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We report the structure of the title compound, C12H12Cl3NO2, which belongs to a group of compounds called blue quinones. It is a remarkable near-IR dye with interest for non-linear optics. It crystallized in monoclinic space group P21/a with one molecule in the asymmetric unit. The molecular structure is approximately planar and exhibits little bond-length alternation, indicating a high degree of charge-transfer from the amine lone pair to the quinone.
Supporting information
CCDC reference: 182611
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- R factor = 0.026
- wR factor = 0.029
- Data-to-parameter ratio = 10.3
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Blue crystals were grown by layered addition of methanol to a toluene solution
of the compound. All non-H atoms were refined anisotropically and H atoms were
refined isotropically.
H atoms were refined isotropically
Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1996); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin et al., 2001); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CRYSTALS (Watkin et al., 2001).
2,3,5-Trichloro-6-(2-diethylaminovinyl)-1,4-benzoquinone
top
Crystal data top
C12H12Cl3NO2 | Dx = 1.562 Mg m−3 |
Mr = 308.59 | Melting point: not measured K |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6548 (2) Å | Cell parameters from 3052 reflections |
b = 15.7782 (4) Å | θ = 1–27° |
c = 10.9114 (4) Å | µ = 0.69 mm−1 |
β = 95.299 (1)° | T = 150 K |
V = 1312.23 (7) Å3 | Plate, blue |
Z = 4 | 0.10 × 0.05 × 0.05 mm |
F(000) = 633.702 | |
Data collection top
Enraf-Nonius KappaCCD diffractometer | 2055 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.01 |
ω scans | θmax = 27.4°, θmin = 4.3° |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1996) | h = −9→9 |
Tmin = 0.959, Tmax = 0.966 | k = −20→20 |
5779 measured reflections | l = −14→14 |
2985 independent reflections | |
Refinement top
Refinement on F | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | All H-atom parameters refined |
wR(F2) = 0.029 | Chebychev polynomial with 3 parameters,
0.365, 0.183, 0.148 (Carruthers & Watkin, 1979) |
S = 1.02 | (Δ/σ)max = 0.001 |
2055 reflections | Δρmax = 0.23 e Å−3 |
199 parameters | Δρmin = −0.26 e Å−3 |
Crystal data top
C12H12Cl3NO2 | V = 1312.23 (7) Å3 |
Mr = 308.59 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 7.6548 (2) Å | µ = 0.69 mm−1 |
b = 15.7782 (4) Å | T = 150 K |
c = 10.9114 (4) Å | 0.10 × 0.05 × 0.05 mm |
β = 95.299 (1)° | |
Data collection top
Enraf-Nonius KappaCCD diffractometer | 2985 independent reflections |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1996) | 2055 reflections with I > 3σ(I) |
Tmin = 0.959, Tmax = 0.966 | Rint = 0.01 |
5779 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 199 parameters |
wR(F2) = 0.029 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.23 e Å−3 |
2055 reflections | Δρmin = −0.26 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl2 | 0.82940 (7) | 0.46506 (3) | 0.08447 (4) | 0.0295 | |
C3 | 0.8234 (2) | 0.36178 (11) | 0.13245 (16) | 0.0193 | |
C4 | 0.7500 (2) | 0.34790 (11) | 0.25361 (15) | 0.0197 | |
O2 | 0.71218 (17) | 0.40966 (8) | 0.31534 (12) | 0.0257 | |
C5 | 0.7306 (2) | 0.26119 (11) | 0.28865 (15) | 0.0187 | |
Cl3 | 0.64567 (6) | 0.24705 (3) | 0.42957 (4) | 0.0227 | |
C6 | 0.7878 (2) | 0.1910 (1) | 0.22649 (15) | 0.0181 | |
C1 | 0.8691 (2) | 0.20800 (11) | 0.10793 (15) | 0.0190 | |
C2 | 0.8828 (2) | 0.29779 (11) | 0.06790 (16) | 0.0203 | |
Cl1 | 0.97748 (6) | 0.31317 (3) | −0.06730 (4) | 0.0277 | |
O1 | 0.91961 (19) | 0.15164 (8) | 0.04343 (12) | 0.0287 | |
C7 | 0.7769 (2) | 0.10804 (11) | 0.27324 (16) | 0.0202 | |
C8 | 0.8486 (2) | 0.03456 (11) | 0.22922 (16) | 0.0204 | |
N1 | 0.85071 (19) | −0.03958 (9) | 0.28544 (13) | 0.0202 | |
C9 | 0.7780 (3) | −0.05276 (12) | 0.40423 (17) | 0.0245 | |
C10 | 0.5858 (3) | −0.07650 (16) | 0.3880 (2) | 0.0359 | |
C11 | 0.9363 (2) | −0.11308 (12) | 0.23380 (18) | 0.0247 | |
C12 | 1.1183 (3) | −0.12854 (14) | 0.2963 (2) | 0.0342 | |
H71 | 0.720 (3) | 0.1042 (13) | 0.348 (2) | 0.0243* | |
H81 | 0.907 (3) | 0.0356 (13) | 0.157 (2) | 0.0245* | |
H91 | 0.849 (3) | −0.0967 (14) | 0.446 (2) | 0.0296* | |
H92 | 0.795 (3) | −0.0018 (14) | 0.453 (2) | 0.0296* | |
H101 | 0.547 (3) | −0.0856 (16) | 0.467 (2) | 0.0437* | |
H102 | 0.569 (3) | −0.1297 (17) | 0.338 (2) | 0.0437* | |
H103 | 0.516 (3) | −0.0327 (16) | 0.345 (2) | 0.0437* | |
H111 | 0.943 (3) | −0.1036 (14) | 0.150 (2) | 0.0297* | |
H112 | 0.861 (3) | −0.1648 (14) | 0.241 (2) | 0.0297* | |
H121 | 1.170 (3) | −0.1774 (16) | 0.257 (2) | 0.0408* | |
H122 | 1.192 (3) | −0.0777 (16) | 0.289 (2) | 0.0408* | |
H123 | 1.111 (3) | −0.1425 (16) | 0.380 (2) | 0.0408* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl2 | 0.0412 (3) | 0.0189 (2) | 0.0292 (2) | −0.00240 (19) | 0.00837 (19) | 0.00560 (18) |
C3 | 0.0192 (8) | 0.0176 (8) | 0.0208 (8) | −0.0022 (6) | 0.0005 (6) | 0.0040 (6) |
C4 | 0.0185 (8) | 0.0224 (9) | 0.0180 (8) | −0.0000 (6) | 0.0003 (6) | −0.0005 (7) |
O2 | 0.0352 (7) | 0.0182 (6) | 0.0244 (6) | 0.0023 (5) | 0.0058 (5) | 0.0000 (5) |
C5 | 0.0208 (8) | 0.0193 (8) | 0.0165 (8) | 0.0005 (6) | 0.0038 (6) | 0.0003 (6) |
Cl3 | 0.0287 (2) | 0.0212 (2) | 0.01910 (19) | 0.00201 (16) | 0.00756 (15) | 0.00142 (16) |
C6 | 0.0177 (7) | 0.0183 (8) | 0.0182 (8) | −0.0001 (6) | 0.0007 (6) | 0.0013 (6) |
C1 | 0.0179 (8) | 0.0215 (9) | 0.0172 (8) | 0.0009 (6) | 0.0003 (6) | 0.0011 (7) |
C2 | 0.0189 (8) | 0.0253 (9) | 0.0169 (8) | −0.0025 (7) | 0.0022 (6) | 0.0028 (7) |
Cl1 | 0.0318 (2) | 0.0309 (2) | 0.0219 (2) | −0.00064 (19) | 0.01013 (17) | 0.00438 (18) |
O1 | 0.0400 (8) | 0.0248 (7) | 0.0230 (6) | 0.0055 (6) | 0.0113 (6) | 0.0001 (5) |
C7 | 0.0224 (8) | 0.0196 (9) | 0.0187 (8) | −0.0006 (7) | 0.0037 (7) | 0.0007 (7) |
C8 | 0.0209 (8) | 0.0214 (8) | 0.0189 (8) | −0.0016 (7) | 0.0016 (6) | 0.0007 (7) |
N1 | 0.0250 (7) | 0.0170 (7) | 0.0188 (7) | 0.0011 (6) | 0.0032 (6) | 0.0003 (6) |
C9 | 0.036 (1) | 0.0195 (9) | 0.0186 (8) | 0.0007 (8) | 0.0046 (7) | 0.0026 (7) |
C10 | 0.0353 (12) | 0.0395 (12) | 0.0345 (11) | −0.0047 (9) | 0.0118 (9) | 0.002 (1) |
C11 | 0.0303 (9) | 0.0187 (9) | 0.0253 (9) | 0.0032 (7) | 0.0043 (7) | −0.0034 (7) |
C12 | 0.0317 (11) | 0.0270 (11) | 0.0433 (12) | 0.0046 (9) | 0.0008 (9) | −0.0012 (9) |
Geometric parameters (Å, º) top
Cl2—C3 | 1.7135 (17) | C8—H81 | 0.95 (2) |
C3—C4 | 1.500 (2) | N1—C9 | 1.472 (2) |
C3—C2 | 1.335 (3) | N1—C11 | 1.470 (2) |
C4—O2 | 1.234 (2) | C9—C10 | 1.513 (3) |
C4—C5 | 1.432 (2) | C9—H91 | 0.97 (2) |
C5—Cl3 | 1.7380 (16) | C9—H92 | 0.97 (2) |
C5—C6 | 1.391 (2) | C10—H101 | 0.95 (3) |
C6—C1 | 1.511 (2) | C10—H102 | 1.00 (3) |
C6—C7 | 1.409 (2) | C10—H103 | 0.96 (3) |
C1—C2 | 1.489 (2) | C11—C12 | 1.513 (3) |
C1—O1 | 1.219 (2) | C11—H111 | 0.93 (2) |
C2—Cl1 | 1.7198 (17) | C11—H112 | 1.01 (2) |
C7—C8 | 1.387 (2) | C12—H121 | 0.98 (3) |
C7—H71 | 0.96 (2) | C12—H122 | 0.99 (3) |
C8—N1 | 1.320 (2) | C12—H123 | 0.94 (3) |
| | | |
Cl2—C3—C4 | 115.53 (13) | C9—N1—C11 | 116.38 (14) |
Cl2—C3—C2 | 122.57 (14) | N1—C9—C10 | 112.02 (16) |
C4—C3—C2 | 121.90 (16) | N1—C9—H91 | 105.9 (13) |
C3—C4—O2 | 119.45 (15) | C10—C9—H91 | 112.0 (13) |
C3—C4—C5 | 115.56 (15) | N1—C9—H92 | 109.1 (13) |
O2—C4—C5 | 124.98 (15) | C10—C9—H92 | 110.6 (12) |
C4—C5—Cl3 | 114.54 (12) | H91—C9—H92 | 107.0 (18) |
C4—C5—C6 | 125.86 (15) | C9—C10—H101 | 108.4 (15) |
Cl3—C5—C6 | 119.31 (13) | C9—C10—H102 | 110.1 (14) |
C5—C6—C1 | 116.68 (14) | H101—C10—H102 | 109 (2) |
C5—C6—C7 | 122.08 (15) | C9—C10—H103 | 111.4 (15) |
C1—C6—C7 | 121.20 (15) | H101—C10—H103 | 110 (2) |
C6—C1—C2 | 117.79 (14) | H102—C10—H103 | 108 (2) |
C6—C1—O1 | 122.83 (15) | N1—C11—C12 | 112.26 (16) |
C2—C1—O1 | 119.35 (15) | N1—C11—H111 | 108.5 (13) |
C3—C2—C1 | 121.90 (15) | C12—C11—H111 | 109.4 (13) |
C3—C2—Cl1 | 122.47 (14) | N1—C11—H112 | 109.3 (12) |
C1—C2—Cl1 | 115.63 (13) | C12—C11—H112 | 110.3 (12) |
C6—C7—C8 | 127.73 (16) | H111—C11—H112 | 106.9 (18) |
C6—C7—H71 | 114.4 (12) | C11—C12—H121 | 108.6 (14) |
C8—C7—H71 | 117.7 (12) | C11—C12—H122 | 109.8 (14) |
C7—C8—N1 | 124.61 (16) | H121—C12—H122 | 110.4 (19) |
C7—C8—H81 | 120.6 (13) | C11—C12—H123 | 109.8 (15) |
N1—C8—H81 | 114.7 (13) | H121—C12—H123 | 108 (2) |
C8—N1—C9 | 123.02 (15) | H122—C12—H123 | 111 (2) |
C8—N1—C11 | 120.52 (14) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H71···Cl3 | 0.96 (2) | 2.51 (2) | 3.008 (2) | 112 (1) |
C8—H81···O1 | 0.94 (2) | 2.22 (2) | 2.832 (2) | 122 (2) |
C9—H91···Cl3i | 0.97 (2) | 2.81 (2) | 3.662 (2) | 147 (2) |
Symmetry code: (i) −x+3/2, y−1/2, −z+1. |
Experimental details
Crystal data |
Chemical formula | C12H12Cl3NO2 |
Mr | 308.59 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 150 |
a, b, c (Å) | 7.6548 (2), 15.7782 (4), 10.9114 (4) |
β (°) | 95.299 (1) |
V (Å3) | 1312.23 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.10 × 0.05 × 0.05 |
|
Data collection |
Diffractometer | Enraf-Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1996) |
Tmin, Tmax | 0.959, 0.966 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 5779, 2985, 2055 |
Rint | 0.01 |
(sin θ/λ)max (Å−1) | 0.648 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.029, 1.02 |
No. of reflections | 2055 |
No. of parameters | 199 |
No. of restraints | ? |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.23, −0.26 |
Selected geometric parameters (Å, º) topCl2—C3 | 1.7135 (17) | C1—C2 | 1.489 (2) |
C3—C4 | 1.500 (2) | C1—O1 | 1.219 (2) |
C3—C2 | 1.335 (3) | C2—Cl1 | 1.7198 (17) |
C4—O2 | 1.234 (2) | C7—C8 | 1.387 (2) |
C4—C5 | 1.432 (2) | C8—N1 | 1.320 (2) |
C5—Cl3 | 1.7380 (16) | N1—C9 | 1.472 (2) |
C5—C6 | 1.391 (2) | N1—C11 | 1.470 (2) |
C6—C1 | 1.511 (2) | C9—C10 | 1.513 (3) |
C6—C7 | 1.409 (2) | C11—C12 | 1.513 (3) |
| | | |
Cl2—C3—C4 | 115.53 (13) | C5—C6—C7 | 122.08 (15) |
Cl2—C3—C2 | 122.57 (14) | C1—C6—C7 | 121.20 (15) |
C4—C3—C2 | 121.90 (16) | C6—C1—C2 | 117.79 (14) |
C3—C4—O2 | 119.45 (15) | C6—C1—O1 | 122.83 (15) |
C3—C4—C5 | 115.56 (15) | C2—C1—O1 | 119.35 (15) |
O2—C4—C5 | 124.98 (15) | C3—C2—Cl1 | 122.47 (14) |
C4—C5—Cl3 | 114.54 (12) | C1—C2—Cl1 | 115.63 (13) |
C4—C5—C6 | 125.86 (15) | C6—C7—C8 | 127.73 (16) |
Cl3—C5—C6 | 119.31 (13) | C7—C8—N1 | 124.61 (16) |
C5—C6—C1 | 116.68 (14) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H71···Cl3 | 0.96 (2) | 2.51 (2) | 3.008 (2) | 112 (1) |
C8—H81···O1 | 0.94 (2) | 2.22 (2) | 2.832 (2) | 122 (2) |
C9—H91···Cl3i | 0.97 (2) | 2.81 (2) | 3.662 (2) | 147 (2) |
Symmetry code: (i) −x+3/2, y−1/2, −z+1. |
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Recently, we isolated the title compound, (I), as a by-product during a porphyrin synthesis. Porphyrins are commonly prepared by the acid-catalyzed reaction of aldehydes with pyrroles, followed by oxidation with p-chloranil (Lindsey et al., 1987). If excess triethylamine is used to neutralize the acid prior to oxidation of the porphyrinogen with p-chloranil, the title compound is formed, as should have been expected from the known reaction of triethylamine with p-chloranil (Buckley, Dunstan & Henbest, 1957; Buckley, Henbest & Slade, 1957). This dye belongs to a class of compounds known as blue quinones. There has recently been renewed interest in these compounds in connection with non-linear optics, because of their remarkable long wavelength absorption (λmax at 680 nm in CH2Cl2) (Alnabari & Bittner, 2000). This absorption has been attributed to intramolecular charge-transfer of the type shown in Scheme 1. The crystal structure presented here (Fig. 1) provides some insight into this resonance. The shortest bond length is N1—C8, which indicates that this bond has a substantial double-bond character, as in structure B (Scheme 1), but the next bond in the π-system C8–C7 is also a partial double bond indicating a contribution from structure A (see bond lengths in Table 1). To the best of our knowledge, this is the first crystal structure of a blue quinone. Short intramolecular contacts occur between O1 an H81 and between Cl3 and H71 (Table 2), both these are shorter than the sum of the van der Waals radii (2.68 and 2.86 Å, respectively) (Rowland, 1996). These interactions cooperate to keep the amine coplanar with quinone and in that way favours π-conjugation.