Trispyrazol-1-ylmethane

Kerscher, T.; Pust, P.; Betz, R.; Klüfers, P.; Mayer, P.

doi:10.1107/S1600536808041767

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o108

doi:10.1107/S1600536808041767

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Trispyrazol-1-ylmethane

Tobias Kerscher,^a Philipp Pust,^a Richard Betz,^a Peter Klüfers ^a ^* and Peter Mayer ^a

^aLudwig-Maximilians Universität, Department Chemie und Biochemie, Butenandtstrasse 5–13 (Haus D), 81377 München, Germany
^*Correspondence e-mail: kluef@cup.uni-muenchen.de

(Received 5 December 2008; accepted 9 December 2008; online 13 December 2008)

In the title compound, C₁₀H₁₀N₆, the three N atoms in the 2-positions of the pyrazole rings (the ones not bridging to the central C atom are acceptors for weak C—H⋯N contacts with H⋯N distances ranging from 2.49 to 2.59 Å). These furnish the formation of layers perpendicular to [100]. An orthorhombic polymorph of the title compound has already been described [McLauchlan et al. (2004 ). Acta Cryst. E60, o1419–o1420].

Related literature

The compound was prepared according to a published procedure (Reger et al., 2000 ). For a structure analysis of the orthorhombic polymorph, see: McLauchlan et al. (2004). For classification of hydrogen bonds, see: Bernstein et al. (1995 ); Etter et al. (1990 ).

Experimental

Crystal data

C₁₀H₁₀N₆
M_r = 214.24
Triclinic, $[P \overline 1]$
a = 7.7216 (9) Å
b = 7.8946 (6) Å
c = 9.4143 (10) Å
α = 99.292 (8)°
β = 100.023 (9)°
γ = 107.045 (9)°
V = 526.36 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 (2) K
0.34 × 0.20 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: analytical (de Meulenaer & Tompa, 1965 ) T_min = 0.975, T_max = 0.989
4340 measured reflections
2117 independent reflections
1054 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.082
S = 0.83
2117 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯N6ⁱ	1.00	2.49	3.451 (2)	161
C6—H6⋯N2ⁱⁱ	0.95	2.51	3.432 (2)	163
C1—H1⋯N4ⁱⁱⁱ	0.95	2.59	3.353 (2)	138
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, z; (iii) -x+1, -y, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, United Kingdom.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd., Abingdon, United Kingdom.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041767/bt2828sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041767/bt2828Isup2.hkl

checkCIF report

Comment top

The title compound was synthesized as a neutral tridentate ligand for coordination studies with transition metals.

In the molecule, three pyrazole moieties are N-bound to a central C atom (Fig. 1). The molecule is found in a non-symmetric conformation in the solid state. The highest possible symmetry C₃_v is broken by the ring containing N4 which is flipped by about 180°.

If only such contacts whose range falls by about 0.2 Å below the sum of van der Waals radii are considered, the crystal structure shows two C–H···N contacts. Infinite strands along [0 1 0] are formed by C6—H6···N2 contacts (Fig. 2). This pattern can be described according to graph-set analysis (Etter et al., 1990; Bernstein et al., 1995) with a C(7) descriptor on the unitary level. In addition, dimeric units are formed by interaction of the H atom of C10 and N6 (Fig. 3). These dimers can be described with a R²₂(8) descriptor on the unitary level. Both these described interactions give rise to tubes along [0 1 0].

Considering also contacts whose range falls below the sum of van der Waals radii by only about 0.1 Å, a second dimeric ring system is obvious with a R²₂(12) descriptor formed by the H atom of C1 and N4 (Fig. 4). In combination with the interactions described above, this second ring system features the formation of layers perpendicular to [1 0 0] (Fig. 5).

The molecular packing is shown in Figure 6.

Related literature top

The compound was prepared according to a published procedure (Reger et al., 2000). For a structure analysis of the orthorhombic polymorph, see: McLauchlan et al. (2004). For classification of hydrogen bonds, see: Bernstein et al. (1995); Etter et al. (1990).

Experimental top

The compound was prepared according to a published procedure (Reger et al., 2000) upon reaction of pyrazole and chloroform in alkaline aqueous media in the presence of a phase-transfer catalyst (tetrabutylammonium chloride).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
	Fig. 2. Strands formed by intermolecular C–H···N contacts in the crystal structure of the title compound, viewed along [1 0 0]. Symmetry codes: ⁱx, y - 1, z; ⁱⁱx, y + 1, z.
	Fig. 3. Dimeric units in the crystal structure of the title compound, formed by intermolecular C–H···N contacts whose ranges fall by about 0.2 Å below the sum of van der Waals radii of the corresponding atoms, viewed along [0 1 0]. Symmetry code: ⁱ -x + 1, -y + 1, -z + 1.
	Fig. 4. Dimeric units in the crystal structure of the title compound, formed by intermolecular C–H···N contacts whose ranges fall by about 0.1 Å below the sum of van der Waals radii of the corresponding atoms, viewed along [0 1 0]. Symmetry code: ⁱ -x + 1, -y, -z.
	Fig. 5. Schematic presentation of the layers formed by C—H···N contacts. Viewing direction approximately along [1 0 0].
	Fig. 6. The packing of the title compound, viewed along [0 1 0].

Tripyrazol-1-ylmethane top

Crystal data top

C₁₀H₁₀N₆	Z = 2
M_r = 214.24	F(000) = 224
Triclinic, P1	D_x = 1.352 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7216 (9) Å	Cell parameters from 1494 reflections
b = 7.8946 (6) Å	θ = 3.9–26.3°
c = 9.4143 (10) Å	µ = 0.09 mm⁻¹
α = 99.292 (8)°	T = 200 K
β = 100.023 (9)°	Block, colourless
γ = 107.045 (9)°	0.34 × 0.20 × 0.14 mm
V = 526.36 (10) Å³

Data collection top

Nonius KappaCCD diffractometer	2117 independent reflections
Radiation source: fine-focus sealed tube	1054 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 26.3°, θ_min = 3.9°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = −9→9
T_min = 0.975, T_max = 0.989	k = −9→9
4340 measured reflections	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 0.83	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
2117 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₀H₁₀N₆	γ = 107.045 (9)°
M_r = 214.24	V = 526.36 (10) Å³
Triclinic, P1	Z = 2
a = 7.7216 (9) Å	Mo Kα radiation
b = 7.8946 (6) Å	µ = 0.09 mm⁻¹
c = 9.4143 (10) Å	T = 200 K
α = 99.292 (8)°	0.34 × 0.20 × 0.14 mm
β = 100.023 (9)°

Data collection top

Nonius KappaCCD diffractometer	2117 independent reflections
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	1054 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.989	R_int = 0.030
4340 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 0.83	Δρ_max = 0.13 e Å⁻³
2117 reflections	Δρ_min = −0.18 e Å⁻³
145 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N5	0.36455 (16)	0.27051 (16)	0.27731 (13)	0.0334 (3)
N1	0.64066 (18)	0.38873 (17)	0.19270 (15)	0.0379 (3)
N6	0.28341 (18)	0.38479 (16)	0.33973 (14)	0.0409 (4)
N3	0.63243 (17)	0.18619 (16)	0.35571 (14)	0.0367 (3)
C10	0.5661 (2)	0.32745 (19)	0.31338 (16)	0.0334 (4)
H10	0.6125	0.4332	0.4005	0.040*
N2	0.78449 (19)	0.54772 (17)	0.22761 (17)	0.0539 (4)
N4	0.6002 (2)	0.02927 (18)	0.25599 (16)	0.0517 (4)
C7	0.1030 (2)	0.2989 (2)	0.28350 (19)	0.0491 (5)
H7	0.0086	0.3453	0.3072	0.059*
C4	0.7280 (2)	0.1888 (2)	0.49067 (19)	0.0489 (5)
H4	0.7652	0.2845	0.5766	0.059*
C9	0.2372 (2)	0.1197 (2)	0.18445 (18)	0.0444 (4)
H9	0.2619	0.0219	0.1283	0.053*
C8	0.0671 (2)	0.1351 (2)	0.18683 (18)	0.0497 (5)
H8	−0.0510	0.0511	0.1335	0.060*
C6	0.6797 (3)	−0.0647 (2)	0.3351 (2)	0.0582 (5)
H6	0.6807	−0.1830	0.2961	0.070*
C1	0.5986 (3)	0.3080 (2)	0.0478 (2)	0.0535 (5)
H1	0.5039	0.1956	−0.0004	0.064*
C2	0.7163 (3)	0.4167 (3)	−0.0163 (2)	0.0641 (6)
H2	0.7215	0.3975	−0.1175	0.077*
C3	0.8267 (3)	0.5611 (3)	0.0972 (3)	0.0656 (6)
H3	0.9231	0.6602	0.0842	0.079*
C5	0.7606 (3)	0.0283 (3)	0.4800 (2)	0.0599 (5)
H5	0.8254	−0.0117	0.5560	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N5	0.0307 (8)	0.0385 (8)	0.0336 (8)	0.0143 (6)	0.0090 (7)	0.0083 (6)
N1	0.0393 (8)	0.0377 (8)	0.0436 (9)	0.0164 (6)	0.0167 (7)	0.0141 (7)
N6	0.0413 (9)	0.0479 (8)	0.0409 (9)	0.0237 (7)	0.0141 (7)	0.0087 (7)
N3	0.0416 (8)	0.0411 (8)	0.0325 (8)	0.0213 (6)	0.0091 (7)	0.0085 (7)
C10	0.0334 (9)	0.0360 (9)	0.0325 (9)	0.0149 (7)	0.0079 (8)	0.0062 (7)
N2	0.0499 (9)	0.0383 (9)	0.0822 (12)	0.0167 (7)	0.0294 (9)	0.0183 (8)
N4	0.0703 (10)	0.0433 (9)	0.0505 (10)	0.0312 (8)	0.0175 (8)	0.0085 (8)
C7	0.0349 (11)	0.0708 (13)	0.0519 (12)	0.0241 (9)	0.0156 (9)	0.0242 (10)
C4	0.0463 (11)	0.0698 (13)	0.0410 (11)	0.0276 (9)	0.0133 (9)	0.0221 (9)
C9	0.0423 (11)	0.0436 (11)	0.0377 (11)	0.0079 (9)	0.0037 (9)	0.0004 (8)
C8	0.0372 (11)	0.0635 (13)	0.0390 (11)	0.0066 (9)	0.0030 (9)	0.0105 (9)
C6	0.0707 (13)	0.0529 (12)	0.0802 (16)	0.0404 (11)	0.0395 (13)	0.0348 (12)
C1	0.0595 (12)	0.0647 (12)	0.0408 (11)	0.0214 (10)	0.0187 (10)	0.0154 (10)
C2	0.0760 (15)	0.0869 (15)	0.0625 (14)	0.0479 (12)	0.0409 (13)	0.0427 (13)
C3	0.0698 (14)	0.0579 (13)	0.0996 (18)	0.0327 (11)	0.0552 (15)	0.0422 (13)
C5	0.0639 (13)	0.0855 (15)	0.0598 (14)	0.0454 (11)	0.0279 (12)	0.0449 (12)

Geometric parameters (Å, º) top

N5—C9	1.3516 (18)	C7—H7	0.9500
N5—N6	1.3565 (15)	C4—C5	1.354 (2)
N5—C10	1.4475 (18)	C4—H4	0.9500
N1—C1	1.348 (2)	C9—C8	1.357 (2)
N1—N2	1.3562 (16)	C9—H9	0.9500
N1—C10	1.4486 (17)	C8—H8	0.9500
N6—C7	1.3243 (19)	C6—C5	1.378 (2)
N3—C4	1.3473 (19)	C6—H6	0.9500
N3—N4	1.3566 (16)	C1—C2	1.351 (2)
N3—C10	1.4397 (18)	C1—H1	0.9500
C10—H10	1.0000	C2—C3	1.373 (3)
N2—C3	1.336 (2)	C2—H2	0.9500
N4—C6	1.330 (2)	C3—H3	0.9500
C7—C8	1.378 (2)	C5—H5	0.9500

C9—N5—N6	111.92 (13)	C5—C4—H4	126.7
C9—N5—C10	130.33 (14)	N5—C9—C8	106.78 (15)
N6—N5—C10	117.71 (12)	N5—C9—H9	126.6
C1—N1—N2	112.14 (13)	C8—C9—H9	126.6
C1—N1—C10	130.61 (13)	C9—C8—C7	105.04 (15)
N2—N1—C10	117.11 (13)	C9—C8—H8	127.5
C7—N6—N5	103.53 (12)	C7—C8—H8	127.5
C4—N3—N4	112.51 (13)	N4—C6—C5	112.70 (17)
C4—N3—C10	126.82 (14)	N4—C6—H6	123.7
N4—N3—C10	120.67 (13)	C5—C6—H6	123.7
N3—C10—N5	111.58 (11)	N1—C1—C2	107.29 (16)
N3—C10—N1	111.25 (11)	N1—C1—H1	126.4
N5—C10—N1	111.28 (12)	C2—C1—H1	126.4
N3—C10—H10	107.5	C1—C2—C3	104.79 (17)
N5—C10—H10	107.5	C1—C2—H2	127.6
N1—C10—H10	107.5	C3—C2—H2	127.6
C3—N2—N1	102.69 (15)	N2—C3—C2	113.08 (16)
C6—N4—N3	102.95 (14)	N2—C3—H3	123.5
N6—C7—C8	112.73 (15)	C2—C3—H3	123.5
N6—C7—H7	123.6	C4—C5—C6	105.23 (17)
C8—C7—H7	123.6	C4—C5—H5	127.4
N3—C4—C5	106.61 (16)	C6—C5—H5	127.4
N3—C4—H4	126.7

C9—N5—N6—C7	0.54 (15)	C10—N3—N4—C6	−179.60 (13)
C10—N5—N6—C7	178.36 (12)	N5—N6—C7—C8	−0.47 (17)
C4—N3—C10—N5	−113.15 (16)	N4—N3—C4—C5	0.17 (17)
N4—N3—C10—N5	66.40 (16)	C10—N3—C4—C5	179.76 (13)
C4—N3—C10—N1	121.92 (15)	N6—N5—C9—C8	−0.41 (17)
N4—N3—C10—N1	−58.53 (17)	C10—N5—C9—C8	−177.88 (13)
C9—N5—C10—N3	−51.4 (2)	N5—C9—C8—C7	0.10 (17)
N6—N5—C10—N3	131.27 (13)	N6—C7—C8—C9	0.24 (19)
C9—N5—C10—N1	73.53 (18)	N3—N4—C6—C5	−0.21 (18)
N6—N5—C10—N1	−103.82 (13)	N2—N1—C1—C2	−0.57 (19)
C1—N1—C10—N3	73.6 (2)	C10—N1—C1—C2	−176.15 (15)
N2—N1—C10—N3	−101.77 (14)	N1—C1—C2—C3	0.2 (2)
C1—N1—C10—N5	−51.5 (2)	N1—N2—C3—C2	−0.5 (2)
N2—N1—C10—N5	133.13 (13)	C1—C2—C3—N2	0.2 (2)
C1—N1—N2—C3	0.65 (17)	N3—C4—C5—C6	−0.28 (18)
C10—N1—N2—C3	176.88 (13)	N4—C6—C5—C4	0.3 (2)
C4—N3—N4—C6	0.02 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N6ⁱ	1.00	2.49	3.451 (2)	161
C6—H6···N2ⁱⁱ	0.95	2.51	3.432 (2)	163
C1—H1···N4ⁱⁱⁱ	0.95	2.59	3.353 (2)	138

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₆
M_r	214.24
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	7.7216 (9), 7.8946 (6), 9.4143 (10)
α, β, γ (°)	99.292 (8), 100.023 (9), 107.045 (9)
V (Å³)	526.36 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.34 × 0.20 × 0.14

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Analytical (de Meulenaer & Tompa, 1965)
T_min, T_max	0.975, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	4340, 2117, 1054
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.082, 0.83
No. of reflections	2117
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.18

Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N6ⁱ	1.00	2.49	3.451 (2)	161
C6—H6···N2ⁱⁱ	0.95	2.51	3.432 (2)	163
C1—H1···N4ⁱⁱⁱ	0.95	2.59	3.353 (2)	138

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

Acknowledgements

TK thanks the Hanns-Seidel-Stiftung for a PhD scholarship financed by the Bundesministerium für Bildung und Forschung.

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