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

Son, K.; Park, J.-E.; Kim, D.; Kang, S.K.

doi:10.1107/S2056989015013195

organic compounds

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Volume 71| Part 8| August 2015| Page o567

https://doi.org/10.1107/S2056989015013195

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

Kyung-sun Son,^a Jong-Eun Park,^a Daeyoung Kim ^a and Sung Kwon Kang ^a ^*

^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.

Keywords: crystal structure; pyrazolyl; pyridyl; C—H⋯N interactions; crystal structure.

CCDC reference: 1411603

1. Related literature

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 ).

2. Experimental

2.1. Crystal data

C₁₂H₁₁N₅
M_r = 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)
R_int = 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
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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 ).

Supporting information

CCDC reference: 1411603

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015013195/tk5373sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015013195/tk5373Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015013195/tk5373Isup3.cml

checkCIF report

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 U_iso(H) = 1.2U_eq(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

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 U_iso(H) = 1.2U_eq(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

	Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability displacement ellipsoids.
	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

C₁₂H₁₁N₅	Z = 2
M_r = 225.26	F(000) = 236
Triclinic, P1	D_x = 1.302 Mg m⁻³
a = 7.5723 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6376 (3) Å	Cell parameters from 2704 reflections
c = 9.7354 (5) Å	θ = 2.2–22.9°
α = 97.539 (2)°	µ = 0.09 mm⁻¹
β = 106.123 (4)°	T = 173 K
γ = 105.510 (5)°	Plate, colourless
V = 574.73 (5) Å³	0.26 × 0.24 × 0.09 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	R_int = 0.089
Radiation source: fine-focus sealed tube	θ_max = 28.4°, θ_min = 2.2°
φ and ω scans	h = −10→10
18045 measured reflections	k = −11→11
2870 independent reflections	l = −12→13
1813 reflections with I > 2σ(I)

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0585P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
2870 reflections	Δρ_max = 0.32 e Å⁻³
153 parameters	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₂H₁₁N₅	γ = 105.510 (5)°
M_r = 225.26	V = 574.73 (5) Å³
Triclinic, P1	Z = 2
a = 7.5723 (3) Å	Mo Kα radiation
b = 8.6376 (3) Å	µ = 0.09 mm⁻¹
c = 9.7354 (5) Å	T = 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 reflections	R_int = 0.089
2870 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 0.98	Δρ_max = 0.32 e Å⁻³
2870 reflections	Δρ_min = −0.26 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	0.2525 (2)	0.40769 (18)	0.78430 (15)	0.0249 (3)
H1	0.3386	0.3778	0.8644	0.030*
N2	0.05923 (18)	0.35498 (16)	0.79587 (13)	0.0289 (3)
N3	−0.09589 (19)	0.34989 (18)	0.68237 (15)	0.0373 (4)
C4	−0.2452 (3)	0.3038 (2)	0.7301 (2)	0.0421 (4)
H4	−0.3725	0.2901	0.6753	0.051*
C5	−0.1886 (3)	0.2781 (2)	0.8731 (2)	0.0488 (4)
H5	−0.2673	0.2452	0.9292	0.059*
C6	0.0106 (3)	0.3128 (2)	0.91191 (18)	0.0382 (4)
H6	0.0940	0.3078	1.0004	0.046*
N7	0.32364 (18)	0.58610 (15)	0.80514 (12)	0.0268 (3)
N8	0.50866 (18)	0.66766 (16)	0.89361 (13)	0.0311 (3)
C9	0.5303 (3)	0.8249 (2)	0.89025 (18)	0.0370 (4)
H9	0.6438	0.9111	0.9418	0.044*
C10	0.3645 (3)	0.8456 (2)	0.80116 (18)	0.0420 (5)
H10	0.3457	0.9437	0.7819	0.050*
C11	0.2343 (3)	0.6900 (2)	0.74763 (18)	0.0382 (4)
H11	0.1080	0.6612	0.6837	0.046*
C12	0.2556 (2)	0.31567 (18)	0.64180 (15)	0.0237 (3)
N13	0.24020 (19)	0.15718 (16)	0.64034 (14)	0.0323 (3)
C14	0.2372 (3)	0.0666 (2)	0.51714 (19)	0.0405 (4)
H14	0.2239	−0.0441	0.5137	0.049*
C15	0.2520 (3)	0.1246 (2)	0.3968 (2)	0.0456 (5)
H15	0.2493	0.0558	0.3138	0.055*
C16	0.2709 (3)	0.2866 (2)	0.40071 (18)	0.0421 (4)
H16	0.2829	0.3305	0.3202	0.050*
C17	0.2721 (2)	0.3854 (2)	0.52497 (16)	0.0326 (4)
H17	0.2837	0.4960	0.5294	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0240 (8)	0.0233 (8)	0.0262 (7)	0.0089 (6)	0.0048 (6)	0.0061 (6)
N2	0.0294 (8)	0.0300 (7)	0.0288 (7)	0.0111 (6)	0.0106 (6)	0.0055 (5)
N3	0.0264 (8)	0.0442 (9)	0.0416 (8)	0.0144 (7)	0.0078 (6)	0.0116 (7)
C4	0.0279 (9)	0.0368 (10)	0.0615 (12)	0.0103 (8)	0.0176 (8)	0.0040 (8)
C5	0.0579 (13)	0.0362 (10)	0.057	0.0060 (9)	0.0400 (8)	−0.0013 (9)
C6	0.0504 (12)	0.0311 (10)	0.0332 (9)	0.0075 (8)	0.0206 (8)	0.0036 (7)
N7	0.0300 (7)	0.0242 (7)	0.0237 (6)	0.0098 (6)	0.0043 (5)	0.0039 (5)
N8	0.0312 (8)	0.0285 (8)	0.0274 (7)	0.0044 (6)	0.0069 (6)	0.0018 (5)
C9	0.0483 (11)	0.0250 (9)	0.0334 (8)	0.0043 (8)	0.0155 (8)	0.0023 (7)
C10	0.0662 (13)	0.0265 (9)	0.0376 (9)	0.0196 (9)	0.0186 (9)	0.0082 (7)
C11	0.0457 (11)	0.0321 (9)	0.0368 (9)	0.0210 (8)	0.0053 (8)	0.0078 (7)
C12	0.0180 (8)	0.0244 (8)	0.0268 (7)	0.0076 (6)	0.0049 (6)	0.0029 (6)
N13	0.0332 (8)	0.0259 (7)	0.0347 (7)	0.0081 (6)	0.0103 (6)	0.0018 (6)
C14	0.0416 (11)	0.0320 (10)	0.0421 (10)	0.0088 (8)	0.0128 (8)	−0.0035 (8)
C15	0.0471 (12)	0.0455 (12)	0.0410 (10)	0.0153 (9)	0.0141 (8)	−0.0009 (8)
C16	0.0478 (11)	0.0506 (12)	0.0324 (9)	0.0205 (9)	0.0162 (8)	0.0076 (8)
C17	0.0371 (10)	0.0318 (9)	0.0321 (8)	0.0152 (8)	0.0119 (7)	0.0076 (7)

Geometric parameters (Å, º) top

C1—N2	1.4527 (19)	C9—C10	1.384 (2)
C1—N7	1.4559 (18)	C9—H9	0.9300
C1—C12	1.515 (2)	C10—C11	1.368 (2)
C1—H1	0.9800	C10—H10	0.9300
N2—C6	1.346 (2)	C11—H11	0.9300
N2—N3	1.3570 (17)	C12—N13	1.3403 (19)
N3—C4	1.323 (2)	C12—C17	1.375 (2)
C4—C5	1.404 (3)	N13—C14	1.334 (2)
C4—H4	0.9300	C14—C15	1.354 (3)
C5—C6	1.386 (2)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.362 (3)
C6—H6	0.9300	C15—H15	0.9300
N7—C11	1.3502 (19)	C16—C17	1.382 (2)
N7—N8	1.3578 (16)	C16—H16	0.9300
N8—C9	1.330 (2)	C17—H17	0.9300

N2—C1—N7	110.59 (12)	N8—C9—H9	123.9
N2—C1—C12	110.54 (12)	C10—C9—H9	123.9
N7—C1—C12	113.54 (12)	C11—C10—C9	104.88 (15)
N2—C1—H1	107.3	C11—C10—H10	127.6
N7—C1—H1	107.3	C9—C10—H10	127.6
C12—C1—H1	107.3	N7—C11—C10	107.06 (15)
C6—N2—N3	112.85 (14)	N7—C11—H11	126.5
C6—N2—C1	127.42 (13)	C10—C11—H11	126.5
N3—N2—C1	119.70 (12)	N13—C12—C17	122.77 (14)
C4—N3—N2	104.30 (14)	N13—C12—C1	113.00 (12)
N3—C4—C5	112.05 (16)	C17—C12—C1	124.22 (13)
N3—C4—H4	124.0	C14—N13—C12	116.65 (14)
C5—C4—H4	124.0	N13—C14—C15	124.63 (17)
C6—C5—C4	104.55 (16)	N13—C14—H14	117.7
C6—C5—H5	127.7	C15—C14—H14	117.7
C4—C5—H5	127.7	C14—C15—C16	118.08 (17)
N2—C6—C5	106.26 (15)	C14—C15—H15	121.0
N2—C6—H6	126.9	C16—C15—H15	121.0
C5—C6—H6	126.9	C15—C16—C17	119.63 (16)
C11—N7—N8	111.66 (13)	C15—C16—H16	120.2
C11—N7—C1	130.08 (13)	C17—C16—H16	120.2
N8—N7—C1	118.25 (11)	C12—C17—C16	118.22 (15)
C9—N8—N7	104.15 (13)	C12—C17—H17	120.9
N8—C9—C10	112.24 (15)	C16—C17—H17	120.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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.

Acknowledgements

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

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 8| August 2015| Page o567

https://doi.org/10.1107/S2056989015013195

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