2,5 Bis(1 piperidinyl­methyl)­benzene 1,4 diol

organic papers

Acta Cryst.(2004). E60, o1321±o1322 DOI: 10.1107/S1600536804016344 Yuan, Zhang, Pan and Ma C₁₈H₂₈N₂O₂

o1321

Structure Reports Online

ISSN 1600-5368

2,5-Bis(1-piperidinylmethyl)benzene-1,4-diol

Dongyan Yuan, Mingjie Zhang,* Zhaohui Pan and Penggao Ma

Department of Chemistry, Tianjin University, Tianjin 300072, People's Republic of China

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.003 AÊ Rfactor = 0.051 wRfactor = 0.128

Data-to-parameter ratio = 14.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C18H28N2O2, is a product of a Mannich

reaction involving hydroquinone, formaldehyde and piper-idine. The molecule occupies a special position on an inversion centre. The structure is stabilized by an intramolecular OÐ H N hydrogen bond linking the phenol OH group and a piperidyl N atom.

Comment

The Mannich reaction is extremely useful for the preparation of nitrogenous molecules (Arend et al., 1998; Zhou et al., 2000). Its popularity (Laobuthee et al., 2001) is due to the widespread occurrence of nitrogen in drugs and natural products, as well as the diversity of this multicomponent reaction. 2,5-Bis(1-piperidinylmethyl)benzene-1,4-diol, (I), has been synthesized by the Mannich reaction (Miller et al., 1965; Shriner et al., 1946). The crystal structure of (I) is reported in this paper.

The molecular structure of (I) is shown in Fig. 1. The mol-ecule occupies a special position on a crystallographic inver-sion centre. The piperidine ring has the usual chair conformation. Because of the steric hindrance between the benzene and piperidine rings, atom C4 has a distorted tetra-hedral geometry, with the N1ÐC4ÐC3 angle [112.28 (17)_]

deviating signi®cantly from the regular tetrahedral value. Intramolecular OÐH N hydrogen bonds (Table 2) stabilize the crystal structure.

Received 7 June 2004 Accepted 5 July 2004 Online 17 July 2004

Figure 1

Experimental

To a suspension of 1 g (33 mmol) of paraformaldehyde and 0.2 g (1.8 mmol) of hydroquinone in 20 ml of stirred ethanol was cautiously added 0.31 g (3.6 mmol) of piperidine. A mildly exothermic reaction ensued. After re¯ux for 6 h, the solvent was evaporated. The crystalline product was separated and recrystallized from ethanol (yield 69%). Colourless prism-shaped single crystals suitable for X-ray structure analysis were obtained (m.p. 469±471 K). Spectroscopic analysis, IR (KBr, , cmÿ1_{): 3432, 2947, 2858, 1480,} 1453, 1378, 869;1_{H NMR (CDCl}

3, p.p.m.): 6.48 (s, 2H), 3.62 (s, 4H), 2.43±2.80 (m, 8H), 1.46±1.65 (m, 12H). Analysis calculated for C18H28N2O2: C 71.02, H 9.27, N 9.20%; found: C 71.13, H 9.60, N 9.31%.

Crystal data

C18H28N2O2

Mr= 304.42

Triclinic,P1

a= 6.372 (2) AÊ

b= 8.184 (3) AÊ

c= 8.649 (3) AÊ

= 72.349 (5)

= 81.745 (6)

= 80.865 (5)

V= 422.2 (3) AÊ3

Z= 1

Dx= 1.197 Mg mÿ3

MoKradiation Cell parameters from 644

re¯ections

= 2.6±25.6

= 0.08 mmÿ1

T= 293 (2) K Prism, colourless 0.200.160.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

'and!scans

Absorption correction: none 2215 measured re¯ections 1487 independent re¯ections 982 re¯ections withI> 2(I)

Rint= 0.017

max= 25.0

h=ÿ7!7

k=ÿ8!9

l=ÿ5!10

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.051}

wR(F2_{) = 0.128}

S= 1.06 1487 re¯ections 101 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0504P)2

+ 0.1017P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001 max= 0.17 e AÊÿ3 min=ÿ0.18 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

O1ÐC1 1.372 (2)

N1ÐC4 1.475 (3) N1ÐC5N1ÐC9 1.464 (3)1.463 (3)

O1ÐC1ÐC2 118.6 (2) O1ÐC1ÐC3i _{121.42 (19)}

N1ÐC4ÐC3 112.28 (17)

N1ÐC5ÐC6 111.31 (19) N1ÐC9ÐC8 111.57 (18)

O1ÐC1ÐC2ÐC3 ÿ179.63 (18)

C2ÐC3ÐC4ÐN1 138.2 (2) N1ÐC5ÐC6ÐC7C7ÐC8ÐC9ÐN1 ÿ56.3 (3)57.1 (2)

Symmetry code: (i)ÿx;ÿy;ÿz.

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O1ÐH1 N1i _{0.82 2.00 2.711 (2) 146} Symmetry code: (i)ÿx;ÿy;ÿz.

All H atoms were located in a difference map and included in the re®nement in the riding-model approximation (OÐH = 0.82 AÊ and CÐH = 0.93±0.97 AÊ), withUiso(H) = 1.2Ueq(C) [Uiso(H) = 1.5Ueq(O) in the case of the hydroxyl H atom].

Data collection:SMART(Bruker, 1997); cell re®nement:SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 1997); software used to prepare material for publication:SHELXTL.

References

Arend, M., Westermann, B. & Risch, N. (1998).Angew. Chem. Int. Ed.37, 1044±1070.

Bruker (1997).SMART, SAINTandSHELXTL.Versions 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Laobuthee, A., Chirachanchai, S., Ishida, H. & Tashiro, K. (2001).J. Am. Chem. Soc.123, 9947±9955.

Miller, J. B., Fields, D. L. & Reynolds, D. D.(1965).J. Org. Chem.30, 247±251. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

GoÈttingen, Germany.

Shriner, R. L., Grillot, G. F. & Teeters, W. O. (1946).J. Am. Chem. Soc.68, 946± 947.

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Acta Cryst. (2004). E60, o1321–o1322

supporting information

Acta Cryst. (2004). E60, o1321–o1322 [https://doi.org/10.1107/S1600536804016344]

2,5-Bis(1-piperidinylmethyl)benzene-1,4-diol

Dongyan Yuan, Mingjie Zhang, Zhaohui Pan and Penggao Ma

2,5-bis(1-piperidinylmethyl)benzene-1,4-diol

Crystal data

C18H28N2O2 Mr = 304.42 Triclinic, P1 Hall symbol: -P 1 a = 6.372 (2) Å b = 8.184 (3) Å c = 8.649 (3) Å α = 72.349 (5)° β = 81.745 (6)° γ = 80.865 (5)° V = 422.2 (3) Å3

Z = 1 F(000) = 166 Dx = 1.197 Mg m−3 Melting point: 469 K

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 644 reflections θ = 2.6–25.6°

µ = 0.08 mm−1 T = 293 K Prism, colourless 0.20 × 0.16 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

2215 measured reflections 1487 independent reflections

982 reflections with I > 2σ(I) Rint = 0.017

θmax = 25.0°, θmin = 2.6° h = −7→7

k = −8→9 l = −5→10

Refinement

Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.051} wR(F2_{) = 0.128} S = 1.06 1479 reflections 101 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(Fo2_{) + (0.0504P)}2 _{+ 0.1017P]}

where P = (Fo2 _{+ 2Fc}2_)/3 (Δ/σ)max < 0.001

Δρmax = 0.17 e Å−3 Δρmin = −0.18 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

O1 −0.3143 (2) 0.1153 (2) −0.20974 (19) 0.0583 (5)

H1 −0.3528 0.0338 −0.2302 0.087*

N1 0.2925 (3) 0.2183 (2) 0.2098 (2) 0.0450 (5)

C1 −0.1591 (3) 0.0548 (3) −0.1044 (2) 0.0436 (5)

C2 −0.0403 (3) 0.1709 (3) −0.0821 (2) 0.0452 (6)

H2 −0.0689 0.2872 −0.1383 0.054*

C3 0.1196 (3) 0.1210 (3) 0.0209 (2) 0.0422 (5)

C4 0.2558 (4) 0.2465 (3) 0.0386 (3) 0.0520 (6)

H4A 0.3923 0.2353 −0.0256 0.062*

H4B 0.1868 0.3632 −0.0040 0.062*

C5 0.4543 (4) 0.3219 (3) 0.2205 (3) 0.0565 (7)

H5A 0.4056 0.4435 0.1746 0.068*

H5B 0.5857 0.2935 0.1570 0.068*

C6 0.4975 (4) 0.2899 (3) 0.3947 (3) 0.0652 (7)

H6A 0.6000 0.3642 0.3983 0.078*

H6B 0.5595 0.1709 0.4371 0.078*

C7 0.2954 (4) 0.3242 (4) 0.5005 (3) 0.0651 (7)

H7A 0.2437 0.4466 0.4683 0.078*

H7B 0.3248 0.2914 0.6136 0.078*

C8 0.1266 (4) 0.2217 (3) 0.4828 (3) 0.0553 (6)

H8A 0.1705 0.0993 0.5290 0.066*

H8B −0.0069 0.2525 0.5428 0.066*

C9 0.0935 (3) 0.2569 (3) 0.3067 (2) 0.0459 (6)

H9A −0.0116 0.1871 0.2983 0.055*

H9B 0.0381 0.3774 0.2634 0.055*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

O1 0.0591 (10) 0.0593 (11) 0.0607 (11) 0.0021 (8) −0.0236 (8) −0.0203 (8)

N1 0.0410 (10) 0.0542 (12) 0.0452 (11) −0.0114 (8) −0.0009 (8) −0.0210 (9)

C1 0.0440 (12) 0.0519 (15) 0.0367 (12) −0.0024 (10) −0.0043 (10) −0.0169 (10)

C2 0.0555 (13) 0.0401 (13) 0.0385 (13) −0.0020 (10) −0.0045 (11) −0.0110 (10)

C3 0.0463 (12) 0.0486 (14) 0.0335 (12) −0.0099 (10) 0.0022 (10) −0.0153 (10)

C4 0.0574 (14) 0.0564 (14) 0.0445 (14) −0.0163 (11) 0.0006 (11) −0.0158 (11)

C5 0.0454 (13) 0.0663 (16) 0.0656 (17) −0.0189 (11) 0.0011 (12) −0.0273 (13)

C6 0.0532 (15) 0.0772 (18) 0.0780 (19) −0.0128 (13) −0.0160 (13) −0.0345 (15)

C7 0.0686 (17) 0.0751 (18) 0.0623 (17) −0.0038 (13) −0.0142 (13) −0.0347 (14)

C8 0.0580 (15) 0.0621 (15) 0.0476 (14) −0.0065 (12) 0.0003 (11) −0.0214 (12)

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Acta Cryst. (2004). E60, o1321–o1322

Geometric parameters (Å, º)

O1—C1 1.372 (2) C5—H5A 0.9700

O1—H1 0.8200 C5—H5B 0.9700

N1—C4 1.475 (3) C6—C7 1.509 (3)

N1—C5 1.464 (3) C6—H6A 0.9700

N1—C9 1.463 (3) C6—H6B 0.9700

C1—C2 1.376 (3) C7—C8 1.515 (3)

C1—C3i _{1.401 (3) C7—H7A 0.9700}

C2—C3 1.381 (3) C7—H7B 0.9700

C2—H2 0.9300 C8—C9 1.501 (3)

C3—C1i _{1.401 (3) C8—H8A 0.9700}

C3—C4 1.500 (3) C8—H8B 0.9700

C4—H4A 0.9700 C9—H9A 0.9700

C4—H4B 0.9700 C9—H9B 0.9700

C5—C6 1.507 (3)

C1—O1—H1 109.5 C5—C6—C7 111.39 (19)

C9—N1—C5 110.46 (16) C5—C6—H6A 109.3

C9—N1—C4 110.95 (17) C7—C6—H6A 109.3

C5—N1—C4 110.96 (17) C5—C6—H6B 109.3

O1—C1—C2 118.6 (2) C7—C6—H6B 109.3

O1—C1—C3i _{121.42 (19) H6A—C6—H6B 108.0}

C2—C1—C3i _{119.97 (19) C6—C7—C8 109.78 (19)}

C1—C2—C3 122.4 (2) C6—C7—H7A 109.7

C1—C2—H2 118.8 C8—C7—H7A 109.7

C3—C2—H2 118.8 C6—C7—H7B 109.7

C2—C3—C1i _{117.66 (19) C8—C7—H7B 109.7}

C2—C3—C4 122.2 (2) H7A—C7—H7B 108.2

C1i_{—C3—C4 120.10 (19) C9—C8—C7 110.86 (19)}

N1—C4—C3 112.28 (17) C9—C8—H8A 109.5

N1—C4—H4A 109.1 C7—C8—H8A 109.5

C3—C4—H4A 109.1 C9—C8—H8B 109.5

N1—C4—H4B 109.1 C7—C8—H8B 109.5

C3—C4—H4B 109.1 H8A—C8—H8B 108.1

H4A—C4—H4B 107.9 N1—C9—C8 111.57 (18)

N1—C5—C6 111.31 (19) N1—C9—H9A 109.3

N1—C5—H5A 109.4 C8—C9—H9A 109.3

C6—C5—H5A 109.4 N1—C9—H9B 109.3

N1—C5—H5B 109.4 C8—C9—H9B 109.3

C6—C5—H5B 109.4 H9A—C9—H9B 108.0

H5A—C5—H5B 108.0

O1—C1—C2—C3 −179.63 (18) C9—N1—C5—C6 58.2 (2)

C3i_{—C1—C2—C3 0.1 (3) C4—N1—C5—C6 −178.33 (18)}

C1—C2—C3—C1i _{−0.1 (3) N1—C5—C6—C7 −56.3 (3)}

C1—C2—C3—C4 176.92 (19) C5—C6—C7—C8 53.5 (3)

C5—N1—C4—C3 170.28 (18) C5—N1—C9—C8 −58.9 (2)

C2—C3—C4—N1 138.2 (2) C4—N1—C9—C8 177.62 (18)

C1i_{—C3—C4—N1 −44.9 (3) C7—C8—C9—N1 57.1 (2)}

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1—H1···N1i _{0.82 2.00 2.711 (2) 146}