Methyl 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4-carboxyl­ate

Bai, X.-G.; Feng, C.

doi:10.1107/S1600536814012380

Methyl 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4-carboxylate

The asymmetric unit of the title compound, C₈H₉N₅O₂, contains two independent molecules (A and B) in which the dihedral angles between the triazole and pyrazole rings are 4.80 (14) and 8.45 (16)°. In the crystal, molecules are linked by N—H

N hydrogen bonds into supramolecular independent A and B chains propagating along the b-axis direction. The crystal structure also features π–π stacking between the aromatic rings of adjacent chains, the centroid–centroid separations being 3.8001 (15), 3.8078 (17), 3.8190 (14) and 3.8421 (15) Å.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814012380/xu5793sup1.cif Contains datablocks I, New_Global_Publ_Block
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536814012380/xu5793Isup2.hkl Contains datablock I

CCDC reference: 1005571

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.053
wR factor = 0.153
Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          2 Check

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.962 Note
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.4 Note
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.4 Note
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      7.867 Check
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5 Why ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.599        125 Why ?
PLAT921_ALERT_1_C R1  in the CIF and FCF Differ by ...............     0.0012 Check
PLAT926_ALERT_1_C Reported and Calculated   R1 Differ by .........     0.0013 Check

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Why ?
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          43 %
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

Comment top

1,2,3-Triazole and its derivatives had attracted considerable attention for the past few decades due to their chemotherapeutical value. Many 1,2,3-triazoles are found to be potent antimicrobial and antiviral agents. Some of them have exhibited antiproliferative and anticancer activities (Danoun et al., 1998). Some 1,2,3-triazoles are used as DNA cleaving agents (Manfredini et al., 2000) and potassium channel activators. Prompted by the chemotherapeutic importance of 1,2,3-triazoles and its derivatives, we have synthesized the title compound and report its crystal structure herein.

The title compound, contains two crystallographically independent molecules and bond lengths and angles are in the normal range(Fig. 1). The dihedral angle between the triazole and pyrazole rings is 4.80 (14)° and 8.45 (16)° respectively. The crystal structure is stabilized by N–H···N hydrogen bonds linking molecules into one-dimensional chains running parallel to the b axis (Fig. 2). The structure is further stabilized by π···π stacking interactions, with centroid-to-centroid separations of 3.8001 (15)–3.8421 (15) Å.

Related literature top

For applications of 1,2,3-triazole and its derivatives, see: Danoun et al. (1998); Manfredini et al. (2000).

Experimental top

3-Azido-1H-pyrazole (20 mmol) was treated with ethyl acetoacetate (24 mmol) in methanol (75 ml) and the mixture was cooled to 273 K. Sodium methoxide (24 mmol) was added to the above mixture and stirred at ambient temperature for 24 h. After completion of the reaction, the mixture was poured on to ice cold water. The precipitated solid was filtered, washed with water and recrystallized from methanol, then 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4- carboxylic acid were obtained. A mixture of 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4- carboxylic acid (0.1 mmol) and Et₃N(0.2 mmol) in methanol (15 ml) was stirred at room temperature until the starting material disappeared. The resulting mixture was filtered and let the filtrate still for 24 h, colorless needle-like crystals were obtained.

Structure description top

For applications of 1,2,3-triazole and its derivatives, see: Danoun et al. (1998); Manfredini et al. (2000).

Computing details top

Data collection: FRAMBO (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. View of the one-dimensional chains of the title compound extending along the b axis. All the hydrogen atoms except those involved in hydrogen bonding have been omitted for clarity. Hydrogen bonds are shown as dashed lines.

Methyl 5-methyl-1-(1H-pyrazol-3-yl)-1H-1,2,3-triazole-4-carboxylate top

Crystal data top

C₈H₉N₅O₂	F(000) = 864
M_r = 207.20	D_x = 1.468 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1802 reflections
a = 15.4576 (6) Å	θ = 3.2–28.8°
b = 16.0945 (9) Å	µ = 0.11 mm⁻¹
c = 7.5348 (3) Å	T = 293 K
β = 90.079 (4)°	Needle, colorless
V = 1874.52 (15) Å³	0.15 × 0.12 × 0.10 mm
Z = 8

Data collection top

Bruker MWPC area-detector diffractometer	2312 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.014
Graphite monochromator	θ_max = 25.2°, θ_min = 2.9°
Detector resolution: 0 pixels mm^-1	h = −18→18
phi and ω scans	k = −13→19
5457 measured reflections	l = −9→8
3247 independent reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0605P)² + 0.760P] where P = (F_o² + 2F_c²)/3
3247 reflections	(Δ/σ)_max = 0.001
275 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₈H₉N₅O₂	V = 1874.52 (15) Å³
M_r = 207.20	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.4576 (6) Å	µ = 0.11 mm⁻¹
b = 16.0945 (9) Å	T = 293 K
c = 7.5348 (3) Å	0.15 × 0.12 × 0.10 mm
β = 90.079 (4)°

Data collection top

Bruker MWPC area-detector diffractometer	2312 reflections with I > 2σ(I)
5457 measured reflections	R_int = 0.014
3247 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.08	Δρ_max = 0.19 e Å⁻³
3247 reflections	Δρ_min = −0.21 e Å⁻³
275 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.02649 (13)	0.54949 (11)	0.2168 (3)	0.0420 (5)
N2	−0.00324 (14)	0.62920 (13)	0.2245 (3)	0.0541 (6)
N3	0.05838 (14)	0.67707 (13)	0.1660 (3)	0.0543 (6)
N4	−0.07242 (14)	0.36437 (14)	0.3301 (3)	0.0537 (6)
H4N	−0.0746	0.3111	0.3380	0.064*
N5	−0.00456 (14)	0.40638 (13)	0.2603 (3)	0.0530 (6)
N6	0.46882 (13)	0.32571 (12)	0.7645 (3)	0.0439 (5)
N7	0.49447 (14)	0.24550 (13)	0.7423 (3)	0.0526 (6)
N8	0.43181 (14)	0.19849 (13)	0.7993 (3)	0.0497 (6)
N9	0.57547 (15)	0.50986 (14)	0.6752 (3)	0.0583 (6)
H9N	0.5810	0.5630	0.6799	0.070*
N10	0.50816 (15)	0.46815 (13)	0.7472 (3)	0.0573 (6)
O1	0.21506 (14)	0.74272 (12)	0.0353 (3)	0.0738 (7)
O2	0.26259 (12)	0.61387 (11)	−0.0124 (3)	0.0578 (5)
O3	0.27863 (13)	0.13456 (11)	0.9465 (3)	0.0632 (6)
O4	0.22679 (11)	0.26408 (11)	0.9707 (3)	0.0539 (5)
C1	−0.02877 (16)	0.48505 (14)	0.2760 (3)	0.0418 (6)
C2	0.12793 (16)	0.62903 (15)	0.1203 (3)	0.0437 (6)
C3	0.10864 (15)	0.54705 (14)	0.1526 (3)	0.0404 (6)
C4	−0.13523 (18)	0.41433 (17)	0.3852 (4)	0.0551 (7)
H4	−0.1872	0.3978	0.4365	0.066*
C5	0.20503 (17)	0.66914 (16)	0.0457 (4)	0.0480 (6)
C6	−0.11000 (18)	0.49401 (16)	0.3534 (4)	0.0543 (7)
H6	−0.1399	0.5428	0.3775	0.065*
C7	0.15978 (18)	0.46989 (16)	0.1315 (4)	0.0597 (8)
H7A	0.1607	0.4401	0.2419	0.090*
H7B	0.2179	0.4837	0.0976	0.090*
H7C	0.1339	0.4358	0.0414	0.090*
C8	0.33943 (19)	0.64841 (19)	−0.0931 (5)	0.0678 (9)
H8A	0.3235	0.6797	−0.1966	0.102*
H8B	0.3778	0.6042	−0.1265	0.102*
H8C	0.3680	0.6843	−0.0098	0.102*
C9	0.52627 (17)	0.38975 (15)	0.7090 (3)	0.0450 (6)
C10	0.36599 (16)	0.24783 (15)	0.8580 (3)	0.0414 (6)
C11	0.38853 (16)	0.32974 (14)	0.8365 (3)	0.0429 (6)
C12	0.28750 (17)	0.20845 (16)	0.9289 (3)	0.0449 (6)
C13	0.6320 (2)	0.46024 (18)	0.5970 (4)	0.0648 (8)
H13	0.6826	0.4764	0.5399	0.078*
C14	0.6020 (2)	0.38078 (18)	0.6156 (4)	0.0655 (8)
H14	0.6271	0.3319	0.5746	0.079*
C15	0.14627 (18)	0.23064 (18)	1.0380 (4)	0.0608 (8)
H15A	0.1207	0.1951	0.9500	0.091*
H15B	0.1074	0.2754	1.0646	0.091*
H15C	0.1574	0.1992	1.1438	0.091*
C16	0.3426 (2)	0.40823 (17)	0.8776 (5)	0.0707 (9)
H16A	0.3720	0.4365	0.9724	0.106*
H16B	0.2844	0.3960	0.9130	0.106*
H16C	0.3418	0.4430	0.7742	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0437 (11)	0.0246 (11)	0.0577 (13)	0.0050 (9)	0.0077 (10)	−0.0008 (9)
N2	0.0512 (13)	0.0265 (11)	0.0846 (16)	0.0056 (10)	0.0190 (12)	0.0008 (11)
N3	0.0536 (13)	0.0297 (12)	0.0797 (16)	0.0022 (10)	0.0166 (12)	0.0000 (11)
N4	0.0569 (14)	0.0294 (12)	0.0749 (15)	−0.0065 (11)	0.0073 (12)	0.0048 (11)
N5	0.0510 (12)	0.0304 (12)	0.0775 (16)	−0.0007 (10)	0.0115 (11)	0.0028 (11)
N6	0.0485 (12)	0.0262 (11)	0.0569 (13)	0.0037 (9)	0.0037 (10)	−0.0012 (9)
N7	0.0490 (13)	0.0283 (12)	0.0806 (16)	0.0044 (10)	0.0112 (11)	−0.0007 (11)
N8	0.0476 (12)	0.0287 (11)	0.0729 (15)	0.0046 (10)	0.0064 (11)	0.0003 (10)
N9	0.0654 (15)	0.0321 (12)	0.0774 (16)	−0.0088 (11)	0.0060 (13)	0.0001 (11)
N10	0.0628 (14)	0.0295 (12)	0.0797 (16)	−0.0052 (11)	0.0098 (13)	−0.0016 (11)
O1	0.0751 (14)	0.0326 (11)	0.1139 (18)	−0.0044 (10)	0.0299 (13)	0.0005 (11)
O2	0.0488 (11)	0.0380 (11)	0.0865 (14)	−0.0008 (9)	0.0176 (10)	0.0030 (9)
O3	0.0636 (12)	0.0309 (10)	0.0953 (15)	−0.0041 (9)	0.0127 (11)	0.0010 (10)
O4	0.0461 (10)	0.0376 (10)	0.0780 (13)	0.0013 (8)	0.0139 (9)	0.0032 (9)
C1	0.0461 (14)	0.0291 (13)	0.0502 (14)	−0.0016 (11)	0.0014 (11)	−0.0004 (11)
C2	0.0452 (14)	0.0308 (13)	0.0552 (15)	0.0034 (11)	0.0046 (12)	−0.0029 (11)
C3	0.0443 (13)	0.0293 (13)	0.0477 (14)	0.0044 (11)	0.0051 (11)	0.0002 (11)
C4	0.0481 (15)	0.0448 (16)	0.0724 (19)	−0.0039 (13)	0.0119 (14)	−0.0014 (14)
C5	0.0517 (15)	0.0316 (14)	0.0608 (16)	0.0005 (12)	0.0060 (13)	−0.0007 (12)
C6	0.0529 (15)	0.0351 (15)	0.0750 (19)	0.0016 (13)	0.0137 (14)	−0.0020 (13)
C7	0.0509 (15)	0.0355 (15)	0.093 (2)	0.0072 (13)	0.0223 (15)	0.0047 (14)
C8	0.0522 (16)	0.0539 (19)	0.097 (2)	−0.0017 (15)	0.0252 (16)	0.0082 (17)
C9	0.0488 (15)	0.0295 (14)	0.0569 (16)	−0.0011 (11)	0.0011 (12)	0.0016 (11)
C10	0.0449 (13)	0.0299 (13)	0.0496 (15)	0.0036 (11)	0.0013 (11)	−0.0025 (11)
C11	0.0466 (14)	0.0277 (13)	0.0543 (15)	0.0027 (11)	0.0050 (11)	−0.0023 (11)
C12	0.0494 (15)	0.0340 (14)	0.0511 (15)	0.0001 (12)	−0.0010 (12)	0.0000 (12)
C13	0.0654 (18)	0.0450 (18)	0.084 (2)	−0.0062 (15)	0.0177 (16)	0.0031 (15)
C14	0.0701 (19)	0.0386 (16)	0.088 (2)	0.0007 (14)	0.0264 (17)	−0.0005 (15)
C15	0.0483 (16)	0.0502 (18)	0.084 (2)	−0.0022 (13)	0.0157 (15)	0.0002 (15)
C16	0.0689 (19)	0.0316 (15)	0.112 (3)	0.0045 (14)	0.0308 (18)	−0.0092 (16)

Geometric parameters (Å, º) top

N1—C3	1.360 (3)	C2—C3	1.374 (3)
N1—N2	1.364 (3)	C2—C5	1.468 (4)
N1—C1	1.416 (3)	C3—C7	1.481 (3)
N2—N3	1.302 (3)	C4—C6	1.362 (4)
N3—C2	1.369 (3)	C4—H4	0.9300
N4—C4	1.328 (3)	C6—H6	0.9300
N4—N5	1.355 (3)	C7—H7A	0.9600
N4—H4N	0.8600	C7—H7B	0.9600
N5—C1	1.326 (3)	C7—H7C	0.9600
N6—C11	1.357 (3)	C8—H8A	0.9600
N6—N7	1.361 (3)	C8—H8B	0.9600
N6—C9	1.424 (3)	C8—H8C	0.9600
N7—N8	1.302 (3)	C9—C14	1.375 (4)
N8—C10	1.365 (3)	C10—C11	1.373 (3)
N9—C13	1.323 (4)	C10—C12	1.470 (4)
N9—N10	1.352 (3)	C11—C16	1.482 (3)
N9—H9N	0.8600	C13—C14	1.368 (4)
N10—C9	1.324 (3)	C13—H13	0.9300
O1—C5	1.197 (3)	C14—H14	0.9300
O2—C5	1.333 (3)	C15—H15A	0.9600
O2—C8	1.446 (3)	C15—H15B	0.9600
O3—C12	1.204 (3)	C15—H15C	0.9600
O4—C12	1.335 (3)	C16—H16A	0.9600
O4—C15	1.448 (3)	C16—H16B	0.9600
C1—C6	1.392 (4)	C16—H16C	0.9600

C3—N1—N2	110.93 (19)	H7A—C7—H7B	109.5
C3—N1—C1	130.9 (2)	C3—C7—H7C	109.5
N2—N1—C1	118.16 (19)	H7A—C7—H7C	109.5
N3—N2—N1	107.18 (19)	H7B—C7—H7C	109.5
N2—N3—C2	109.0 (2)	O2—C8—H8A	109.5
C4—N4—N5	112.7 (2)	O2—C8—H8B	109.5
C4—N4—H4N	123.6	H8A—C8—H8B	109.5
N5—N4—H4N	123.6	O2—C8—H8C	109.5
C1—N5—N4	102.9 (2)	H8A—C8—H8C	109.5
C11—N6—N7	111.2 (2)	H8B—C8—H8C	109.5
C11—N6—C9	130.9 (2)	N10—C9—C14	113.1 (2)
N7—N6—C9	118.0 (2)	N10—C9—N6	119.6 (2)
N8—N7—N6	107.08 (19)	C14—C9—N6	127.3 (2)
N7—N8—C10	108.9 (2)	N8—C10—C11	109.3 (2)
C13—N9—N10	112.8 (2)	N8—C10—C12	118.9 (2)
C13—N9—H9N	123.6	C11—C10—C12	131.8 (2)
N10—N9—H9N	123.6	N6—C11—C10	103.5 (2)
C9—N10—N9	102.9 (2)	N6—C11—C16	124.3 (2)
C5—O2—C8	115.5 (2)	C10—C11—C16	132.2 (2)
C12—O4—C15	116.0 (2)	O3—C12—O4	123.8 (2)
N5—C1—C6	113.0 (2)	O3—C12—C10	124.1 (2)
N5—C1—N1	120.0 (2)	O4—C12—C10	112.2 (2)
C6—C1—N1	126.9 (2)	N9—C13—C14	107.1 (3)
N3—C2—C3	109.1 (2)	N9—C13—H13	126.4
N3—C2—C5	119.1 (2)	C14—C13—H13	126.4
C3—C2—C5	131.8 (2)	C13—C14—C9	104.1 (3)
N1—C3—C2	103.8 (2)	C13—C14—H14	128.0
N1—C3—C7	124.1 (2)	C9—C14—H14	128.0
C2—C3—C7	132.1 (2)	O4—C15—H15A	109.5
N4—C4—C6	107.8 (2)	O4—C15—H15B	109.5
N4—C4—H4	126.1	H15A—C15—H15B	109.5
C6—C4—H4	126.1	O4—C15—H15C	109.5
O1—C5—O2	123.5 (3)	H15A—C15—H15C	109.5
O1—C5—C2	124.4 (2)	H15B—C15—H15C	109.5
O2—C5—C2	112.0 (2)	C11—C16—H16A	109.5
C4—C6—C1	103.6 (2)	C11—C16—H16B	109.5
C4—C6—H6	128.2	H16A—C16—H16B	109.5
C1—C6—H6	128.2	C11—C16—H16C	109.5
C3—C7—H7A	109.5	H16A—C16—H16C	109.5
C3—C7—H7B	109.5	H16B—C16—H16C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···N3ⁱ	0.86	2.17	3.022 (3)	170
N9—H9N···N8ⁱⁱ	0.86	2.20	3.044 (3)	169

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+3/2.