C5A | −76.9 (17) | N2—C11—C12—C13 | −178.2 (5) |
C2A—C1—C6A—C5A | 2.3 (16) | C16—C11—C12—C13 | 1.6 (8) |
C7—C1—C6A—C5A | −180.0 (10) | C11—C12—C13—C14 | −1.3 (8) |
C6B—C1—C2B—C3B | 1.1 (18) | C12—C13—C14—C15 | −0.5 (8) |
C6A—C1—C2B—C3B | −32.9 (16) | C12—C13—C14—N14 | 179.3 (5) |
C2A—C1—C2B—C3B | 81.1 (19) | C13—C14—C15—C16 | 1.9 (8) |
C7—C1—C2B—C3B | −179.1 (10) | N14—C14—C15—C16 | −177.9 (4) |
C1—C2B—C3B—C4 | −0.5 (19) | C14—C15—C16—C11 | −1.5 (8) |
C5B—C4—C3B—C2B | −2.8 (17) | N2—C11—C16—C15 | 179.6 (5) |
C3A—C4—C3B—C2B | −77.7 (17) | C12—C11—C16—C15 | −0.3 (8) |
C5A—C4—C3B—C2B | 33.2 (13) | C13—C14—N14—O41 | −1.4 (7) |
I4—C4—C3B—C2B | 179.0 (9) | C15—C14—N14—O41 | 178.4 (5) |
C3A—C4—C5B—C6B | 36.9 (17) | C13—C14—N14—O42 | 178.3 (5) |
C3B—C4—C5B—C6B | 5 (2) | C15—C14—N14—O42 | −1.9 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O42i | 0.86 | 2.29 | 3.117 (7) | 163 |
C16—H16···O41i | 0.93 | 2.44 | 3.330 (7) | 159 |
Symmetry code: (i) x+1, −y+1, z−1/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C13H9IN4O4 | C13H9IN4O4 | C13H10IN3O2 |
Mr | 412.14 | 412.14 | 367.14 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Monoclinic, Cc |
Temperature (K) | 120 | 120 | 291 |
a, b, c (Å) | 30.0604 (9), 13.5628 (4), 7.0263 (2) | 32.359 (2), 4.6293 (3), 18.4169 (15) | 4.9348 (4), 27.825 (2), 10.3893 (9) |
β (°) | 101.390 (2) | 97.631 (3) | 101.076 (2) |
V (Å3) | 2808.23 (14) | 2734.4 (3) | 1399.99 (19) |
Z | 8 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 2.31 | 2.37 | 2.29 |
Crystal size (mm) | 0.45 × 0.25 × 0.02 | 0.45 × 0.04 × 0.02 | 0.42 × 0.20 × 0.04 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) | Multi-scan (DENZO–SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.424, 0.955 | 0.416, 0.954 | 0.447, 0.914 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17244, 3220, 2545 | 12789, 3074, 1686 | 7191, 4058, 1686 |
Rint | 0.052 | 0.118 | 0.029 |
(sin θ/λ)max (Å−1) | 0.649 | 0.651 | 0.756 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.070, 1.02 | 0.046, 0.087, 0.94 | 0.044, 0.106, 0.88 |
No. of reflections | 3220 | 3074 | 4058 |
No. of parameters | 199 | 199 | 169 |
No. of restraints | 0 | 0 | 2 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −1.32 | 0.82, −1.09 | 0.48, −0.44 |
Absolute structure | ? | ? | Flack (1983), 1511 Friedel pairs |
Absolute structure parameter | ? | ? | 0.01 (3) |
Selected torsion angles (º) for (I) topC2—C1—C7—N1 | 0.7 (4) | N1—N2—C11—C12 | 176.9 (2) |
C1—C7—N1—N2 | 179.6 (2) | C11—C12—N12—O21 | −4.5 (4) |
C7—N1—N2—C11 | −172.6 (3) | C13—C14—N14—O41 | 4.1 (4) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O21 | 0.88 | 1.98 | 2.607 (3) | 127 |
N2—H2A···O21i | 0.88 | 2.45 | 3.289 (3) | 160 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Selected torsion angles (º) for (II) topC2—C1—C7—N1 | −1.2 (9) | N1—N2—C11—C12 | 177.1 (5) |
C1—C7—N1—N2 | 178.8 (5) | C11—C12—N12—O21 | −7.5 (7) |
C7—N1—N2—C11 | 176.2 (5) | C13—C14—N14—O41 | 4.1 (7) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O21 | 0.88 | 2.04 | 2.640 (5) | 125 |
N2—H2A···O21i | 0.88 | 2.56 | 3.353 (6) | 150 |
C13—H13···O41ii | 0.95 | 2.37 | 3.310 (6) | 175 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2. |
Selected torsion angles (º) for (III) topC2A—C1—C7—N1 | 10.4 (11) | C7—N1—N2—C11 | −176.5 (5) |
C2B—C1—C7—N1 | −24.5 (11) | N1—N2—C11—C12 | −7.7 (8) |
C1—C7—N1—N2 | 176.5 (5) | C13—C14—N14—O41 | −1.4 (7) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O42i | 0.86 | 2.29 | 3.117 (7) | 163 |
C16—H16···O41i | 0.93 | 2.44 | 3.330 (7) | 159 |
Symmetry code: (i) x+1, −y+1, z−1/2. |
We report here the molecular and supramolecular structures of the title compounds, (I)–(III), and we compare their supramolecular behaviours with those of the related compounds (IV) and (V), which we reported recently (Glidewell et al., 2003). In no two of these compounds does the interplay of hard and soft hydrogen bonds with the iodo–nitro interactions generate the same pattern of supramolecular aggregation.
The molecules of (I)–(III) are all nearly planar, as shown by the key torsional angles (Tables 1,3 and 5); the sole exception concerns the minor orientation of the iodinated ring in (III). The bond distances and interbond angles present no unusual features and the principal structural interest lies in the intermolecular interactions and their consequences.
Although the isomeric compounds (I) and (II) both crystallize in space group C2/c, they have very different unit-cell dimensions (see Experimental). However, we discuss the supramolecular structures of these two compounds together, as they have a number of features in common.
There are neither iodo–nitro interactions nor aromatic π···π stacking interactions in the structures of (I) and (II), and N—H···π(arene) and C—H···π(arene) hydrogen bonds are also absent from both. Instead, the supramolecular structure of both compounds is determined by a three-centre N—H···(O)2 hydrogen bond, augmented by two-centre C—H···O hydrogen bonds (Tables 2 and 4). While the effect of the three-centre interaction is identical in (I) and (II), the effect of the C—H···O hydrogen bonds is different in the two compounds, and it is this difference that generates their different overall structures. In both compounds, however, the dominant C—H···O hydrogen bond involves the C—H bond that lies between the two nitro groups and which may therefore be expected to be the most acidic C—H bond in the molecule.
In both compounds (Figs. 1 and 2), hydrazone atom N2 acts as a donor in a three-centre hydrogen bond, in which the two acceptors are, firstly, atom O21 in the same molecule at (x, y, z), giving rise to an S(6) motif (Bernstein et al., 1995), and secondly, atom O21 in the molecule at (1 − x, 1 − y, 1 − z), producing a centrosymmetric dimer centred at (1/2, 1/2, 1/2), which contains an unusual sequence of three fused rings with graph-set descriptor S(6)R22(4)S(6) (Fig. 3). In both compounds, these dimeric aggregates are linked into chains by a single C—H···O hydrogen bond, but in (I), the chain is generated by translation, while in (II) it is generated by the action of a twofold rotation axis.
In (I), atom C13 in the molecule at (x, y, z), which is a component of the dimer centred at (1/2, 1/2, 1/2), acts as hydrogen-bond donor to nitro atom O41 in the molecule at (1 − x, −2 − y, 1 − z), which is a component of the dimer centred at (1/2, 1.5, 1/2), so forming an R22(10) motif (Fig. 3). Propagation of this single interaction by inversion and translation then generates a chain of rings running parallel to the [010] direction. This chain is further reinforced, albeit rather weakly, by a second C—H···O hydrogen bond, in which atom C5 at (x, y, z) acts as a donor to nitro atom O42 in the molecule at (x, −1 + y, z), which is a component of the dimer centred at (1/2, −0.5, 1/2), so completing the formation of a continuous chain of edge-fused rings containing four different types of ring, namely S(6), R22(4), R22(10) and R33(16) (Fig. 3). This nearly-planar structure can alternatively be regarded as a multiply perforated ribbon.
In (II), by contrast, atom C13 in the molecule at (x, y, z), itself a component of the R22(4) dimer centred at (1/2, 1/2, 1/2), acts as a hydrogen-bond donor to nitro atom O41 in the molecule at (1 − x, y, 0.5 − z), which is a component of the dimer centred at (1/2, 1/2, 0). In turn, atom C13 at (1 − x, y, 0.5 − z) acts as a donor to atom O4 at (x, y, z), so that the R22(10) motif in this compound is generated by the twofold rotation axis along (1/2, y, 1/4). Propagation of this single C—H···O hydrogen bond then generates, by rotation and inversion, a deeply folded chain of rings running parallel to the [001] direction and containing three distinct types of ring (Fig. 4). The iodophenyl ring plays no part in the supramolecular aggregation.
The supramolecular structures of (I) and (II) (Figs 3 and 4) may be contrasted with that of the isomeric 2-iodobenzaldehyde-2,4-dinitrophenylhydrazone, (IV) (Glidewell et al., 2003). In the crystal structure of (IV), the whole molecule is disordered over two sets of sites; for the major orientation, there are no direction-specific interactions between the molecules, while for the minor orientation, a single C—H···O hydrogen bond generates centrosymmetric R22(10) dimers. As in (I) and (II), it is the C—H bond between the two nitro groups that is involved.
In (III), the molecules (Fig. 5) are linked into a zigzag chain of rings by means of a cooperative combination of N—H···O and C—H···O hydrogen bonds (Table 6). Hydrazone atom N2 and aryl atom C16 in the molecule at (x, y, z) act as hydrogen-bond donors to nitro atoms O42 and O41, respectively, in the molecule at (1 + x, 1 − y, −0.5 + z), so producing a C(6) C(8)[R22(8)] chain of rings running parallel to the [20–1] direction and generated by the c-glide plane at y = 0.5 (Fig. 6). A second such chain, related to the first by the C-centring operation, is generated by the c-glide plane at y = 0, but there are neither X—H···π(arene) hydrogen bonds (X = C or N) nor aromatic π···π stacking interactions between or within the chains.
There are, however, two long two-centre iodo–nitro interactions between the molecules. Atom I4 in the molecule at (x, y, z) makes contacts with nitro atom O41 in the molecule at (1.5 + x, 0.5 − y, −0.5 + z) [I···O = 3.537 (4) Å and C—I···O = 142.9 (2)°], and with nitro atom O42 in the molecule at (1.5 + x, −0.5 + y, z) [I···O = 3.525 (4) Å and C—I···O = 140.4 (2)°]. If these two interactions are regarded as structurally significant then it is a straightforward matter to show that they generate a continuous three-dimensional structure, independent of the contribution of the hydrogen bonding. The two I···O interactions individually generate C(14) chains (Starbuck et al., 1999) running parallel to the [30–1] and [3–10] directions, respectively (Fig. 7). In addition, the action of the glide planes generates chains running parallel to the [310] direction. Finally, the combination of the two interactions together generates a chain running parallel to the [010] direction (Fig. C3). Atom I4 in the molecule at (1.5 + x, 0.5 − y, −0.5 + z) makes an I···O contact with atom O42 at (3 + x, 1 − y, −0.5 + z), while atom O41 in this molecule at (3 + x, 1 − y, −0.5 + z) makes an I···O contact with atom I4 in the molecule at (1.5 + x, 0.5 + y, z), which is in turn directly linked to the molecule at (x, 1 + y, z), so generating a C22(28) chain parallel to [010] (Fig. 7). The combination of the [10], [310], [31–0] and [30–1] iodo–nitro chains is sufficient to generate a three-dimensional framework.
In 2-iodobenzaldehyde-4-nitrophenylhydrazone, (V) (Glidewell et al., 2003), an isomer of (III), a combination of an N—H···O hydrogen bond and a single two-centre iodo–nitro interaction link the molecules into a chain of edge-fused R33(18) rings. It is unfortunate that we cannot discuss here the supramolecular structure of the further isomer 3-iodobenzaldehyde-4-nitrophenylhydrazone, but repeated attempts to prepare this compound in pure crystalline form have been unsuccessful.