organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Crystal structure of 2-[bis­(1H-pyrazol-1-yl)meth­yl]pyridine

aDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
*Correspondence e-mail: skkang@cnu.ac.kr

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 7 July 2015; accepted 9 July 2015; online 15 July 2015)

The title compound, C12H11N5, was synthesized as a potential tridentate ligand to make catalytic metal complexes. The dihedral angle between the pyrazolyl rings is 67.9 (1)°. The most prominent feature in the crystal packing are C—H⋯N hydrogen-bonding inter­actions that link the mol­ecules into a supra­molecular tape along the b-axis direction.

1. Related literature

For the synthesis of the title compound, see: Park et al. (2015[Park, J.-E., Kang, S. K., Woo, J. O. & Son, K.-s. (2015). Dalton Trans. 44, 9964-9969.]); Hoffmann et al. (2010[Hoffmann, A., Flörke, U., Schürmann, M. & Herres-Pawlis, S. (2010). Eur. J. Org. Chem. pp. 4136-4144.]). For metal complexes of the similar ligands, see: Anderson et al. (2000[Anderson, P. A., Astley, T., Hitchman, M. A., Keene, F. R., Moubaraki, B., Murray, K. S., Skelton, B. W., Tiekink, E. R. T., Toftlund, H. & White, A. H. (2000). J. Chem. Soc. Dalton Trans. pp. 3505-3512.]); Liu et al. (2011[Liu, J.-C., Guo, G.-Z., Xiao, C.-H., Song, X.-Y. & Li, M. (2011). Acta Cryst. E67, m1691.]); Xiao et al. (2012[Xiao, C.-H., Song, X.-Y., Sun, Z., Cao, P. & Pang, T. (2012). Acta Cryst. E68, m857.]). For potential applications of similar ligands in catalysis, see: Park et al. (2015[Park, J.-E., Kang, S. K., Woo, J. O. & Son, K.-s. (2015). Dalton Trans. 44, 9964-9969.]); Zhang et al. (2009[Zhang, J., Li, A. & Hor, T. S. A. (2009). Organometallics, 28, 2935-2937.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C12H11N5

  • Mr = 225.26

  • Triclinic, [P \overline 1]

  • a = 7.5723 (3) Å

  • b = 8.6376 (3) Å

  • c = 9.7354 (5) Å

  • α = 97.539 (2)°

  • β = 106.123 (4)°

  • γ = 105.510 (5)°

  • V = 574.73 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 173 K

  • 0.26 × 0.24 × 0.09 mm

2.2. Data collection

  • Bruker SMART CCD area-detector diffractometer

  • 18045 measured reflections

  • 2870 independent reflections

  • 1813 reflections with I > 2σ(I)

  • Rint = 0.089

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.123

  • S = 0.98

  • 2870 reflections

  • 153 parameters

  • H-atom parameters constrained

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1⋯N8i 0.98 2.45 3.3974 (18) 162
C10—H10⋯N13ii 0.93 2.60 3.496 (2) 161
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x, y+1, z.

Data collection: SMART (Bruker, 2002[Bruker (2002). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: publCIF (Westrip,2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Experimental top

Synthesis and crystallization top

In a 50 ml Schlenk flask, NaH (0.24 g, 10 mmol) was added in dry tetra­hydro­furan (THF; 10 ml) and stirred at 0 °C. Pyrazole (0.68 g, 10 mmol) was added gradually to the mixture over 10 min. and the stirring was continued for 40 min. at 0 °C, resulting in a pale-yellow solution. Thio­nyl chloride (0.38 mL, 5 mmol) was added drop wise to this mixture at 0 °C. After stirring for 1 h, pyridine-2-aldehyde (0.48 ml, 5 mmol) and a catalytic amount of cobalt(II) chloride were added and the resulting solution was refluxed overnight. The reaction mixture was allowed to cool to room temperature, and di­ethyl ether and water (1:1) were added. The bi-phasic solution was stirred for 45 min. to quench the cobalt catalyst. The aqueous layer was extracted three times with di­ethyl ether. The combined organic layers were dried over sodium sulfate and filtered. The solvent in the filtrate was removed in vacuo and the resulting solid was purified by column chromatography on silica gel, with ethyl acetate as the eluent. An off-white solid was obtained in 33% yield. Single crystals of the title compound were obtained by slow diffusion of hexane into a concentrated solution of the product in THF at room temperature.

Refinement top

All H atoms were positioned geometrically and refined using riding model, with d(C—H) = 0.93–0.98 Å, and with Uiso(H) = 1.2Ueq(C).

Related literature top

For the synthesis of the title compound, see: Park et al. (2015); Hoffmann et al. (2010). For metal complexes of the similar ligands, see: Anderson et al. (2000); Liu et al. (2011); Xiao et al. (2012). For potential applications of similar ligands in catalysis, see: Park et al. (2015); Zhang et al. (2009).

Structure description top

For the synthesis of the title compound, see: Park et al. (2015); Hoffmann et al. (2010). For metal complexes of the similar ligands, see: Anderson et al. (2000); Liu et al. (2011); Xiao et al. (2012). For potential applications of similar ligands in catalysis, see: Park et al. (2015); Zhang et al. (2009).

Synthesis and crystallization top

In a 50 ml Schlenk flask, NaH (0.24 g, 10 mmol) was added in dry tetra­hydro­furan (THF; 10 ml) and stirred at 0 °C. Pyrazole (0.68 g, 10 mmol) was added gradually to the mixture over 10 min. and the stirring was continued for 40 min. at 0 °C, resulting in a pale-yellow solution. Thio­nyl chloride (0.38 mL, 5 mmol) was added drop wise to this mixture at 0 °C. After stirring for 1 h, pyridine-2-aldehyde (0.48 ml, 5 mmol) and a catalytic amount of cobalt(II) chloride were added and the resulting solution was refluxed overnight. The reaction mixture was allowed to cool to room temperature, and di­ethyl ether and water (1:1) were added. The bi-phasic solution was stirred for 45 min. to quench the cobalt catalyst. The aqueous layer was extracted three times with di­ethyl ether. The combined organic layers were dried over sodium sulfate and filtered. The solvent in the filtrate was removed in vacuo and the resulting solid was purified by column chromatography on silica gel, with ethyl acetate as the eluent. An off-white solid was obtained in 33% yield. Single crystals of the title compound were obtained by slow diffusion of hexane into a concentrated solution of the product in THF at room temperature.

Refinement details top

All H atoms were positioned geometrically and refined using riding model, with d(C—H) = 0.93–0.98 Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip,2010).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. Part of the crystal structure of the title compound, showing supramolecular tapes aligned along the b axis and sustained by C—H···N hydrogen bonds (dashed lines).
2-[Bis(1H-pyrazol-1-yl)methyl]pyridine top
Crystal data top
C12H11N5Z = 2
Mr = 225.26F(000) = 236
Triclinic, P1Dx = 1.302 Mg m3
a = 7.5723 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.6376 (3) ÅCell parameters from 2704 reflections
c = 9.7354 (5) Åθ = 2.2–22.9°
α = 97.539 (2)°µ = 0.09 mm1
β = 106.123 (4)°T = 173 K
γ = 105.510 (5)°Plate, colourless
V = 574.73 (5) Å30.26 × 0.24 × 0.09 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
Rint = 0.089
Radiation source: fine-focus sealed tubeθmax = 28.4°, θmin = 2.2°
φ and ω scansh = 1010
18045 measured reflectionsk = 1111
2870 independent reflectionsl = 1213
1813 reflections with I > 2σ(I)
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.123 w = 1/[σ2(Fo2) + (0.0585P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
2870 reflectionsΔρmax = 0.32 e Å3
153 parametersΔρmin = 0.26 e Å3
Crystal data top
C12H11N5γ = 105.510 (5)°
Mr = 225.26V = 574.73 (5) Å3
Triclinic, P1Z = 2
a = 7.5723 (3) ÅMo Kα radiation
b = 8.6376 (3) ŵ = 0.09 mm1
c = 9.7354 (5) ÅT = 173 K
α = 97.539 (2)°0.26 × 0.24 × 0.09 mm
β = 106.123 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1813 reflections with I > 2σ(I)
18045 measured reflectionsRint = 0.089
2870 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 0.98Δρmax = 0.32 e Å3
2870 reflectionsΔρmin = 0.26 e Å3
153 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2525 (2)0.40769 (18)0.78430 (15)0.0249 (3)
H10.33860.37780.86440.030*
N20.05923 (18)0.35498 (16)0.79587 (13)0.0289 (3)
N30.09589 (19)0.34989 (18)0.68237 (15)0.0373 (4)
C40.2452 (3)0.3038 (2)0.7301 (2)0.0421 (4)
H40.37250.29010.67530.051*
C50.1886 (3)0.2781 (2)0.8731 (2)0.0488 (4)
H50.26730.24520.92920.059*
C60.0106 (3)0.3128 (2)0.91191 (18)0.0382 (4)
H60.09400.30781.00040.046*
N70.32364 (18)0.58610 (15)0.80514 (12)0.0268 (3)
N80.50866 (18)0.66766 (16)0.89361 (13)0.0311 (3)
C90.5303 (3)0.8249 (2)0.89025 (18)0.0370 (4)
H90.64380.91110.94180.044*
C100.3645 (3)0.8456 (2)0.80116 (18)0.0420 (5)
H100.34570.94370.78190.050*
C110.2343 (3)0.6900 (2)0.74763 (18)0.0382 (4)
H110.10800.66120.68370.046*
C120.2556 (2)0.31567 (18)0.64180 (15)0.0237 (3)
N130.24020 (19)0.15718 (16)0.64034 (14)0.0323 (3)
C140.2372 (3)0.0666 (2)0.51714 (19)0.0405 (4)
H140.22390.04410.51370.049*
C150.2520 (3)0.1246 (2)0.3968 (2)0.0456 (5)
H150.24930.05580.31380.055*
C160.2709 (3)0.2866 (2)0.40071 (18)0.0421 (4)
H160.28290.33050.32020.050*
C170.2721 (2)0.3854 (2)0.52497 (16)0.0326 (4)
H170.28370.49600.52940.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0240 (8)0.0233 (8)0.0262 (7)0.0089 (6)0.0048 (6)0.0061 (6)
N20.0294 (8)0.0300 (7)0.0288 (7)0.0111 (6)0.0106 (6)0.0055 (5)
N30.0264 (8)0.0442 (9)0.0416 (8)0.0144 (7)0.0078 (6)0.0116 (7)
C40.0279 (9)0.0368 (10)0.0615 (12)0.0103 (8)0.0176 (8)0.0040 (8)
C50.0579 (13)0.0362 (10)0.0570.0060 (9)0.0400 (8)0.0013 (9)
C60.0504 (12)0.0311 (10)0.0332 (9)0.0075 (8)0.0206 (8)0.0036 (7)
N70.0300 (7)0.0242 (7)0.0237 (6)0.0098 (6)0.0043 (5)0.0039 (5)
N80.0312 (8)0.0285 (8)0.0274 (7)0.0044 (6)0.0069 (6)0.0018 (5)
C90.0483 (11)0.0250 (9)0.0334 (8)0.0043 (8)0.0155 (8)0.0023 (7)
C100.0662 (13)0.0265 (9)0.0376 (9)0.0196 (9)0.0186 (9)0.0082 (7)
C110.0457 (11)0.0321 (9)0.0368 (9)0.0210 (8)0.0053 (8)0.0078 (7)
C120.0180 (8)0.0244 (8)0.0268 (7)0.0076 (6)0.0049 (6)0.0029 (6)
N130.0332 (8)0.0259 (7)0.0347 (7)0.0081 (6)0.0103 (6)0.0018 (6)
C140.0416 (11)0.0320 (10)0.0421 (10)0.0088 (8)0.0128 (8)0.0035 (8)
C150.0471 (12)0.0455 (12)0.0410 (10)0.0153 (9)0.0141 (8)0.0009 (8)
C160.0478 (11)0.0506 (12)0.0324 (9)0.0205 (9)0.0162 (8)0.0076 (8)
C170.0371 (10)0.0318 (9)0.0321 (8)0.0152 (8)0.0119 (7)0.0076 (7)
Geometric parameters (Å, º) top
C1—N21.4527 (19)C9—C101.384 (2)
C1—N71.4559 (18)C9—H90.9300
C1—C121.515 (2)C10—C111.368 (2)
C1—H10.9800C10—H100.9300
N2—C61.346 (2)C11—H110.9300
N2—N31.3570 (17)C12—N131.3403 (19)
N3—C41.323 (2)C12—C171.375 (2)
C4—C51.404 (3)N13—C141.334 (2)
C4—H40.9300C14—C151.354 (3)
C5—C61.386 (2)C14—H140.9300
C5—H50.9300C15—C161.362 (3)
C6—H60.9300C15—H150.9300
N7—C111.3502 (19)C16—C171.382 (2)
N7—N81.3578 (16)C16—H160.9300
N8—C91.330 (2)C17—H170.9300
N2—C1—N7110.59 (12)N8—C9—H9123.9
N2—C1—C12110.54 (12)C10—C9—H9123.9
N7—C1—C12113.54 (12)C11—C10—C9104.88 (15)
N2—C1—H1107.3C11—C10—H10127.6
N7—C1—H1107.3C9—C10—H10127.6
C12—C1—H1107.3N7—C11—C10107.06 (15)
C6—N2—N3112.85 (14)N7—C11—H11126.5
C6—N2—C1127.42 (13)C10—C11—H11126.5
N3—N2—C1119.70 (12)N13—C12—C17122.77 (14)
C4—N3—N2104.30 (14)N13—C12—C1113.00 (12)
N3—C4—C5112.05 (16)C17—C12—C1124.22 (13)
N3—C4—H4124.0C14—N13—C12116.65 (14)
C5—C4—H4124.0N13—C14—C15124.63 (17)
C6—C5—C4104.55 (16)N13—C14—H14117.7
C6—C5—H5127.7C15—C14—H14117.7
C4—C5—H5127.7C14—C15—C16118.08 (17)
N2—C6—C5106.26 (15)C14—C15—H15121.0
N2—C6—H6126.9C16—C15—H15121.0
C5—C6—H6126.9C15—C16—C17119.63 (16)
C11—N7—N8111.66 (13)C15—C16—H16120.2
C11—N7—C1130.08 (13)C17—C16—H16120.2
N8—N7—C1118.25 (11)C12—C17—C16118.22 (15)
C9—N8—N7104.15 (13)C12—C17—H17120.9
N8—C9—C10112.24 (15)C16—C17—H17120.9
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N8i0.982.453.3974 (18)162
C10—H10···N13ii0.932.603.496 (2)161
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N8i0.982.453.3974 (18)162
C10—H10···N13ii0.932.603.496 (2)161
Symmetry codes: (i) x+1, y+1, z+2; (ii) x, y+1, z.
 

Acknowledgements

This work was supported by the research fund of Chungnam National University.

References

First citationAnderson, P. A., Astley, T., Hitchman, M. A., Keene, F. R., Moubaraki, B., Murray, K. S., Skelton, B. W., Tiekink, E. R. T., Toftlund, H. & White, A. H. (2000). J. Chem. Soc. Dalton Trans. pp. 3505–3512.  Web of Science CrossRef Google Scholar
First citationBruker (2002). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationHoffmann, A., Flörke, U., Schürmann, M. & Herres-Pawlis, S. (2010). Eur. J. Org. Chem. pp. 4136-4144.  Web of Science CSD CrossRef Google Scholar
First citationLiu, J.-C., Guo, G.-Z., Xiao, C.-H., Song, X.-Y. & Li, M. (2011). Acta Cryst. E67, m1691.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationPark, J.-E., Kang, S. K., Woo, J. O. & Son, K.-s. (2015). Dalton Trans. 44, 9964–9969.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationXiao, C.-H., Song, X.-Y., Sun, Z., Cao, P. & Pang, T. (2012). Acta Cryst. E68, m857.  CSD CrossRef IUCr Journals Google Scholar
First citationZhang, J., Li, A. & Hor, T. S. A. (2009). Organometallics, 28, 2935–2937.  Web of Science CSD CrossRef CAS Google Scholar

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