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

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.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.123
• Data-to-parameter ratio = 18.8

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S1. Experimental

S1.1. Synthesis and crystallization

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.

S1.2. Refinement

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

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

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

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

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

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

	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

Crystal data

C12H11N5	Z = 2
Mr = 225.26	F(000) = 236
Triclinic, P1	Dx = 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) Å^3	0.26 × 0.24 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer	Rint = 0.089
Radiation source: fine-focus sealed tube	θmax = 28.4°, θmin = 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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0585P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
2870 reflections	Δρmax = 0.32 e Å^−3
153 parameters	Δρmin = −0.26 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N8^i	0.98	2.45	3.3974 (18)	162
C10—H10···N13^ii	0.93	2.60	3.496 (2)	161

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y+1, z.