Bis(3,5-dimethyl­pyrazol-1-yl)acetic acid

Nguyen, Q.T.; Jeong, J.H.

doi:10.1107/S1600536807066391

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o319

https://doi.org/10.1107/S1600536807066391

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Bis(3,5-dimethylpyrazol-1-yl)acetic acid

Quang Trung Nguyen ^a and Jong Hwa Jeong ^a ^*

^aDepartment of Chemistry, Kyungpook National University, Taegu 702-701, Republic of Korea
^*Correspondence e-mail: jeongjh@knu.ac.kr

(Received 18 October 2007; accepted 10 December 2007; online 21 December 2007)

In the title compound, C₁₂H₁₆N₄O₂, the dihedral angle between the two pyrazole rings is 78.17 (7)°. Intermolecular O—H⋯N hydrogen bonds link the molecules into one-dimensional chains along the c axis.

Related literature

For the synthesis of bis(3,5-dimethylpyrazol-1-yl)acetic acid, see: Otero et al. (2004 ).

Experimental

Crystal data

C₁₂H₁₆N₄O₂
M_r = 248.29
Monoclinic, P 2₁ /c
a = 8.4317 (8) Å
b = 18.8569 (16) Å
c = 8.6083 (7) Å
β = 114.576 (7)°
V = 1244.69 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.50 × 0.40 × 0.35 mm

Data collection

Enraf–Nonius CAD-4 four-circle diffractometer
Absorption correction: none
2526 measured reflections
2305 independent reflections
1924 reflections with I > 2σ(I)
R_int = 0.007
3 standard reflections frequency: 60 min intensity decay: 0.2%

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.120
S = 1.08
2305 reflections
171 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 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
O2—H2⋯N4ⁱ	0.97 (3)	1.71 (3)	2.676 (2)	172 (3)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD (McArdle, 1999 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807066391/kj2077sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066391/kj2077Isup2.hkl

checkCIF report

Comment top

The title compound, C₁₂H₁₆N₄O₂, was synthesized through the protonation of bis(3,5-dimethylpyrazol-1-yl)acetate. This compound was used to prepare 2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol, which was the reagent for the NNO monoanionic heteroscorpionate ligand (Otero et al., 2004). Intermolecular O—H···N hydrogen bonds link the molecules into one-dimensional chains along the c axis (Fig. 2 and Table 1). The dihedral angle between the two pyrazol rings is 78.17 (7)°.

Related literature top

For the synthesis of bis(3,5-dimethylpyrazol-1-yl)acetic acid, see: Otero et al. (2004).

Experimental top

The title compound was synthesized according to the literature procedure (Otero et al., 2004). Single crystals of the compound suitable for X-ray analysis were obtained by diffusion of ether into a THF solution.

Structure description top

For the synthesis of bis(3,5-dimethylpyrazol-1-yl)acetic acid, see: Otero et al. (2004).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD (McArdle, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. A view of the title compound. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A packing diagram of the title compound viewed approximately perpendicular to the bc plane. Hydrogen bonds are indicated by dashed lines. H atoms of the methyl groups were omitted for clarity.

Bis(3,5-dimethylpyrazol-1-yl)acetic acid top

Crystal data top

C₁₂H₁₆N₄O₂	F(000) = 528
M_r = 248.29	D_x = 1.325 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.4317 (8) Å	θ = 9.3–11.6°
b = 18.8569 (16) Å	µ = 0.09 mm⁻¹
c = 8.6083 (7) Å	T = 293 K
β = 114.576 (7)°	Block, colourless
V = 1244.69 (19) Å³	0.50 × 0.40 × 0.35 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 four-circle diffractometer	R_int = 0.007
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.8°
Graphite monochromator	h = 0→10
ω/2θ scans	k = 0→22
2526 measured reflections	l = −10→9
2305 independent reflections	3 standard reflections every 60 min
1924 reflections with I > 2σ(I)	intensity decay: 0.2%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0687P)² + 0.2835P] where P = (F_o² + 2F_c²)/3
2305 reflections	(Δ/σ)_max < 0.001
171 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₂H₁₆N₄O₂	V = 1244.69 (19) Å³
M_r = 248.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4317 (8) Å	µ = 0.09 mm⁻¹
b = 18.8569 (16) Å	T = 293 K
c = 8.6083 (7) Å	0.50 × 0.40 × 0.35 mm
β = 114.576 (7)°

Data collection top

Enraf–Nonius CAD-4 four-circle diffractometer	R_int = 0.007
2526 measured reflections	3 standard reflections every 60 min
2305 independent reflections	intensity decay: 0.2%
1924 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.23 e Å⁻³
2305 reflections	Δρ_min = −0.26 e Å⁻³
171 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.01420 (18)	0.19070 (8)	0.40486 (18)	0.0328 (3)
H1A	0.0399	0.2115	0.3135	0.039*
N1	0.17999 (15)	0.17643 (7)	0.54704 (15)	0.0337 (3)
N2	0.19887 (16)	0.18728 (7)	0.71087 (15)	0.0363 (3)
C2	0.36285 (19)	0.16958 (8)	0.80788 (19)	0.0342 (3)
C3	0.4348 (2)	0.17514 (10)	0.9979 (2)	0.0444 (4)
H3A	0.3425	0.1868	1.0313	0.067*
H3B	0.5223	0.2115	1.0366	0.067*
H3C	0.4858	0.1306	1.0481	0.067*
C4	0.4481 (2)	0.14729 (9)	0.7074 (2)	0.0389 (4)
H4A	0.5633	0.1323	0.7462	0.047*
C5	0.3290 (2)	0.15185 (8)	0.5408 (2)	0.0359 (4)
C6	0.3447 (2)	0.13593 (11)	0.3783 (2)	0.0521 (5)
H6A	0.2877	0.0918	0.3328	0.078*
H6B	0.4657	0.1326	0.4000	0.078*
H6C	0.2908	0.1732	0.2975	0.078*
N3	−0.08641 (16)	0.12648 (7)	0.33639 (15)	0.0332 (3)
N4	−0.10877 (16)	0.10578 (7)	0.17637 (15)	0.0341 (3)
C7	−0.1927 (2)	0.04440 (8)	0.1485 (2)	0.0380 (4)
C8	−0.2378 (3)	0.00510 (10)	−0.0153 (2)	0.0554 (5)
H8A	−0.1900	0.0296	−0.0838	0.083*
H8B	−0.3623	0.0023	−0.0763	0.083*
H8C	−0.1900	−0.0419	0.0089	0.083*
C9	−0.2243 (2)	0.02556 (9)	0.2895 (2)	0.0435 (4)
H9A	−0.2817	−0.0150	0.3004	0.052*
C10	−0.15508 (19)	0.07794 (8)	0.4088 (2)	0.0379 (4)
C11	−0.1488 (3)	0.08317 (11)	0.5835 (2)	0.0524 (5)
H11A	−0.0345	0.0981	0.6619	0.079*
H11B	−0.1743	0.0377	0.6178	0.079*
H11C	−0.2335	0.1171	0.5838	0.079*
C12	−0.0880 (2)	0.24644 (8)	0.45592 (19)	0.0379 (4)
O1	−0.22573 (17)	0.23504 (8)	0.4587 (2)	0.0652 (4)
O2	−0.00521 (16)	0.30749 (6)	0.49036 (15)	0.0442 (3)
H2	−0.052 (3)	0.3382 (14)	0.551 (3)	0.081 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0339 (8)	0.0349 (8)	0.0287 (7)	−0.0003 (6)	0.0123 (6)	0.0000 (6)
N1	0.0312 (6)	0.0405 (7)	0.0293 (6)	0.0031 (5)	0.0126 (5)	−0.0017 (5)
N2	0.0350 (7)	0.0436 (7)	0.0308 (6)	0.0018 (5)	0.0141 (5)	−0.0015 (5)
C2	0.0332 (8)	0.0334 (7)	0.0345 (8)	−0.0007 (6)	0.0126 (6)	0.0020 (6)
C3	0.0430 (9)	0.0520 (10)	0.0347 (8)	0.0046 (7)	0.0127 (7)	0.0033 (7)
C4	0.0326 (8)	0.0428 (8)	0.0412 (8)	0.0068 (6)	0.0154 (6)	0.0044 (7)
C5	0.0360 (8)	0.0351 (8)	0.0395 (8)	0.0031 (6)	0.0187 (7)	0.0009 (6)
C6	0.0519 (10)	0.0673 (12)	0.0419 (9)	0.0139 (9)	0.0242 (8)	−0.0018 (8)
N3	0.0350 (7)	0.0345 (7)	0.0312 (6)	−0.0013 (5)	0.0149 (5)	0.0007 (5)
N4	0.0360 (7)	0.0339 (7)	0.0306 (6)	−0.0017 (5)	0.0121 (5)	−0.0009 (5)
C7	0.0373 (8)	0.0312 (7)	0.0394 (8)	−0.0002 (6)	0.0100 (6)	0.0009 (6)
C8	0.0637 (12)	0.0465 (10)	0.0476 (10)	−0.0099 (9)	0.0147 (9)	−0.0102 (8)
C9	0.0408 (9)	0.0371 (8)	0.0502 (10)	−0.0053 (7)	0.0165 (7)	0.0064 (7)
C10	0.0333 (8)	0.0412 (9)	0.0399 (8)	0.0027 (6)	0.0160 (6)	0.0077 (6)
C11	0.0513 (10)	0.0659 (12)	0.0472 (10)	−0.0005 (9)	0.0277 (8)	0.0084 (8)
C12	0.0355 (8)	0.0407 (8)	0.0332 (8)	0.0044 (6)	0.0101 (6)	−0.0002 (6)
O1	0.0395 (7)	0.0564 (8)	0.1023 (12)	0.0023 (6)	0.0320 (7)	−0.0173 (8)
O2	0.0562 (7)	0.0363 (6)	0.0463 (6)	0.0003 (5)	0.0276 (6)	−0.0049 (5)

Geometric parameters (Å, º) top

C1—N1	1.4496 (18)	N3—C10	1.3644 (19)
C1—N3	1.4551 (19)	N3—N4	1.3673 (17)
C1—C12	1.535 (2)	N4—C7	1.325 (2)
C1—H1A	0.9800	C7—C9	1.392 (2)
N1—C5	1.3608 (19)	C7—C8	1.496 (2)
N1—N2	1.3673 (17)	C8—H8A	0.9600
N2—C2	1.327 (2)	C8—H8B	0.9600
C2—C4	1.400 (2)	C8—H8C	0.9600
C2—C3	1.493 (2)	C9—C10	1.369 (2)
C3—H3A	0.9600	C9—H9A	0.9300
C3—H3B	0.9600	C10—C11	1.486 (2)
C3—H3C	0.9600	C11—H11A	0.9600
C4—C5	1.369 (2)	C11—H11B	0.9600
C4—H4A	0.9300	C11—H11C	0.9600
C5—C6	1.489 (2)	C12—O1	1.1910 (19)
C6—H6A	0.9600	C12—O2	1.315 (2)
C6—H6B	0.9600	O2—H2	0.97 (3)
C6—H6C	0.9600

N1—C1—N3	112.50 (12)	H6B—C6—H6C	109.5
N1—C1—C12	110.15 (11)	C10—N3—N4	111.21 (12)
N3—C1—C12	112.56 (12)	C10—N3—C1	131.29 (12)
N1—C1—H1A	107.1	N4—N3—C1	117.30 (11)
N3—C1—H1A	107.1	C7—N4—N3	105.74 (12)
C12—C1—H1A	107.1	N4—C7—C9	110.26 (14)
C5—N1—N2	112.22 (12)	N4—C7—C8	120.71 (15)
C5—N1—C1	127.72 (12)	C9—C7—C8	129.02 (15)
N2—N1—C1	120.06 (11)	C7—C8—H8A	109.5
C2—N2—N1	104.80 (12)	C7—C8—H8B	109.5
N2—C2—C4	110.80 (13)	H8A—C8—H8B	109.5
N2—C2—C3	120.94 (14)	C7—C8—H8C	109.5
C4—C2—C3	128.26 (14)	H8A—C8—H8C	109.5
C2—C3—H3A	109.5	H8B—C8—H8C	109.5
C2—C3—H3B	109.5	C10—C9—C7	107.06 (14)
H3A—C3—H3B	109.5	C10—C9—H9A	126.5
C2—C3—H3C	109.5	C7—C9—H9A	126.5
H3A—C3—H3C	109.5	N3—C10—C9	105.72 (14)
H3B—C3—H3C	109.5	N3—C10—C11	125.07 (15)
C5—C4—C2	106.67 (14)	C9—C10—C11	129.20 (15)
C5—C4—H4A	126.7	C10—C11—H11A	109.5
C2—C4—H4A	126.7	C10—C11—H11B	109.5
N1—C5—C4	105.51 (13)	H11A—C11—H11B	109.5
N1—C5—C6	123.35 (14)	C10—C11—H11C	109.5
C4—C5—C6	131.13 (15)	H11A—C11—H11C	109.5
C5—C6—H6A	109.5	H11B—C11—H11C	109.5
C5—C6—H6B	109.5	O1—C12—O2	125.75 (15)
H6A—C6—H6B	109.5	O1—C12—C1	123.40 (15)
C5—C6—H6C	109.5	O2—C12—C1	110.83 (13)
H6A—C6—H6C	109.5	C12—O2—H2	110.3 (15)

N3—C1—N1—C5	78.86 (18)	N1—C1—N3—N4	−111.63 (13)
C12—C1—N1—C5	−154.68 (15)	C12—C1—N3—N4	123.21 (13)
N3—C1—N1—N2	−100.73 (15)	C10—N3—N4—C7	0.43 (16)
C12—C1—N1—N2	25.73 (18)	C1—N3—N4—C7	175.80 (12)
C5—N1—N2—C2	0.43 (17)	N3—N4—C7—C9	−0.02 (16)
C1—N1—N2—C2	−179.92 (13)	N3—N4—C7—C8	−179.15 (14)
N1—N2—C2—C4	−0.27 (17)	N4—C7—C9—C10	−0.39 (18)
N1—N2—C2—C3	179.31 (14)	C8—C7—C9—C10	178.65 (16)
N2—C2—C4—C5	0.02 (19)	N4—N3—C10—C9	−0.66 (17)
C3—C2—C4—C5	−179.52 (15)	C1—N3—C10—C9	−175.19 (14)
N2—N1—C5—C4	−0.42 (17)	N4—N3—C10—C11	178.27 (14)
C1—N1—C5—C4	179.97 (14)	C1—N3—C10—C11	3.7 (3)
N2—N1—C5—C6	−179.67 (15)	C7—C9—C10—N3	0.62 (18)
C1—N1—C5—C6	0.7 (2)	C7—C9—C10—C11	−178.25 (16)
C2—C4—C5—N1	0.24 (17)	N1—C1—C12—O1	−117.82 (17)
C2—C4—C5—C6	179.40 (17)	N3—C1—C12—O1	8.6 (2)
N1—C1—N3—C10	62.62 (19)	N1—C1—C12—O2	63.93 (16)
C12—C1—N3—C10	−62.5 (2)	N3—C1—C12—O2	−169.64 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N4ⁱ	0.97 (3)	1.71 (3)	2.676 (2)	172 (3)

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₄O₂
M_r	248.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.4317 (8), 18.8569 (16), 8.6083 (7)
β (°)	114.576 (7)
V (Å³)	1244.69 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.40 × 0.35

Data collection
Diffractometer	Enraf–Nonius CAD-4 four-circle
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2526, 2305, 1924
R_int	0.007
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.120, 1.08
No. of reflections	2305
No. of parameters	171
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.26

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD (McArdle, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N4ⁱ	0.97 (3)	1.71 (3)	2.676 (2)	172 (3)

Symmetry code: (i) x, −y+1/2, z+1/2.

References

Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
McArdle, P. (1999). XCAD. National University of Ireland, Galway, Ireland. Google Scholar
Otero, A., Fernández-Baeza, J., Antiñolo, A., Tejeda, J., Lara-Sánchez, A., Sánchez-Barba, L. & Rodríguez, A. M. (2004). Eur. J. Inorg. Chem. pp. 260–266. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

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Volume 64| Part 1| January 2008| Page o319

https://doi.org/10.1107/S1600536807066391

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