2,3,5-Tri­chloro-6-(4-methyl­piperidin-1-yl)-1,4-benzo­quinone: a synchrotron study

Bowes, K.F.; Cole, J.M.; Szablewski, M.

doi:10.1107/S1600536805004010

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o696-o698

https://doi.org/10.1107/S1600536805004010

2,3,5-Trichloro-6-(4-methylpiperidin-1-yl)-1,4-benzoquinone: a synchrotron study

Katharine F. Bowes,^a Jacqueline M. Cole ^a ^*‡ and Marek Szablewski ^b

^aDepartment of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England, and ^bDepartment of Physics, University of Durham, South Road, Durham DH1 3LE, England
^*Correspondence e-mail: jmc61@cam.ac.uk

(Received 19 January 2005; accepted 4 February 2005; online 19 February 2005)

The title compound, C₁₂H₁₂Cl₃NO₂, is a purple chromophore with an absorption at 563 nm in acetone solution. The benzenoid ring in the structure exhibits strong quinoid-like character. In the crystal structure, the molecules pack in alternating layers that are stabilized by close Cl⋯Cl intermolecular contacts.

Comment

The reactions of primary, secondary and tertiary amines with 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil), which yield highly coloured products, are well documented (Sivadjian, 1935 ; Buckley et al., 1957 ; Buckley & Henbest, 1956 ), and indeed the differently coloured products have been used as qualitative indicators of the degree of substitution on amines (Buuhoi et al., 1954 ).

Recent interest has focused on the reactions of enamines derived from tertiary amines with chloranil (Krivokapic & Anderson, 2002 ; Alnabari & Bittner, 2000 ) and other symmetrical quinoidal (Szablewski, 1994 ) systems, yielding conjugated chromophores with long-wavelength absorptions which are of interest for non-linear optics.

The title compound, (I), is the result of a reaction between the secondary amine 4-methylpiperidine and chloranil. Although reactions between chloranil and heterocyclic secondary amines have been investigated (Smith & Davis, 1984 ; Muralikrishna & Krishnamurthy, 1984 ), as have been photo-induced reactions of the products (Kallmayer & Fritzen, 1992 ), we believe that no structure of such a compound has been reported to date.

The molecular structure of (I) is illustrated in Fig. 1. The benzenoid ring exhibits strong quinoidal character (see Table 1) due to the strong electronic influence of the two keto groups, substituted para to each other on the ring. The saturated ring displays a typical chair conformation.

In the crystal structure, the molecules pack in alternating AB layers; A and B being related by a center of symmetry (Fig. 2). The crystal packing is stabilized by close Cl⋯Cl intermolecular contacts [Cl1ⁱ⋯Cl1ⁱⁱ = 3.2333 (12) Å]. Another, albeit much weaker, Cl⋯Cl intermolecular contact [Cl3ⁱⁱ⋯Cl3ⁱⁱⁱ = 3.5450 (14) Å] is also present (see Fig. 2 for details).

Figure 1
The molecular structure of compound (I

). Anisotropic displacement parameters are displayed at the 50% probability level.

Figure 2
The crystal packing of compound (I

), viewed down the a axis. The Cl⋯Cl contacts are illustrated by dashed lines [Symmetry codes: (i) x, y, z; (ii) 1 − x, 1 − y, 1 − z; (iii) x + 1, y − 1, z + 1.]

Experimental

2,3,5,6-Tetrachloro-1,4-benzoquinone (1 g, 4 × 10⁻³ mol) was stirred in toluene (250 ml) with 4-methylpiperidine (0.8 g, 8 × 10⁻³ mol) at room temperature for 3 h. The solution very rapidly became dark purple in colour. Column chromatography of the reaction mixture performed on neutral silica gel with dichloromethane eluent was used to purify the product. After evaporating the solvent from the product-containing fraction in vacuo, the purified compound was recrystallized from hot dichloromethane, yielding purple microcrystals (0.260 g, 21%). Microanalysis calculated for C₁₂H₁₂Cl₃NO₂: C 46.71, N 4.54, H 3.92%; found: C 47.01, N 4.81, H 3.98%. ¹H NMR (400 Hz, CD₂Cl₂): δ 1.00 (doublet, 1 × CH₃), 1.40 (quartet, 2 × ¹H), 1.65 (multiplet, —CH—), 1.75 (doublet, 2 × ¹H), 3.25 (triplet, 2 × ¹H), 3.75 (doublet, 2 × ¹H). ¹³C NMR (400 Hz, CD₂Cl₂): δ 22, 30, 35, 118, 138, 141, 171, 175. MS: m/z, M⁺(EI+) 306.89. (100% molecular ion). The product displayed positive (bathochromic) solvatochromism (λ_max = 549 nm in hexane, 554 nm in diethyl ether, 556 nm in acetone, 571 nm in nitromethane and 576 nm in dichloromethane).

Crystal data

C₁₂H₁₂Cl₃NO₂
M_r = 308.58
Triclinic, $[P\overline 1]$
a = 6.9577 (14) Å
b = 9.3611 (19) Å
c = 10.724 (2) Å
α = 70.64 (3)°
β = 83.96 (3)°
γ = 82.27 (3)°
V = 651.6 (2) Å³
Z = 2
D_x = 1.573 Mg m⁻³
Synchrotron radiation, λ = 0.6928 Å
Cell parameters from 3573 reflections
θ = 2.5–27.6°
μ = 0.70 mm⁻¹
T = 150 (2) K
Needle, deep purple
0.09 × 0.04 × 0.02 mm

Data collection

Bruker SMART CCD diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.91, T_max = 0.99
4339 measured reflections
3099 independent reflections
2932 reflections with I > 2σ(I)
R_int = 0.024
θ_max = 28.3°
h = −9 → 8
k = −12 → 10
l = −13 → 14

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.092
S = 1.05
3099 reflections
163 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0527P)² + 0.1747P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected bond lengths (Å)

C1—C6	1.3741 (18)
C3—C4	1.3363 (18)
C1—C2	1.5192 (17)
C2—C3	1.4914 (18)
C4—C5	1.4979 (18)
C5—C6	1.4564 (18)

The H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.98–1.00 Å and U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for methyl H atoms.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805004010/su6166sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805004010/su6166Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

2,3,5-Trichloro-6-(4-methylpiperidin-1-yl)-1,4-benzoquinone top

Crystal data top

C₁₂H₁₂Cl₃NO₂	Z = 2
M_r = 308.58	F(000) = 316
Triclinic, P1	D_x = 1.573 Mg m⁻³
Hall symbol: -P 1	Synchrotron radiation, λ = 0.6928 Å
a = 6.9577 (14) Å	Cell parameters from 3573 reflections
b = 9.3611 (19) Å	θ = 2.5–27.6°
c = 10.724 (2) Å	µ = 0.70 mm⁻¹
α = 70.64 (3)°	T = 150 K
β = 83.96 (3)°	Needle, deep purple
γ = 82.27 (3)°	0.09 × 0.04 × 0.02 mm
V = 651.6 (2) Å³

Data collection top

Bruker SMART diffractometer	3099 independent reflections
Radiation source: Station 9.8, SRS, Daresbury labs, UK	2932 reflections with I > 2σ(I)
Si (111) monochromator	R_int = 0.024
CCD scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→8
T_min = 0.91, T_max = 0.99	k = −12→10
4339 measured reflections	l = −13→14

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
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) = 0.092	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0527P)² + 0.1747P] where P = (F_o² + 2F_c²)/3
3099 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Special details top

Experimental. H atoms were positioned according to idealized geometries and treated as riding atoms [U_iso(H) = 1.2U_eq(C) for non-methyl H atoms; U_iso(H) = 1.5U_eq(C) for methyl H atoms].

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	U_iso*/U_eq
Cl1	0.40844 (5)	0.67593 (3)	0.46314 (3)	0.02639 (10)
Cl2	0.12225 (5)	1.17185 (4)	0.59392 (3)	0.02531 (10)
Cl3	0.52239 (5)	0.88092 (4)	0.16632 (3)	0.02700 (11)
O2	0.23842 (15)	0.85730 (12)	0.62530 (10)	0.0287 (2)
O1	0.38847 (15)	1.19610 (11)	0.12496 (9)	0.0279 (2)
C5	0.26794 (17)	0.93849 (14)	0.51072 (12)	0.0202 (2)
N1	0.23548 (16)	1.35048 (12)	0.29519 (11)	0.0223 (2)
C2	0.36597 (18)	1.12306 (14)	0.24144 (12)	0.0201 (2)
C1	0.27294 (17)	1.19709 (14)	0.34266 (12)	0.0192 (2)
C6	0.22229 (17)	1.10331 (15)	0.46732 (12)	0.0197 (2)
C4	0.36487 (17)	0.86981 (14)	0.40931 (12)	0.0198 (2)
C7	0.38420 (18)	1.44789 (14)	0.21613 (12)	0.0219 (2)
H7A	0.4948	1.3836	0.1894	0.026*
H7B	0.4335	1.4999	0.2711	0.026*
C11	0.05998 (19)	1.43523 (15)	0.33421 (14)	0.0261 (3)
H11A	0.0924	1.4867	0.3952	0.031*
H11B	−0.0372	1.3642	0.3811	0.031*
C8	0.3023 (2)	1.56646 (15)	0.09304 (13)	0.0249 (3)
H8A	0.2685	1.5149	0.0325	0.030*
H8B	0.4024	1.6347	0.0461	0.030*
C3	0.41441 (17)	0.95444 (14)	0.28565 (12)	0.0201 (2)
C9	0.1219 (2)	1.66056 (15)	0.12904 (14)	0.0270 (3)
H9A	0.1611	1.7167	0.1854	0.032*
C10	−0.0247 (2)	1.55350 (15)	0.21080 (15)	0.0279 (3)
H10A	−0.0696	1.5003	0.1551	0.033*
H10B	−0.1390	1.6140	0.2382	0.033*
C12	0.0382 (3)	1.77758 (19)	0.00529 (17)	0.0406 (4)
H12A	−0.0777	1.8362	0.0309	0.061*
H12B	0.0029	1.7251	−0.0530	0.061*
H12C	0.1356	1.8466	−0.0415	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.03073 (19)	0.01802 (16)	0.02813 (18)	−0.00103 (12)	−0.00157 (13)	−0.00509 (12)
Cl2	0.02420 (17)	0.03121 (18)	0.02312 (17)	−0.00301 (12)	0.00309 (12)	−0.01355 (13)
Cl3	0.03295 (19)	0.02597 (18)	0.02271 (17)	0.00095 (13)	0.00197 (12)	−0.01137 (13)
O2	0.0344 (5)	0.0274 (5)	0.0209 (5)	−0.0057 (4)	0.0029 (4)	−0.0037 (4)
O1	0.0370 (5)	0.0247 (5)	0.0194 (4)	−0.0033 (4)	0.0020 (4)	−0.0046 (4)
C5	0.0167 (6)	0.0235 (6)	0.0205 (6)	−0.0045 (4)	−0.0007 (4)	−0.0065 (5)
N1	0.0195 (5)	0.0195 (5)	0.0261 (5)	−0.0018 (4)	0.0045 (4)	−0.0069 (4)
C2	0.0186 (5)	0.0214 (6)	0.0203 (6)	−0.0025 (4)	−0.0004 (4)	−0.0071 (5)
C1	0.0163 (5)	0.0206 (6)	0.0215 (6)	−0.0024 (4)	−0.0004 (4)	−0.0080 (5)
C6	0.0174 (5)	0.0237 (6)	0.0198 (6)	−0.0027 (4)	0.0004 (4)	−0.0098 (5)
C4	0.0182 (5)	0.0183 (5)	0.0230 (6)	−0.0018 (4)	−0.0025 (4)	−0.0065 (4)
C7	0.0209 (6)	0.0214 (6)	0.0229 (6)	−0.0054 (4)	0.0021 (4)	−0.0062 (5)
C11	0.0233 (6)	0.0222 (6)	0.0306 (7)	−0.0013 (5)	0.0065 (5)	−0.0086 (5)
C8	0.0274 (6)	0.0226 (6)	0.0227 (6)	−0.0023 (5)	0.0017 (5)	−0.0058 (5)
C3	0.0186 (6)	0.0221 (6)	0.0211 (6)	−0.0006 (4)	−0.0014 (4)	−0.0096 (5)
C9	0.0285 (7)	0.0221 (6)	0.0291 (7)	0.0002 (5)	0.0001 (5)	−0.0083 (5)
C10	0.0236 (6)	0.0238 (6)	0.0362 (7)	0.0004 (5)	−0.0004 (5)	−0.0112 (5)
C12	0.0421 (9)	0.0309 (8)	0.0392 (8)	0.0074 (6)	−0.0042 (7)	−0.0022 (6)

Geometric parameters (Å, º) top

Cl1—C4	1.7069 (13)	C7—H7B	0.9900
Cl2—C6	1.7315 (13)	C11—C10	1.530 (2)
Cl3—C3	1.7083 (13)	C11—H11A	0.9900
O2—C5	1.2245 (16)	C11—H11B	0.9900
O1—C2	1.2139 (16)	C8—C9	1.5254 (19)
N1—C1	1.3534 (16)	C8—H8A	0.9900
N1—C11	1.4653 (16)	C8—H8B	0.9900
N1—C7	1.4757 (17)	C9—C10	1.522 (2)
C1—C6	1.3741 (18)	C9—C12	1.526 (2)
C3—C4	1.3363 (18)	C9—H9A	1.0000
C1—C2	1.5192 (17)	C10—H10A	0.9900
C2—C3	1.4914 (18)	C10—H10B	0.9900
C4—C5	1.4979 (18)	C12—H12A	0.9800
C5—C6	1.4564 (18)	C12—H12B	0.9800
C7—C8	1.5219 (19)	C12—H12C	0.9800
C7—H7A	0.9900

O2—C5—C6	123.14 (12)	H11A—C11—H11B	108.2
O2—C5—C4	119.91 (12)	C7—C8—C9	111.12 (11)
C6—C5—C4	116.88 (11)	C7—C8—H8A	109.4
C1—N1—C11	123.69 (11)	C9—C8—H8A	109.4
C1—N1—C7	121.70 (11)	C7—C8—H8B	109.4
C11—N1—C7	113.90 (10)	C9—C8—H8B	109.4
O1—C2—C3	119.68 (12)	H8A—C8—H8B	108.0
O1—C2—C1	121.60 (11)	C4—C3—C2	120.51 (11)
C3—C2—C1	118.51 (11)	C4—C3—Cl3	123.93 (10)
N1—C1—C6	127.03 (12)	C2—C3—Cl3	115.47 (9)
N1—C1—C2	114.93 (11)	C10—C9—C8	108.97 (11)
C6—C1—C2	117.83 (11)	C10—C9—C12	112.57 (13)
C1—C6—C5	123.64 (11)	C8—C9—C12	111.00 (12)
C1—C6—Cl2	122.83 (10)	C10—C9—H9A	108.1
C5—C6—Cl2	113.15 (9)	C8—C9—H9A	108.1
C3—C4—C5	122.34 (11)	C12—C9—H9A	108.1
C3—C4—Cl1	122.41 (10)	C9—C10—C11	112.52 (12)
C5—C4—Cl1	115.24 (9)	C9—C10—H10A	109.1
N1—C7—C8	111.48 (11)	C11—C10—H10A	109.1
N1—C7—H7A	109.3	C9—C10—H10B	109.1
C8—C7—H7A	109.3	C11—C10—H10B	109.1
N1—C7—H7B	109.3	H10A—C10—H10B	107.8
C8—C7—H7B	109.3	C9—C12—H12A	109.5
H7A—C7—H7B	108.0	C9—C12—H12B	109.5
N1—C11—C10	109.52 (11)	H12A—C12—H12B	109.5
N1—C11—H11A	109.8	C9—C12—H12C	109.5
C10—C11—H11A	109.8	H12A—C12—H12C	109.5
N1—C11—H11B	109.8	H12B—C12—H12C	109.5
C10—C11—H11B	109.8

Footnotes

‡Mailing address: St Catharine's College, Cambridge CB2 1RL, England

Acknowledgements

The authors acknowledge Simon J. Teat (CCLRC Daresbury Laboratory) for local synchrotron support and the Synchrotron Radiation Source, CCLRC Daresbury Laboratory, England, for access to scientific facilities. JMC also thanks the Royal Society for a University Research Fellowship and St Catharine's College, Cambridge, for a Bibby Research Fellowship. KFB is grateful to the EPSRC for a PhD studentship (0280020X) and the Centre of Molecular Structure and Dynamics (CMSD), CCLRC, for a CASE sponsorship.

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