3(5),4-Dimethyl- and 3,4,5-trimethylpyrazole at 200 K. X-ray crystallography and quantum-chemical analysis

The crystal and molecular structures of 3(5),4-dimethylpyrazole, C₅H₈N₂, (I), and of 3,4,5-trimethylpyrazole, C₆H₁₀N₂, (II), have been determined at 200 K. In (I) the 4,5-dimethylpyrazole tautomer is present in the solid state and the six independent molecules in the asymmetric unit form trimers via NH...N hydrogen bonds related by a pseudo centre of symmetry. The asymmetric unit of (II) contains one and a half molecules: these exhibit NH proton disorder and are hydrogen bonded to each other via their respective NH groups to form chains. Ab initio calculations at HF and B3LYP/6-31G** levels indicate that the 3,4-dimethylpyrazole tautomer is more stable than the 4,5-dimethylpyrazole tautomer by only approximately 0.5  kcal  mol⁻¹ (1 kcal mol⁻¹ = 4.184 kJ mol⁻¹).

Computing details

For both compounds, data collection: Philips PW1100 (Hornstra & Vossers, 1973); cell refinement: LSUCRE (Appleman, 1984); data reduction: xtal_DIFDAT_SORTRF_ADDREF; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: xtal_CRYLSQ (Hall et al., 1997); molecular graphics: xtal_ORTEP; software used to prepare material for publication: xtal_BONDLA_CIFIO.

(Ib) 4,5-dimethylpyrazole

Crystal data

C5H8N2	Z = 12
Mr = 96.13	F(000) = 624
Triclinic, P1	Dx = 1.109 Mg m^−3
Hall symbol: -P 1	Melting point: 331 K
a = 14.417 (1) Å	Cu Kα radiation, λ = 1.5418 Å
b = 12.020 (1) Å	Cell parameters from 74 reflections
c = 12.042 (1) Å	θ = 4.2–44.1°
α = 119.990 (7)°	µ = 0.56 mm^−1
β = 105.991 (7)°	T = 200 K
γ = 87.224 (10)°	Sheet, colourless
V = 1727.5 (3) Å^3	0.60 × 0.40 × 0.17 mm

Data collection

Philips PW1100 diffractometer	Rint = 0
Radiation source: xray_tube	θmax = 64.8°, θmin = 3.2°
Graphite monochromator	h = −16→16
ω/2θ scans	k = −13→12
5733 measured reflections	l = 0→12
5733 independent reflections	2 standard reflections every 90 min
4543 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F	0 constraints
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.075	w = k/[(A + B Fo)^2(C + D(sinθ)/λ)]
wR(F^2) = 0.105	(Δ/σ)max = 0.03
S = 0.86	Δρmax = 0.30 e Å^−3
4543 reflections	Δρmin = −0.42 e Å^−3
571 parameters	Extinction correction: Zachariasen, Eq22_p292_"Cryst._Comp."_Munksgaard_1970
0 restraints	Extinction coefficient: 8.4E02 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N11	0.1263 (2)	0.9490 (2)	0.8749 (2)	0.0450 (10)
N12	0.1136 (2)	0.9932 (2)	0.7889 (2)	0.0506 (10)
C13	0.1079 (2)	1.1196 (3)	0.8621 (3)	0.0491 (12)
C14	0.1158 (2)	1.1562 (3)	0.9940 (3)	0.0451 (11)
C15	0.1278 (2)	1.0442 (3)	0.9983 (3)	0.0427 (10)
C16	0.1128 (3)	1.2893 (3)	1.1064 (4)	0.0668 (15)
C17	0.1391 (3)	1.0208 (4)	1.1120 (3)	0.0616 (16)
N21	0.1299 (2)	0.5914 (2)	0.6354 (2)	0.0452 (10)
N22	0.1363 (2)	0.6765 (2)	0.7654 (2)	0.0484 (10)
C23	0.1340 (2)	0.6044 (3)	0.8202 (3)	0.0505 (12)
C24	0.1265 (2)	0.4734 (3)	0.7272 (3)	0.0439 (11)
C25	0.1241 (2)	0.4697 (2)	0.6105 (3)	0.0420 (10)
C26	0.1226 (3)	0.3620 (4)	0.7502 (5)	0.0667 (17)
C27	0.1155 (3)	0.3567 (3)	0.4732 (3)	0.0626 (15)
N31	0.1239 (2)	0.8333 (2)	0.5196 (2)	0.0442 (9)
N32	0.1331 (2)	0.7061 (2)	0.4767 (2)	0.0512 (11)
C33	0.1394 (3)	0.6544 (3)	0.3524 (3)	0.0505 (12)
C34	0.1343 (2)	0.7467 (3)	0.3136 (3)	0.0441 (11)
C35	0.1249 (2)	0.8601 (2)	0.4235 (3)	0.0408 (10)
C36	0.1388 (4)	0.7278 (4)	0.1823 (4)	0.0657 (18)
C37	0.1167 (3)	0.9936 (3)	0.4459 (4)	0.0554 (13)
N41	0.3811 (2)	−0.0505 (2)	0.1160 (2)	0.0446 (10)
N42	0.3864 (2)	−0.0946 (2)	0.2009 (2)	0.0483 (10)
C43	0.3902 (2)	−0.2224 (3)	0.1292 (3)	0.0494 (12)
C44	0.3875 (2)	−0.2608 (2)	−0.0010 (3)	0.0452 (10)
C45	0.3816 (2)	−0.1483 (3)	−0.0062 (3)	0.0439 (11)
C46	0.3901 (3)	−0.3945 (3)	−0.1122 (4)	0.0696 (15)
C47	0.3755 (3)	−0.1264 (4)	−0.1193 (4)	0.0640 (16)
N51	0.3696 (2)	0.3030 (2)	0.3534 (2)	0.0463 (10)
N52	0.3767 (2)	0.2238 (2)	0.2280 (2)	0.0519 (11)
C53	0.3812 (3)	0.2986 (3)	0.1774 (3)	0.0524 (13)
C54	0.3778 (2)	0.4279 (3)	0.2703 (3)	0.0446 (11)
C55	0.3703 (2)	0.4253 (2)	0.3809 (3)	0.0412 (10)
C56	0.3819 (4)	0.5420 (4)	0.2518 (5)	0.0706 (19)
C57	0.3642 (3)	0.5338 (3)	0.5135 (3)	0.0578 (13)
N61	0.3736 (2)	0.0632 (2)	0.4689 (2)	0.0459 (10)
N62	0.3595 (2)	0.1887 (2)	0.5099 (2)	0.0520 (11)
C63	0.3517 (2)	0.2405 (3)	0.6341 (3)	0.0487 (12)
C64	0.3602 (2)	0.1496 (3)	0.6739 (3)	0.0432 (11)
C65	0.3740 (2)	0.0374 (3)	0.5654 (3)	0.0415 (10)
C66	0.3551 (3)	0.1666 (4)	0.8041 (3)	0.0612 (16)
C67	0.3876 (3)	−0.0944 (3)	0.5478 (4)	0.0599 (14)
H11	0.122 (3)	0.866 (4)	0.842 (4)	0.031 (9)*
H13	0.103 (4)	1.170 (6)	0.821 (6)	0.069 (16)*
H161	0.112 (4)	1.354 (6)	1.068 (6)	0.074 (17)*
H162	0.058 (5)	1.294 (6)	1.146 (7)	0.081 (18)*
H163	0.169 (5)	1.318 (6)	1.182 (6)	0.073 (17)*
H171	0.166 (5)	0.943 (7)	1.097 (7)	0.082 (19)*
H172	0.199 (5)	1.090 (7)	1.196 (7)	0.09 (2)*
H173	0.092 (5)	1.032 (7)	1.140 (7)	0.09 (2)*
H21	0.137 (4)	0.631 (5)	0.582 (5)	0.057 (13)*
H23	0.132 (4)	0.663 (5)	0.916 (6)	0.062 (14)*
H261	0.117 (7)	0.404 (10)	0.851 (11)	0.15 (4)*
H262	0.062 (6)	0.294 (8)	0.686 (8)	0.10 (2)*
H263	0.173 (4)	0.308 (6)	0.736 (5)	0.062 (14)*
H271	0.085 (4)	0.366 (6)	0.395 (7)	0.075 (17)*
H272	0.183 (6)	0.322 (7)	0.463 (7)	0.10 (2)*
H273	0.077 (5)	0.293 (7)	0.461 (7)	0.09 (2)*
H31	0.119 (6)	0.892 (8)	0.629 (8)	0.12 (3)*
H33	0.148 (3)	0.574 (4)	0.306 (4)	0.025 (8)*
H361	0.127 (6)	0.627 (8)	0.118 (8)	0.12 (3)*
H362	0.087 (5)	0.759 (6)	0.139 (7)	0.079 (18)*
H363	0.190 (5)	0.778 (7)	0.195 (7)	0.08 (2)*
H371	0.128 (7)	1.065 (9)	0.549 (10)	0.13 (3)*
H372	0.166 (7)	1.005 (9)	0.400 (10)	0.14 (3)*
H373	0.049 (6)	0.999 (7)	0.381 (8)	0.10 (2)*
H41	0.375 (4)	0.040 (5)	0.140 (5)	0.060 (14)*
H43	0.394 (4)	−0.272 (5)	0.174 (5)	0.058 (13)*
H461	0.406 (7)	−0.452 (9)	−0.071 (10)	0.14 (3)*
H462	0.334 (7)	−0.443 (9)	−0.195 (10)	0.13 (3)*
H463	0.432 (6)	−0.406 (8)	−0.169 (8)	0.11 (3)*
H471	0.355 (7)	−0.033 (10)	−0.090 (10)	0.14 (3)*
H472	0.425 (6)	−0.158 (8)	−0.158 (8)	0.11 (3)*
H473	0.316 (5)	−0.181 (6)	−0.204 (7)	0.082 (18)*
H51	0.366 (4)	0.244 (6)	0.393 (6)	0.072 (16)*
H53	0.393 (4)	0.266 (5)	0.089 (5)	0.057 (13)*
H561	0.383 (5)	0.517 (7)	0.148 (8)	0.10 (2)*
H562	0.338 (4)	0.594 (6)	0.284 (6)	0.067 (15)*
H563	0.447 (6)	0.603 (7)	0.327 (8)	0.10 (2)*
H571	0.339 (6)	0.502 (8)	0.567 (9)	0.12 (3)*
H572	0.420 (5)	0.602 (6)	0.566 (7)	0.080 (18)*
H573	0.317 (6)	0.602 (8)	0.504 (8)	0.12 (3)*
H61	0.364 (5)	−0.004 (7)	0.359 (7)	0.09 (2)*
H63	0.344 (3)	0.329 (4)	0.683 (4)	0.030 (9)*
H661	0.350 (7)	0.260 (9)	0.865 (9)	0.13 (3)*
H662	0.305 (4)	0.116 (6)	0.787 (6)	0.063 (15)*
H663	0.413 (4)	0.132 (5)	0.845 (5)	0.054 (12)*
H671	0.408 (6)	−0.139 (9)	0.469 (10)	0.12 (3)*
H672	0.451 (5)	−0.097 (6)	0.617 (7)	0.09 (2)*
H673	0.328 (5)	−0.132 (7)	0.556 (7)	0.09 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0693 (15)	0.0294 (11)	0.0338 (11)	0.0081 (9)	0.0138 (10)	0.0151 (9)
N12	0.0784 (17)	0.0406 (12)	0.0329 (11)	0.0112 (11)	0.0187 (11)	0.0179 (10)
C13	0.0732 (19)	0.0384 (13)	0.0377 (14)	0.0113 (12)	0.0178 (12)	0.0202 (12)
C14	0.0559 (16)	0.0357 (13)	0.0321 (13)	0.0040 (11)	0.0108 (11)	0.0097 (11)
C15	0.0528 (15)	0.0420 (13)	0.0306 (12)	0.0048 (10)	0.0111 (10)	0.0169 (11)
C16	0.080 (2)	0.0439 (17)	0.0446 (17)	0.0103 (15)	0.0133 (16)	0.0025 (14)
C17	0.075 (2)	0.075 (2)	0.0440 (17)	0.0092 (18)	0.0147 (15)	0.0381 (17)
N21	0.0673 (15)	0.0388 (11)	0.0335 (11)	0.0105 (10)	0.0162 (10)	0.0209 (9)
N22	0.0743 (16)	0.0358 (11)	0.0356 (12)	0.0107 (10)	0.0171 (11)	0.0183 (9)
C23	0.0706 (19)	0.0480 (15)	0.0386 (14)	0.0116 (13)	0.0200 (12)	0.0244 (12)
C24	0.0567 (15)	0.0384 (13)	0.0453 (14)	0.0089 (11)	0.0162 (11)	0.0269 (11)
C25	0.0534 (15)	0.0337 (12)	0.0388 (14)	0.0078 (10)	0.0125 (11)	0.0189 (11)
C26	0.087 (3)	0.0548 (18)	0.087 (3)	0.0163 (18)	0.034 (2)	0.053 (2)
C27	0.085 (2)	0.0431 (16)	0.0434 (17)	0.0108 (16)	0.0168 (15)	0.0112 (13)
N31	0.0658 (14)	0.0368 (11)	0.0312 (11)	0.0114 (9)	0.0143 (9)	0.0185 (9)
N32	0.0848 (18)	0.0414 (12)	0.0359 (12)	0.0159 (11)	0.0240 (11)	0.0231 (10)
C33	0.078 (2)	0.0404 (15)	0.0325 (13)	0.0156 (13)	0.0195 (12)	0.0175 (12)
C34	0.0622 (16)	0.0479 (14)	0.0270 (12)	0.0104 (11)	0.0156 (11)	0.0213 (11)
C35	0.0525 (15)	0.0372 (13)	0.0346 (12)	0.0059 (10)	0.0100 (10)	0.0209 (10)
C36	0.095 (3)	0.079 (2)	0.0421 (17)	0.027 (2)	0.0316 (17)	0.0405 (17)
C37	0.067 (2)	0.0422 (15)	0.0602 (19)	0.0080 (13)	0.0095 (15)	0.0331 (14)
N41	0.0658 (15)	0.0315 (11)	0.0370 (11)	0.0091 (9)	0.0164 (10)	0.0174 (9)
N42	0.0720 (16)	0.0382 (11)	0.0343 (11)	0.0067 (10)	0.0179 (10)	0.0170 (9)
C43	0.0708 (19)	0.0379 (13)	0.0448 (15)	0.0076 (12)	0.0196 (13)	0.0234 (12)
C44	0.0555 (15)	0.0333 (13)	0.0377 (13)	0.0032 (10)	0.0148 (11)	0.0107 (11)
C45	0.0551 (15)	0.0419 (13)	0.0309 (12)	0.0066 (11)	0.0121 (11)	0.0161 (11)
C46	0.089 (3)	0.0362 (15)	0.057 (2)	0.0056 (15)	0.0272 (18)	0.0014 (14)
C47	0.086 (2)	0.071 (2)	0.0455 (17)	0.0121 (18)	0.0215 (17)	0.0360 (16)
N51	0.0706 (15)	0.0370 (11)	0.0370 (12)	0.0114 (10)	0.0190 (10)	0.0216 (9)
N52	0.0848 (18)	0.0375 (11)	0.0393 (12)	0.0095 (11)	0.0249 (12)	0.0204 (10)
C53	0.084 (2)	0.0417 (14)	0.0391 (15)	0.0122 (13)	0.0255 (14)	0.0226 (12)
C54	0.0612 (16)	0.0361 (13)	0.0469 (15)	0.0115 (11)	0.0214 (12)	0.0261 (12)
C55	0.0520 (14)	0.0348 (12)	0.0353 (13)	0.0076 (10)	0.0119 (10)	0.0173 (10)
C56	0.105 (3)	0.0540 (18)	0.086 (3)	0.028 (2)	0.048 (2)	0.051 (2)
C57	0.073 (2)	0.0449 (15)	0.0411 (15)	0.0133 (14)	0.0173 (14)	0.0115 (13)
N61	0.0649 (15)	0.0404 (11)	0.0330 (11)	0.0068 (10)	0.0161 (10)	0.0181 (9)
N62	0.0822 (18)	0.0438 (12)	0.0379 (12)	0.0103 (11)	0.0242 (11)	0.0232 (10)
C63	0.0709 (19)	0.0384 (14)	0.0334 (13)	0.0078 (12)	0.0172 (12)	0.0151 (11)
C64	0.0560 (15)	0.0456 (14)	0.0285 (12)	0.0034 (11)	0.0109 (10)	0.0197 (10)
C65	0.0503 (14)	0.0386 (13)	0.0361 (13)	0.0042 (10)	0.0096 (10)	0.0207 (11)
C66	0.077 (2)	0.079 (2)	0.0377 (15)	0.0099 (18)	0.0182 (14)	0.0364 (16)
C67	0.071 (2)	0.0473 (16)	0.067 (2)	0.0093 (14)	0.0145 (16)	0.0363 (16)

Geometric parameters (Å, º)

N11—N12	1.351 (4)	N41—N42	1.352 (5)
N11—C15	1.343 (3)	N41—C45	1.349 (3)
N11—H11	0.87 (5)	N41—H41	0.98 (6)
N12—C13	1.335 (4)	N42—C43	1.342 (4)
C13—C14	1.391 (5)	C43—C44	1.385 (5)
C13—H13	0.95 (9)	C43—H43	0.97 (8)
C14—C15	1.374 (5)	C44—C45	1.382 (5)
C14—C16	1.501 (4)	C44—C46	1.499 (4)
C15—C17	1.495 (6)	C45—C47	1.491 (7)
C16—H161	1.09 (9)	C46—H461	1.03 (14)
C16—H162	1.01 (8)	C46—H462	1.01 (8)
C16—H163	0.96 (6)	C46—H463	0.99 (11)
C17—H171	0.94 (8)	C47—H471	1.05 (11)
C17—H172	1.10 (6)	C47—H472	0.92 (9)
C17—H173	0.82 (9)	C47—H473	1.06 (6)
N21—N22	1.354 (3)	N51—N52	1.355 (4)
N21—C25	1.340 (4)	N51—C55	1.336 (4)
N21—H21	1.00 (8)	N51—H51	1.04 (9)
N22—C23	1.331 (6)	N52—C53	1.326 (6)
C23—C24	1.391 (4)	C53—C54	1.398 (4)
C23—H23	1.01 (6)	C53—H53	0.99 (7)
C24—C25	1.374 (5)	C54—C55	1.381 (5)
C24—C26	1.503 (7)	C54—C56	1.502 (7)
C25—C27	1.501 (4)	C55—C57	1.498 (4)
C26—H261	1.08 (13)	C56—H561	1.14 (10)
C26—H262	1.05 (7)	C56—H562	0.90 (6)
C26—H263	0.94 (6)	C56—H563	1.08 (7)
C27—H271	0.99 (8)	C57—H571	1.03 (12)
C27—H272	1.05 (8)	C57—H572	1.00 (6)
C27—H273	0.89 (9)	C57—H573	1.07 (10)
N31—N32	1.361 (4)	N61—N62	1.357 (4)
N31—C35	1.351 (5)	N61—C65	1.342 (5)
N31—H31	1.17 (9)	N61—H61	1.12 (7)
N32—C33	1.333 (4)	N62—C63	1.339 (4)
C33—C34	1.394 (6)	C63—C64	1.384 (5)
C33—H33	0.86 (4)	C63—H63	0.95 (4)
C34—C35	1.381 (3)	C64—C65	1.386 (3)
C34—C36	1.502 (6)	C64—C66	1.499 (6)
C35—C37	1.492 (5)	C65—C67	1.500 (5)
C36—H361	1.05 (8)	C66—H661	1.00 (9)
C36—H362	0.96 (8)	C66—H662	0.88 (7)
C36—H363	0.90 (8)	C66—H663	1.02 (6)
C37—H371	1.07 (9)	C67—H671	0.95 (11)
C37—H372	1.06 (13)	C67—H672	1.06 (7)
C37—H373	1.09 (8)	C67—H673	1.04 (9)
N12—N11—C15	111.5 (3)	N42—N41—C45	110.7 (3)
N12—N11—H11	118 (3)	N42—N41—H41	124 (4)
C15—N11—H11	130 (4)	C45—N41—H41	125 (4)
N11—N12—C13	105.0 (3)	N41—N42—C43	105.6 (3)
N12—C13—C14	111.3 (3)	N42—C43—C44	111.2 (3)
N12—C13—H13	118 (3)	N42—C43—H43	118 (3)
C14—C13—H13	131 (3)	C44—C43—H43	131 (3)
C13—C14—C15	104.7 (2)	C43—C44—C45	104.6 (2)
C13—C14—C16	127.3 (3)	C43—C44—C46	127.9 (4)
C15—C14—C16	127.9 (3)	C45—C44—C46	127.4 (4)
N11—C15—C14	107.4 (3)	N41—C45—C44	107.8 (3)
N11—C15—C17	122.4 (3)	N41—C45—C47	121.8 (3)
C14—C15—C17	130.2 (3)	C44—C45—C47	130.4 (3)
C14—C16—H161	106 (3)	C44—C46—H461	107 (5)
C14—C16—H162	113 (3)	C44—C46—H462	123 (6)
C14—C16—H163	113 (4)	C44—C46—H463	118 (5)
H161—C16—H162	115 (6)	H461—C46—H462	106 (9)
H161—C16—H163	107 (6)	H461—C46—H463	112 (8)
H162—C16—H163	103 (6)	H462—C46—H463	89 (8)
C15—C17—H171	113 (5)	C45—C47—H471	106 (7)
C15—C17—H172	108 (5)	C45—C47—H472	114 (7)
C15—C17—H173	115 (6)	C45—C47—H473	113 (5)
H171—C17—H172	99 (5)	H471—C47—H472	124 (10)
H171—C17—H173	114 (8)	H471—C47—H473	100 (6)
H172—C17—H173	106 (6)	H472—C47—H473	99 (6)
N22—N21—C25	110.7 (3)	N52—N51—C55	110.4 (3)
N22—N21—H21	115 (2)	N52—N51—H51	106 (3)
C25—N21—H21	134 (3)	C55—N51—H51	143 (3)
N21—N22—C23	105.3 (2)	N51—N52—C53	106.3 (2)
N22—C23—C24	111.5 (3)	N52—C53—C54	110.8 (3)
N22—C23—H23	109 (4)	N52—C53—H53	123 (4)
C24—C23—H23	139 (4)	C54—C53—H53	126 (4)
C23—C24—C25	104.1 (3)	C53—C54—C55	104.2 (3)
C23—C24—C26	127.6 (4)	C53—C54—C56	127.1 (4)
C25—C24—C26	128.3 (3)	C55—C54—C56	128.7 (3)
N21—C25—C24	108.3 (2)	N51—C55—C54	108.4 (2)
N21—C25—C27	121.4 (3)	N51—C55—C57	121.7 (3)
C24—C25—C27	130.3 (3)	C54—C55—C57	129.9 (3)
C24—C26—H261	105 (7)	C54—C56—H561	115 (4)
C24—C26—H262	114 (6)	C54—C56—H562	109 (6)
C24—C26—H263	118 (5)	C54—C56—H563	106 (6)
H261—C26—H262	107 (8)	H561—C56—H562	116 (6)
H261—C26—H263	112 (7)	H561—C56—H563	111 (7)
H262—C26—H263	100 (5)	H562—C56—H563	99 (5)
C25—C27—H271	119 (3)	C55—C57—H571	113 (4)
C25—C27—H272	112 (3)	C55—C57—H572	116 (4)
C25—C27—H273	107 (5)	C55—C57—H573	113 (5)
H271—C27—H272	107 (7)	H571—C57—H572	116 (6)
H271—C27—H273	104 (6)	H571—C57—H573	107 (8)
H272—C27—H273	107 (7)	H572—C57—H573	91 (6)
N32—N31—C35	110.7 (2)	N62—N61—C65	110.1 (2)
N32—N31—H31	113 (5)	N62—N61—H61	118 (5)
C35—N31—H31	136 (5)	C65—N61—H61	130 (5)
N31—N32—C33	105.6 (3)	N61—N62—C63	106.1 (3)
N32—C33—C34	111.4 (3)	N62—C63—C64	111.0 (3)
N32—C33—H33	122 (4)	N62—C63—H63	120 (3)
C34—C33—H33	127 (4)	C64—C63—H63	129 (3)
C33—C34—C35	104.7 (3)	C63—C64—C65	104.5 (3)
C33—C34—C36	127.9 (3)	C63—C64—C66	128.4 (3)
C35—C34—C36	127.4 (4)	C65—C64—C66	127.2 (4)
N31—C35—C34	107.7 (3)	N61—C65—C64	108.3 (3)
N31—C35—C37	121.3 (3)	N61—C65—C67	122.0 (3)
C34—C35—C37	131.0 (4)	C64—C65—C67	129.7 (4)
C34—C36—H361	104 (7)	C64—C66—H661	109 (8)
C34—C36—H362	116 (5)	C64—C66—H662	108 (4)
C34—C36—H363	110 (5)	C64—C66—H663	111 (4)
H361—C36—H362	104 (6)	H661—C66—H662	113 (7)
H361—C36—H363	124 (7)	H661—C66—H663	113 (6)
H362—C36—H363	99 (7)	H662—C66—H663	103 (6)
C35—C37—H371	113 (7)	C65—C67—H671	104 (7)
C35—C37—H372	105 (6)	C65—C67—H672	114 (4)
C35—C37—H373	112 (4)	C65—C67—H673	111 (4)
H371—C37—H372	115 (8)	H671—C67—H672	98 (7)
H371—C37—H373	113 (7)	H671—C67—H673	121 (7)
H372—C37—H373	99 (8)	H672—C67—H673	108 (7)
N12—N11—C15—C17	178.9 (3)	N11—N12—N31—N32	6.1 (3)
N12—C13—C14—C16	−180.0 (3)	N12—N31—N32—N21	4.1 (3)
N22—N21—C25—C27	179.5 (3)	N31—N32—N21—N22	−11.5 (3)
N22—C23—C24—C26	179.5 (3)	N32—N21—N22—N11	8.7 (3)
N32—N31—C35—C37	−179.5 (3)	N21—N22—N11—N12	0.5 (4)
N32—C33—C34—C36	179.9 (3)	N22—N11—N12—N31	−8.8 (3)
N42—N41—C45—C47	179.4 (3)	N61—N62—N51—N52	8.4 (3)
N42—C43—C44—C46	−179.9 (3)	N62—N51—N52—N41	0.2 (3)
N52—N51—C55—C57	−179.6 (3)	N51—N52—N41—N42	−6.9 (3)
N52—C53—C54—C56	179.5 (3)	N52—N41—N42—N61	6.4 (3)
N62—N61—C65—C67	179.6 (3)	N41—N42—N61—N62	1.4 (3)
N62—C63—C64—C66	−179.6 (3)	N42—N61—N62—N51	−8.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···N22	0.87 (5)	2.01 (5)	2.869 (3)	171 (4)
N21—H21···N32	1.00 (8)	1.88 (8)	2.871 (5)	173 (5)
N31—H31···N12	1.17 (9)	1.71 (8)	2.870 (3)	173 (9)
N41—H41···N52	0.98 (6)	1.92 (6)	2.877 (3)	167 (5)
N51—H51···N62	1.04 (9)	1.86 (9)	2.868 (5)	162 (4)
N61—H61···N42	1.12 (7)	1.78 (8)	2.867 (3)	163 (6)
C17—H173···CEN1^i	0.82 (9)	3.06 (8)	3.788 (5)	149 (5)
C46—H462···CEN2^ii	1.01 (8)	2.86 (10)	3.678 (5)	139 (7)
C67—H673···CEN3^iii	1.04 (9)	2.84 (7)	3.725 (4)	142 (6)
C16—H163···CEN5^iv	0.96 (6)	2.85 (6)	3.702 (4)	148 (6)
C26—H262···CEN3^v	1.05 (7)	2.68 (8)	3.620 (4)	149 (6)
C66—H663···CEN4^vi	1.02 (6)	2.79 (5)	3.627 (4)	140 (5)
C57—H572···CEN5^vii	1.00 (6)	2.91 (6)	3.776 (4)	146 (6)
C37—H372···CEN6^viii	1.06 (13)	2.97 (9)	3.599 (4)	119 (6)

Symmetry codes: (i) −x, −y+2, −z+2; (ii) x, y−1, z−1; (iii) x, y−1, z; (iv) x, y+1, z+1; (v) −x, −y+1, −z+1; (vi) x, y, z+1; (vii) −x+1, −y+1, −z+1; (viii) x, y+1, z.

(II) 3,4,5-trimethylpyrazole

Crystal data

C6H10N2	F(000) = 720
Mr = 110.2	Dx = 1.12 Mg m^−3
Monoclinic, I2/a	Melting point = 411–412 K
Hall symbol: -I 2ya	Cu Kα radiation, λ = 1.5418 Å
a = 14.1911 (9) Å	Cell parameters from 43 reflections
b = 8.2520 (6) Å	θ = 5.2–45.0°
c = 16.7382 (19) Å	µ = 0.55 mm^−1
β = 90.696 (9)°	T = 200 K
V = 1960.0 (3) Å^3	Rectangular prism, colourless
Z = 12	0.67 × 0.27 × 0.17 mm

Data collection

Philips PW1100 diffractometer	Rint = 0.024
Radiation source: xray_tube	θmax = 65.1°, θmin = 5.3°
Graphite monochromator	h = −16→16
ω/2θ scans	k = 0→9
1863 measured reflections	l = 0→19
1680 independent reflections	2 standard reflections every 90 min
1372 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F	0 constraints
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.048	w = k/[(A + B Fo)^2(C + D(sinθ)/λ)]
wR(F^2) = 0.063	(Δ/σ)max = 0.07
S = 0.91	Δρmax = 0.22 e Å^−3
1366 reflections	Δρmin = −0.20 e Å^−3
182 parameters	Extinction correction: Zachariasen, Eq22_p292_"Cryst._Comp."_Munksgaard_1970
0 restraints	Extinction coefficient: 3.9E02 (1)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N21	0.35536 (12)	0.7225 (2)	0.13030 (10)	0.0433 (8)
N22	0.33361 (11)	0.7844 (2)	0.20287 (9)	0.0415 (8)
C23	0.40460 (13)	0.8798 (2)	0.22683 (11)	0.0410 (9)
C24	0.47360 (13)	0.8813 (2)	0.16877 (11)	0.0407 (9)
C25	0.43939 (13)	0.7802 (2)	0.10908 (11)	0.0428 (9)
C26	0.40211 (19)	0.9656 (3)	0.30554 (14)	0.0586 (13)
C27	0.56448 (16)	0.9731 (3)	0.16994 (15)	0.0577 (13)
C28	0.48383 (19)	0.7345 (3)	0.03184 (14)	0.0594 (13)
N12	0.26997 (11)	0.4612 (2)	0.03667 (10)	0.0414 (8)
C13	0.28248 (12)	0.3071 (2)	0.05999 (11)	0.0410 (9)
C14	0.25000	0.2043 (3)	0.00000	0.0398 (12)
C16	0.32655 (19)	0.2663 (4)	0.13847 (14)	0.0605 (13)
C17	0.25000	0.0223 (4)	0.00000	0.064 (2)
H21	0.324 (3)	0.655 (6)	0.107 (3)	0.010 (9)*
H22	0.281 (3)	0.761 (5)	0.230 (3)	0.016 (10)*
H26a	0.400 (3)	1.080 (7)	0.300 (3)	0.094 (15)*
H26b	0.344 (4)	0.951 (6)	0.330 (3)	0.090 (14)*
H26c	0.448 (4)	0.936 (7)	0.341 (3)	0.096 (15)*
H27a	0.584 (3)	1.026 (6)	0.220 (3)	0.076 (11)*
H27b	0.570 (3)	1.058 (6)	0.127 (3)	0.077 (12)*
H27c	0.619 (3)	0.912 (6)	0.160 (3)	0.088 (13)*
H28a	0.448 (3)	0.664 (6)	−0.000 (3)	0.084 (13)*
H28b	0.494 (3)	0.827 (6)	−0.003 (3)	0.075 (11)*
H28c	0.544 (3)	0.682 (5)	0.036 (2)	0.072 (11)*
H12	0.284 (2)	0.543 (6)	0.061 (2)	0.002 (8)*
H16a	0.388 (3)	0.237 (5)	0.136 (3)	0.074 (12)*
H16b	0.319 (4)	0.348 (7)	0.177 (3)	0.103 (17)*
H16c	0.288 (4)	0.196 (6)	0.169 (3)	0.092 (14)*
H17a	0.177 (5)	−0.023 (8)	−0.008 (4)	0.045 (15)*
H17b	0.287 (6)	−0.021 (10)	−0.040 (5)	0.06 (2)*
H17c	0.266 (4)	−0.023 (7)	0.057 (4)	0.030 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N21	0.0495 (9)	0.0359 (8)	0.0444 (8)	−0.0024 (7)	−0.0017 (7)	−0.0055 (7)
N22	0.0419 (8)	0.0401 (8)	0.0425 (8)	−0.0021 (6)	0.0040 (6)	−0.0026 (6)
C23	0.0449 (9)	0.0334 (8)	0.0446 (9)	0.0014 (7)	0.0005 (7)	−0.0006 (7)
C24	0.0410 (9)	0.0354 (8)	0.0456 (9)	0.0022 (7)	−0.0008 (7)	0.0003 (7)
C25	0.0470 (9)	0.0371 (9)	0.0443 (9)	0.0051 (7)	−0.0004 (7)	−0.0006 (8)
C26	0.0663 (14)	0.0570 (13)	0.0527 (12)	−0.0027 (11)	0.0049 (10)	−0.0141 (10)
C27	0.0463 (11)	0.0640 (14)	0.0628 (13)	−0.0108 (10)	−0.0014 (9)	0.0024 (11)
C28	0.0696 (14)	0.0606 (13)	0.0484 (11)	0.0056 (11)	0.0102 (10)	−0.0073 (10)
N12	0.0486 (8)	0.0382 (9)	0.0374 (7)	−0.0027 (7)	−0.0017 (6)	−0.0019 (7)
C13	0.0385 (8)	0.0437 (10)	0.0408 (9)	0.0019 (7)	0.0030 (7)	0.0033 (7)
C14	0.0359 (11)	0.0355 (13)	0.0481 (13)	0.00000	0.0055 (10)	0.00000
C16	0.0635 (14)	0.0688 (15)	0.0490 (12)	0.0089 (11)	−0.0086 (10)	0.0082 (11)
C17	0.073 (2)	0.0382 (16)	0.080 (2)	0.00000	0.017 (2)	0.00000

Geometric parameters (Å, º)

N21—N22	1.357 (2)	C28—H28c	0.96 (4)
N21—C25	1.336 (3)	N12—C13	1.341 (3)
N21—H21	0.81 (5)	N12—H12	0.81 (4)
N22—C23	1.336 (2)	N12—N12^i	1.346 (2)
N22—H22	0.89 (5)	C13—C14	1.389 (2)
C23—C24	1.388 (3)	C13—C16	1.487 (3)
C23—C26	1.496 (3)	C14—C17	1.502 (4)
C24—C25	1.385 (3)	C16—H16a	0.90 (5)
C24—C27	1.496 (3)	C16—H16b	0.94 (6)
C25—C28	1.494 (3)	C16—H16c	0.95 (5)
C26—H26a	0.95 (6)	C17—H17a	1.10 (7)
C26—H26b	0.93 (5)	C17—H17b	0.92 (9)
C26—H26c	0.92 (5)	C17—H17c	1.05 (6)
C27—H27a	0.99 (5)	C17—H17a^i	1.10 (7)
C27—H27b	1.00 (5)	C17—H17b^i	0.92 (9)
C27—H27c	0.94 (5)	C17—H17c^i	1.05 (6)
C28—H28a	0.94 (5)	H17b—H17c^i	0.80 (11)
C28—H28b	0.97 (5)
N22—N21—C25	108.49 (16)	N12—C13—C14	109.10 (16)
N22—N21—H21	124 (3)	N12—C13—C16	121.66 (19)
C25—N21—H21	127 (3)	C14—C13—C16	129.2 (2)
N21—N22—C23	108.16 (15)	C13—C14—C17	127.66 (11)
N21—N22—H22	125 (3)	C13—C14—C13^i	104.7 (2)
C23—N22—H22	127 (3)	C17—C14—C13^i	127.66 (11)
N22—C23—C24	109.30 (16)	C13—C16—H16a	114 (3)
N22—C23—C26	121.13 (18)	C13—C16—H16b	113 (3)
C24—C23—C26	129.57 (18)	C13—C16—H16c	113 (3)
C23—C24—C25	104.83 (16)	H16a—C16—H16b	110 (4)
C23—C24—C27	127.63 (18)	H16a—C16—H16c	115 (4)
C25—C24—C27	127.53 (18)	H16b—C16—H16c	90 (5)
N21—C25—C24	109.22 (16)	C14—C17—H17a	110 (3)
N21—C25—C28	121.84 (18)	C14—C17—H17b	113 (5)
C24—C25—C28	128.94 (18)	C14—C17—H17c	111 (3)
C23—C26—H26a	112 (3)	C14—C17—H17a^i	110 (3)
C23—C26—H26b	111 (3)	C14—C17—H17b^i	113 (5)
C23—C26—H26c	115 (3)	C14—C17—H17c^i	111 (3)
H26a—C26—H26b	99 (4)	H17a—C17—H17b	109 (7)
H26a—C26—H26c	110 (5)	H17a—C17—H17c	100 (5)
H26b—C26—H26c	108 (4)	H17a—C17—H17a^i	141 (5)
C24—C27—H27a	118 (3)	H17a—C17—H17b^i	55 (7)
C24—C27—H27b	114 (2)	H17a—C17—H17c^i	65 (5)
C24—C27—H27c	116 (3)	H17b—C17—H17c	114 (6)
H27a—C27—H27b	106 (4)	H17b—C17—H17a^i	55 (7)
H27a—C27—H27c	99 (4)	H17b—C17—H17b^i	135 (7)
H27b—C27—H27c	100 (4)	H17b—C17—H17c^i	47 (6)
C25—C28—H28a	115 (3)	H17c—C17—H17a^i	65 (5)
C25—C28—H28b	113 (3)	H17c—C17—H17b^i	47 (6)
C25—C28—H28c	116 (2)	H17c—C17—H17c^i	138 (4)
H28a—C28—H28b	103 (4)	H17a^i—C17—H17b^i	109 (7)
H28a—C28—H28c	104 (4)	H17a^i—C17—H17c^i	100 (5)
H28b—C28—H28c	105 (4)	H17b^i—C17—H17c^i	114 (6)
C13—N12—H12	128 (3)	C17—H17b—H17c^i	75 (8)
C13—N12—N12^i	108.56 (16)	C17—H17c—H17b^i	58 (7)
H12—N12—N12^i	123 (3)
N12^i—N12—C13—C16	179.19 (18)	N22—C23—C24—C27	179.1 (2)
N12—C13—C14—C17	179.93 (9)	N22—N21—C25—C28	179.83 (18)
N21—N22—C23—C26	−179.51 (18)

Symmetry code: (i) −x+1/2, y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12···N21	0.81 (4)	2.13 (4)	2.920 (2)	165 (4)
N21—H21···N12	0.81 (5)	2.12 (5)	2.920 (2)	168 (4)
N22—H22···N22^ii	0.89 (5)	2.03 (5)	2.921 (2)	176 (4)
C17—H17c···CEN2^iii	1.05 (6)	2.99 (6)	3.9255 (17)	149 (4)
C17—H17a···CEN2^iv	1.10 (7)	3.20 (7)	3.9255 (17)	124 (4)
C27—H27a···CEN2^v	0.99 (5)	3.01 (5)	3.913 (3)	153 (3)
C28—H28c···CEN1^vi	0.96 (4)	3.00 (4)	3.881 (3)	153 (3)

Symmetry codes: (ii) −x+1/2, −y+3/2, −z+1/2; (iii) x, y−1, z; (iv) −x+1/2, y−1, −z; (v) −x+1, y+1/2, −z+1/2; (vi) −x+1, −y+1, −z.