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The title compounds, 4-hydroxy-5-oxo-1,3,6-cycloheptatriene-1-carbonitrile, C
8H
5NO
2, (I), and 2-hydroxy-5-nitro-2,4,6-cycloheptatrien-1-one, C
7H
5NO
4, (II), have intra- and intermolecular hydrogen bonds. The structure of (II) contains two crystallographically independent molecules, (II
a) and (II
b). An intermolecular π–π interaction and an intermolecular NO
2π–π interaction are present in (I) and (II), respectively.
Supporting information
CCDC references: 164666; 164667
Compound (I) was synthesized by diazotization and cyanidation of
5-aminotropolone (Cook et al., 1954). Compound (II) was synthesized by
the nitration of tropolone (Doering & Knox, 1951). The single crystals of (I)
and (II) were obtained by recrystallization from chloroform.
All H atoms were located at ideal positions with C—H 0.93 Å and O—H 0.82 Å, and restrained with Uiso held fixed to 1.2 times Ueq of
the parent atoms.
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990). Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for (I); SIR97 (Altomare et al., 1997) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal_GX (Hall & du Boulay, 1995); software used to prepare material for publication: SHELXL97.
Crystal data top
C8H5NO2 | Z = 2 |
Mr = 147.13 | F(000) = 152 |
Triclinic, P1 | Dx = 1.443 Mg m−3 |
a = 7.1995 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.6309 (14) Å | Cell parameters from 25 reflections |
c = 3.7913 (3) Å | θ = 6.8–18.4° |
α = 90.805 (9)° | µ = 0.11 mm−1 |
β = 99.905 (7)° | T = 296 K |
γ = 94.116 (8)° | Prism, yellow |
V = 338.63 (5) Å3 | 0.53 × 0.30 × 0.13 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | 1311 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.011 |
Graphite monochromator | θmax = 28.0°, θmin = 2.9° |
ω–2θ scans | h = −9→9 |
Absorption correction: ψ via ψ scans (North et al.,, 1968) | k = −16→16 |
Tmin = 0.918, Tmax = 0.986 | l = −4→0 |
1854 measured reflections | 3 standard reflections every 120 min |
1611 independent reflections | intensity decay: 2.2% |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0569P)2 + 0.060P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1611 reflections | Δρmax = 0.28 e Å−3 |
102 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.120 (17) |
Crystal data top
C8H5NO2 | γ = 94.116 (8)° |
Mr = 147.13 | V = 338.63 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.1995 (5) Å | Mo Kα radiation |
b = 12.6309 (14) Å | µ = 0.11 mm−1 |
c = 3.7913 (3) Å | T = 296 K |
α = 90.805 (9)° | 0.53 × 0.30 × 0.13 mm |
β = 99.905 (7)° | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 1311 reflections with I > 2σ(I) |
Absorption correction: ψ via ψ scans (North et al.,, 1968) | Rint = 0.011 |
Tmin = 0.918, Tmax = 0.986 | 3 standard reflections every 120 min |
1854 measured reflections | intensity decay: 2.2% |
1611 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.28 e Å−3 |
1611 reflections | Δρmin = −0.14 e Å−3 |
102 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 1.2110 (2) | 0.06845 (11) | 1.4031 (4) | 0.0607 (4) | |
O1 | 0.70738 (14) | 0.46957 (8) | 0.5649 (3) | 0.0525 (3) | |
O2 | 0.43186 (13) | 0.34112 (8) | 0.6722 (3) | 0.0542 (3) | |
H2 | 0.4400 | 0.4019 | 0.6006 | 0.081* | |
C1 | 0.75720 (17) | 0.38706 (9) | 0.7189 (3) | 0.0351 (3) | |
C2 | 0.60469 (17) | 0.30987 (10) | 0.7836 (3) | 0.0369 (3) | |
C3 | 0.61546 (18) | 0.21179 (10) | 0.9332 (4) | 0.0408 (3) | |
H3 | 0.4995 | 0.1752 | 0.9410 | 0.049* | |
C4 | 0.77349 (18) | 0.15816 (10) | 1.0760 (3) | 0.0387 (3) | |
H4 | 0.7480 | 0.0913 | 1.1638 | 0.046* | |
C5 | 0.96163 (17) | 0.19141 (9) | 1.1035 (3) | 0.0356 (3) | |
C6 | 1.04004 (17) | 0.28809 (10) | 0.9865 (3) | 0.0371 (3) | |
H6 | 1.1714 | 0.2966 | 1.0311 | 0.045* | |
C7 | 0.95330 (17) | 0.37035 (9) | 0.8195 (3) | 0.0360 (3) | |
H7 | 1.0353 | 0.4249 | 0.7607 | 0.043* | |
C8 | 1.0987 (2) | 0.12109 (10) | 1.2707 (4) | 0.0433 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0551 (8) | 0.0517 (7) | 0.0737 (9) | 0.0164 (6) | 0.0007 (7) | 0.0174 (6) |
O1 | 0.0404 (5) | 0.0425 (5) | 0.0751 (7) | 0.0076 (4) | 0.0079 (5) | 0.0263 (5) |
O2 | 0.0307 (5) | 0.0480 (6) | 0.0839 (8) | 0.0057 (4) | 0.0069 (5) | 0.0267 (5) |
C1 | 0.0350 (6) | 0.0323 (6) | 0.0383 (6) | 0.0032 (4) | 0.0065 (5) | 0.0076 (4) |
C2 | 0.0313 (6) | 0.0382 (6) | 0.0414 (7) | 0.0040 (5) | 0.0061 (5) | 0.0078 (5) |
C3 | 0.0348 (6) | 0.0372 (6) | 0.0503 (7) | −0.0011 (5) | 0.0079 (5) | 0.0102 (5) |
C4 | 0.0438 (7) | 0.0311 (6) | 0.0414 (7) | 0.0030 (5) | 0.0077 (5) | 0.0080 (5) |
C5 | 0.0395 (6) | 0.0333 (6) | 0.0345 (6) | 0.0084 (5) | 0.0049 (5) | 0.0046 (4) |
C6 | 0.0303 (5) | 0.0392 (6) | 0.0417 (7) | 0.0037 (4) | 0.0048 (5) | 0.0047 (5) |
C7 | 0.0325 (6) | 0.0337 (6) | 0.0418 (7) | −0.0002 (4) | 0.0071 (5) | 0.0068 (5) |
C8 | 0.0454 (7) | 0.0377 (6) | 0.0466 (7) | 0.0079 (5) | 0.0052 (6) | 0.0085 (5) |
Geometric parameters (Å, º) top
N1—C8 | 1.1377 (18) | C3—H3 | 0.9300 |
O1—C1 | 1.2468 (14) | C4—C5 | 1.3750 (18) |
O2—C2 | 1.3330 (15) | C4—H4 | 0.9300 |
O2—H2 | 0.8200 | C5—C6 | 1.4175 (17) |
C1—C7 | 1.4294 (17) | C5—C8 | 1.4461 (16) |
C1—C2 | 1.4704 (16) | C6—C7 | 1.3588 (17) |
C2—C3 | 1.3716 (17) | C6—H6 | 0.9300 |
C3—C4 | 1.3984 (18) | C7—H7 | 0.9300 |
| | | |
C2—O2—H2 | 109.5 | C3—C4—H4 | 115.8 |
O1—C1—C7 | 120.41 (11) | C4—C5—C6 | 127.61 (11) |
O1—C1—C2 | 116.39 (11) | C4—C5—C8 | 117.53 (11) |
C7—C1—C2 | 123.19 (10) | C6—C5—C8 | 114.85 (11) |
O2—C2—C3 | 116.69 (11) | C7—C6—C5 | 130.11 (12) |
O2—C2—C1 | 113.70 (10) | C7—C6—H6 | 114.9 |
C3—C2—C1 | 129.60 (11) | C5—C6—H6 | 114.9 |
C2—C3—C4 | 130.12 (12) | C6—C7—C1 | 130.84 (11) |
C2—C3—H3 | 114.9 | C6—C7—H7 | 114.6 |
C4—C3—H3 | 114.9 | C1—C7—H7 | 114.6 |
C5—C4—C3 | 128.47 (11) | N1—C8—C5 | 177.77 (15) |
C5—C4—H4 | 115.8 | | |
| | | |
O1—C1—C2—O2 | −1.32 (18) | C3—C4—C5—C8 | 178.70 (13) |
C7—C1—C2—O2 | 179.44 (12) | C4—C5—C6—C7 | −0.6 (2) |
O1—C1—C2—C3 | 177.41 (14) | C8—C5—C6—C7 | 179.49 (13) |
C7—C1—C2—C3 | −1.8 (2) | C5—C6—C7—C1 | 2.2 (2) |
O2—C2—C3—C4 | −179.31 (14) | O1—C1—C7—C6 | −179.95 (13) |
C1—C2—C3—C4 | 2.0 (3) | C2—C1—C7—C6 | −0.7 (2) |
C2—C3—C4—C5 | 0.3 (2) | C4—C5—C8—N1 | −166 (4) |
C3—C4—C5—C6 | −1.2 (2) | C6—C5—C8—N1 | 14 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 2.05 | 2.761 (2) | 145 |
O2—H2···O1 | 0.82 | 2.08 | 2.563 (2) | 118 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Crystal data top
C7H5NO4 | Z = 4 |
Mr = 167.12 | F(000) = 344 |
Triclinic, P1 | Dx = 1.617 Mg m−3 |
a = 7.5701 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.496 (3) Å | Cell parameters from 25 reflections |
c = 6.4945 (7) Å | θ = 10.8–18.3° |
α = 90.751 (14)° | µ = 0.14 mm−1 |
β = 104.796 (8)° | T = 296 K |
γ = 94.410 (13)° | Prism, yellow |
V = 686.7 (2) Å3 | 0.40 × 0.30 × 0.23 mm |
Data collection top
Enraf-Nonius CAD4 diffractometer | 2493 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.009 |
Graphite monochromator | θmax = 28.0°, θmin = 2.8° |
ω–2θ scans | h = −9→9 |
Absorption correction: ψ via ψ scans (North et al., 1968) | k = −19→0 |
Tmin = 0.914, Tmax = 0.969 | l = −8→8 |
3438 measured reflections | 3 standard reflections every 120 min |
3309 independent reflections | intensity decay: 0.5% |
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0603P)2 + 0.1579P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3309 reflections | Δρmax = 0.29 e Å−3 |
220 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.141 (9) |
Crystal data top
C7H5NO4 | γ = 94.410 (13)° |
Mr = 167.12 | V = 686.7 (2) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.5701 (10) Å | Mo Kα radiation |
b = 14.496 (3) Å | µ = 0.14 mm−1 |
c = 6.4945 (7) Å | T = 296 K |
α = 90.751 (14)° | 0.40 × 0.30 × 0.23 mm |
β = 104.796 (8)° | |
Data collection top
Enraf-Nonius CAD4 diffractometer | 2493 reflections with I > 2σ(I) |
Absorption correction: ψ via ψ scans (North et al., 1968) | Rint = 0.009 |
Tmin = 0.914, Tmax = 0.969 | 3 standard reflections every 120 min |
3438 measured reflections | intensity decay: 0.5% |
3309 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.29 e Å−3 |
3309 reflections | Δρmin = −0.18 e Å−3 |
220 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | −0.25178 (18) | 0.30941 (10) | 0.1946 (2) | 0.0470 (3) | |
O1 | 0.28301 (16) | 0.47812 (9) | 0.94339 (18) | 0.0542 (3) | |
O2 | 0.48839 (15) | 0.43210 (10) | 0.70233 (19) | 0.0569 (3) | |
H2 | 0.5094 | 0.4555 | 0.8227 | 0.085* | |
O3 | −0.23379 (19) | 0.28045 (13) | 0.0255 (2) | 0.0798 (5) | |
O4 | −0.40023 (17) | 0.31145 (12) | 0.2321 (2) | 0.0768 (5) | |
C1 | 0.1988 (2) | 0.43735 (10) | 0.7734 (2) | 0.0379 (3) | |
C2 | 0.30936 (19) | 0.41137 (11) | 0.6274 (2) | 0.0390 (3) | |
C3 | 0.2522 (2) | 0.37069 (11) | 0.4275 (2) | 0.0408 (3) | |
H3 | 0.3455 | 0.3612 | 0.3620 | 0.049* | |
C4 | 0.0752 (2) | 0.34116 (10) | 0.3061 (2) | 0.0380 (3) | |
H4 | 0.0671 | 0.3158 | 0.1714 | 0.046* | |
C5 | −0.08634 (19) | 0.34488 (10) | 0.3604 (2) | 0.0358 (3) | |
C6 | −0.1194 (2) | 0.37814 (10) | 0.5509 (2) | 0.0390 (3) | |
H6 | −0.2410 | 0.3724 | 0.5577 | 0.047* | |
C7 | 0.0037 (2) | 0.41758 (11) | 0.7260 (2) | 0.0396 (3) | |
H7 | −0.0479 | 0.4349 | 0.8347 | 0.048* | |
N11 | 0.13714 (17) | 0.18383 (9) | 0.7945 (2) | 0.0407 (3) | |
O11 | 0.31610 (16) | 0.02160 (9) | 0.05243 (17) | 0.0510 (3) | |
O12 | 0.63329 (15) | 0.08343 (10) | 0.28423 (19) | 0.0543 (3) | |
H12 | 0.5973 | 0.0556 | 0.1685 | 0.081* | |
O13 | −0.02239 (17) | 0.15694 (10) | 0.7807 (2) | 0.0636 (4) | |
O14 | 0.22838 (18) | 0.23618 (9) | 0.9379 (2) | 0.0575 (4) | |
C11 | 0.31226 (19) | 0.06151 (10) | 0.2222 (2) | 0.0369 (3) | |
C12 | 0.49053 (19) | 0.09777 (11) | 0.3617 (2) | 0.0388 (3) | |
C13 | 0.52839 (19) | 0.14325 (11) | 0.5555 (2) | 0.0426 (4) | |
H13 | 0.6519 | 0.1609 | 0.6151 | 0.051* | |
C14 | 0.4102 (2) | 0.16753 (10) | 0.6789 (2) | 0.0387 (3) | |
H14 | 0.4652 | 0.1985 | 0.8084 | 0.046* | |
C15 | 0.22434 (19) | 0.15096 (9) | 0.6306 (2) | 0.0338 (3) | |
C16 | 0.10273 (18) | 0.10841 (10) | 0.4486 (2) | 0.0368 (3) | |
H16 | −0.0207 | 0.1052 | 0.4476 | 0.044* | |
C17 | 0.14100 (19) | 0.07114 (11) | 0.2729 (2) | 0.0396 (3) | |
H17 | 0.0384 | 0.0480 | 0.1678 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0367 (7) | 0.0564 (8) | 0.0448 (7) | −0.0021 (6) | 0.0076 (6) | −0.0126 (6) |
O1 | 0.0455 (6) | 0.0709 (8) | 0.0417 (6) | 0.0002 (5) | 0.0053 (5) | −0.0168 (5) |
O2 | 0.0321 (6) | 0.0888 (9) | 0.0468 (7) | 0.0026 (6) | 0.0064 (5) | −0.0165 (6) |
O3 | 0.0514 (8) | 0.1265 (13) | 0.0560 (8) | −0.0107 (8) | 0.0112 (6) | −0.0454 (8) |
O4 | 0.0333 (6) | 0.1205 (13) | 0.0739 (9) | −0.0065 (7) | 0.0144 (6) | −0.0332 (9) |
C1 | 0.0394 (7) | 0.0410 (8) | 0.0325 (7) | 0.0047 (6) | 0.0078 (6) | −0.0023 (6) |
C2 | 0.0293 (6) | 0.0474 (8) | 0.0404 (8) | 0.0061 (6) | 0.0082 (6) | 0.0004 (6) |
C3 | 0.0324 (7) | 0.0537 (9) | 0.0396 (7) | 0.0088 (6) | 0.0137 (6) | −0.0049 (6) |
C4 | 0.0374 (7) | 0.0443 (8) | 0.0336 (7) | 0.0064 (6) | 0.0109 (6) | −0.0069 (6) |
C5 | 0.0320 (7) | 0.0383 (7) | 0.0360 (7) | 0.0022 (5) | 0.0072 (5) | −0.0049 (6) |
C6 | 0.0332 (7) | 0.0464 (8) | 0.0402 (7) | 0.0033 (6) | 0.0149 (6) | −0.0038 (6) |
C7 | 0.0391 (7) | 0.0476 (8) | 0.0354 (7) | 0.0041 (6) | 0.0156 (6) | −0.0050 (6) |
N11 | 0.0404 (7) | 0.0466 (7) | 0.0370 (6) | 0.0103 (5) | 0.0118 (5) | −0.0059 (5) |
O11 | 0.0456 (6) | 0.0713 (8) | 0.0372 (6) | 0.0120 (5) | 0.0111 (5) | −0.0135 (5) |
O12 | 0.0345 (6) | 0.0798 (9) | 0.0508 (7) | 0.0045 (5) | 0.0162 (5) | −0.0179 (6) |
O13 | 0.0396 (6) | 0.0951 (10) | 0.0600 (8) | 0.0035 (6) | 0.0219 (6) | −0.0199 (7) |
O14 | 0.0568 (7) | 0.0658 (8) | 0.0497 (7) | 0.0027 (6) | 0.0154 (6) | −0.0263 (6) |
C11 | 0.0353 (7) | 0.0445 (8) | 0.0307 (7) | 0.0068 (6) | 0.0073 (5) | −0.0025 (6) |
C12 | 0.0303 (7) | 0.0471 (8) | 0.0407 (7) | 0.0060 (6) | 0.0116 (6) | −0.0010 (6) |
C13 | 0.0271 (6) | 0.0548 (9) | 0.0433 (8) | 0.0005 (6) | 0.0055 (6) | −0.0089 (7) |
C14 | 0.0345 (7) | 0.0454 (8) | 0.0336 (7) | 0.0022 (6) | 0.0050 (5) | −0.0083 (6) |
C15 | 0.0338 (7) | 0.0366 (7) | 0.0323 (7) | 0.0055 (5) | 0.0101 (5) | −0.0035 (5) |
C16 | 0.0275 (6) | 0.0453 (8) | 0.0372 (7) | 0.0034 (5) | 0.0079 (5) | −0.0044 (6) |
C17 | 0.0310 (7) | 0.0512 (8) | 0.0336 (7) | 0.0011 (6) | 0.0040 (5) | −0.0089 (6) |
Geometric parameters (Å, º) top
N1—O4 | 1.2117 (18) | N11—O13 | 1.2205 (17) |
N1—O3 | 1.2139 (18) | N11—O14 | 1.2220 (17) |
N1—C5 | 1.4800 (19) | N11—C15 | 1.4796 (17) |
O1—C1 | 1.2411 (17) | O11—C11 | 1.2463 (17) |
O2—C2 | 1.3268 (18) | O12—C12 | 1.3317 (17) |
O2—H2 | 0.8200 | O12—H12 | 0.8200 |
C1—C7 | 1.435 (2) | C11—C17 | 1.433 (2) |
C1—C2 | 1.478 (2) | C11—C12 | 1.474 (2) |
C2—C3 | 1.370 (2) | C12—C13 | 1.366 (2) |
C3—C4 | 1.401 (2) | C13—C14 | 1.405 (2) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.361 (2) | C14—C15 | 1.3626 (19) |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.4096 (19) | C15—C16 | 1.4012 (19) |
C6—C7 | 1.359 (2) | C16—C17 | 1.3620 (19) |
C6—H6 | 0.9300 | C16—H16 | 0.9300 |
C7—H7 | 0.9300 | C17—H17 | 0.9300 |
| | | |
O4—N1—O3 | 122.57 (14) | O13—N11—O14 | 123.05 (13) |
O4—N1—C5 | 118.62 (13) | O13—N11—C15 | 118.43 (12) |
O3—N1—C5 | 118.81 (13) | O14—N11—C15 | 118.52 (13) |
C2—O2—H2 | 109.5 | C12—O12—H12 | 109.5 |
O1—C1—C7 | 120.24 (13) | O11—C11—C17 | 120.36 (13) |
O1—C1—C2 | 116.69 (14) | O11—C11—C12 | 116.42 (13) |
C7—C1—C2 | 123.07 (13) | C17—C11—C12 | 123.22 (12) |
O2—C2—C3 | 116.53 (13) | O12—C12—C13 | 116.56 (13) |
O2—C2—C1 | 114.40 (13) | O12—C12—C11 | 114.07 (13) |
C3—C2—C1 | 129.06 (13) | C13—C12—C11 | 129.37 (13) |
C2—C3—C4 | 130.09 (13) | C12—C13—C14 | 130.18 (14) |
C2—C3—H3 | 115.0 | C12—C13—H13 | 114.9 |
C4—C3—H3 | 115.0 | C14—C13—H13 | 114.9 |
C5—C4—C3 | 128.22 (13) | C15—C14—C13 | 127.50 (14) |
C5—C4—H4 | 115.9 | C15—C14—H14 | 116.3 |
C3—C4—H4 | 115.9 | C13—C14—H14 | 116.3 |
C4—C5—C6 | 129.51 (13) | C14—C15—C16 | 129.92 (13) |
C4—C5—N1 | 115.29 (13) | C14—C15—N11 | 115.11 (12) |
C6—C5—N1 | 115.20 (12) | C16—C15—N11 | 114.97 (12) |
C7—C6—C5 | 128.31 (14) | C17—C16—C15 | 128.69 (13) |
C7—C6—H6 | 115.8 | C17—C16—H16 | 115.7 |
C5—C6—H6 | 115.8 | C15—C16—H16 | 115.7 |
C6—C7—C1 | 131.63 (13) | C16—C17—C11 | 131.05 (13) |
C6—C7—H7 | 114.2 | C16—C17—H17 | 114.5 |
C1—C7—H7 | 114.2 | C11—C17—H17 | 114.5 |
| | | |
O1—C1—C2—O2 | 2.6 (2) | O11—C11—C12—O12 | 0.7 (2) |
C7—C1—C2—O2 | −177.42 (15) | C17—C11—C12—O12 | −178.70 (14) |
O1—C1—C2—C3 | −176.34 (16) | O11—C11—C12—C13 | −179.38 (16) |
C7—C1—C2—C3 | 3.6 (3) | C17—C11—C12—C13 | 1.2 (3) |
O2—C2—C3—C4 | −179.91 (16) | O12—C12—C13—C14 | −179.17 (17) |
C1—C2—C3—C4 | −1.0 (3) | C11—C12—C13—C14 | 0.9 (3) |
C2—C3—C4—C5 | −0.9 (3) | C12—C13—C14—C15 | −0.4 (3) |
C3—C4—C5—C6 | −0.6 (3) | C13—C14—C15—C16 | −1.6 (3) |
C3—C4—C5—N1 | 178.94 (15) | C13—C14—C15—N11 | 179.16 (15) |
O4—N1—C5—C4 | −179.41 (16) | O13—N11—C15—C14 | −166.88 (15) |
O3—N1—C5—C4 | −0.3 (2) | O14—N11—C15—C14 | 12.7 (2) |
O4—N1—C5—C6 | 0.2 (2) | O13—N11—C15—C16 | 13.8 (2) |
O3—N1—C5—C6 | 179.31 (16) | O14—N11—C15—C16 | −166.65 (14) |
C4—C5—C6—C7 | 2.2 (3) | C14—C15—C16—C17 | 1.1 (3) |
N1—C5—C6—C7 | −177.32 (15) | N11—C15—C16—C17 | −179.65 (15) |
C5—C6—C7—C1 | −0.2 (3) | C15—C16—C17—C11 | 1.9 (3) |
O1—C1—C7—C6 | 176.81 (16) | O11—C11—C17—C16 | 177.43 (16) |
C2—C1—C7—C6 | −3.1 (3) | C12—C11—C17—C16 | −3.2 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 2.05 | 2.743 (2) | 142 |
O2—H2···O1 | 0.82 | 2.10 | 2.586 (2) | 117 |
O12—H12···O11ii | 0.82 | 2.07 | 2.771 (2) | 143 |
O12—H12···O11 | 0.82 | 2.09 | 2.573 (2) | 118 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C8H5NO2 | C7H5NO4 |
Mr | 147.13 | 167.12 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 7.1995 (5), 12.6309 (14), 3.7913 (3) | 7.5701 (10), 14.496 (3), 6.4945 (7) |
α, β, γ (°) | 90.805 (9), 99.905 (7), 94.116 (8) | 90.751 (14), 104.796 (8), 94.410 (13) |
V (Å3) | 338.63 (5) | 686.7 (2) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.14 |
Crystal size (mm) | 0.53 × 0.30 × 0.13 | 0.40 × 0.30 × 0.23 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD4 diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | ψ via ψ scans (North et al.,, 1968) | ψ via ψ scans (North et al., 1968) |
Tmin, Tmax | 0.918, 0.986 | 0.914, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1854, 1611, 1311 | 3438, 3309, 2493 |
Rint | 0.011 | 0.009 |
(sin θ/λ)max (Å−1) | 0.660 | 0.660 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.106, 1.03 | 0.039, 0.119, 1.03 |
No. of reflections | 1611 | 3309 |
No. of parameters | 102 | 220 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.14 | 0.29, −0.18 |
Selected bond lengths (Å) for (I) topN1—C8 | 1.1377 (18) | C3—C4 | 1.3984 (18) |
O1—C1 | 1.2468 (14) | C4—C5 | 1.3750 (18) |
O2—C2 | 1.3330 (15) | C5—C6 | 1.4175 (17) |
C1—C7 | 1.4294 (17) | C5—C8 | 1.4461 (16) |
C1—C2 | 1.4704 (16) | C6—C7 | 1.3588 (17) |
C2—C3 | 1.3716 (17) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 2.05 | 2.761 (2) | 145 |
O2—H2···O1 | 0.82 | 2.08 | 2.563 (2) | 118 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Selected bond lengths (Å) for (II) topN1—O4 | 1.2117 (18) | N11—O13 | 1.2205 (17) |
N1—O3 | 1.2139 (18) | N11—O14 | 1.2220 (17) |
N1—C5 | 1.4800 (19) | N11—C15 | 1.4796 (17) |
O1—C1 | 1.2411 (17) | O11—C11 | 1.2463 (17) |
O2—C2 | 1.3268 (18) | O12—C12 | 1.3317 (17) |
C1—C7 | 1.435 (2) | C11—C17 | 1.433 (2) |
C1—C2 | 1.478 (2) | C11—C12 | 1.474 (2) |
C2—C3 | 1.370 (2) | C12—C13 | 1.366 (2) |
C3—C4 | 1.401 (2) | C13—C14 | 1.405 (2) |
C4—C5 | 1.361 (2) | C14—C15 | 1.3626 (19) |
C5—C6 | 1.4096 (19) | C15—C16 | 1.4012 (19) |
C6—C7 | 1.359 (2) | C16—C17 | 1.3620 (19) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 2.05 | 2.743 (2) | 142 |
O2—H2···O1 | 0.82 | 2.10 | 2.586 (2) | 117 |
O12—H12···O11ii | 0.82 | 2.07 | 2.771 (2) | 143 |
O12—H12···O11 | 0.82 | 2.09 | 2.573 (2) | 118 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z. |
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Troponoids have been an important building block for constructing liquid crystals (Mori et al., 1992; Mori & Takeshita, 1995), ionophores (Mori et al., 1996; Kubo et al., 1999) and dyes (Takeshita et al., 1989; Mori et al., 1993). The troponoid moiety plays an important role to generate new properties in molecular assemblies. Recently, we have prepared liquid crystals with a tropolone core such as 5-hydroxy- (Mori & Takeshita, 1995), 5-phenyl- (Mori et al., 1992), 5-nitro- and 5-cyanotropolones (Hashimoto et al., 2000). The cores enhanced formation of smectic phases when compared with the corresponding benzenoids. The crystal structure analyses of tropolone (Shimanouchi & Sasada, 1973) and of metal complexes such as copper (Berg et al., 1978) and iron (Hamor & Watkin, 1969) tropolones have been carried out. However, the crystal structures of 5-hydroxy-, 5-phenyl-, 5-nitro- and 5-cyanotropolone have not been elucidated. We now report the structures of 5-cyano- and 5-nitrotropolone, (I) and (II), with the aim of contributing to a deeper understanding of troponoids and molecular assemblies. \sch
The structure of (II) contains two crystallographically independent molecules, (IIa) and (IIb), related by a non-crystallographic screw axis in the a axis direction located at x, 1/4, 1/2. The planarities of (I) and (II) are fairly good; the deviations of atoms from the least-squares plane of (I), (IIa), and (IIb) are within 0.03 (1), 0.07 (2) and and 0.23 (2) Å for (IIb), respectively. The C—C bond-length patterns of the seven-membered ring of (I), (IIa), and (IIb) are similar to those of tropolone (Shimanouchi & Sasada, 1973).
Compounds (I) and (II) form hydrogen-bonded dimers about inversion centres, in which the OH group and an intermolecular component, carbonyl oxygen O1 being the acceptor in both cases. These bonds are tabulated in Tables 2 and 4, and illustrated in Figs. 3 and 4. The distances are close to that [2.746 Å] of tropolone. Intermolecular π—π interactions between the tropolone dimer planes (head-to-head) of (I) and between the tropolone dimer planes (head-to-tail) of (II) are observed. The distances between intermolecular tropolone planes are 3.791 (5) Å for C1—C1iv (iv: x, y, z - 1) of (I) and 3.399 (2) Å for C1—C5v (v: -x, 1 - y, 1 - z) of (II), respectively, which are within the range associated with π—π interaction (3.3–3.8 Å). The value is similar to that (3.715 Å) of the intermolecular C1—C3vi (vi: 1 + x, 1/2 - y, 1/2 + z) of tropolone (Shimanouchi & Sasada, 1973) and the type of π—π packing of (I) and (II) are distinct from that of tropolone (Shimanouchi & Sasada, 1973).
Compound (II) has two independent molecules in the lattice. Furthermore, intermolecular interaction between a nitro group and a seven-membered ring of (II) is observed. The distances between a nitro group and a seven-membered ring are 3.611 (2) Å for C7—N11 3.602 (2) Å for C6—O13 3.123 (2) Å for C1—O14, respectively. Thus, the substituent at C-5 differentiated the crystal packing in the lattice.