Crystal structure of tris-(3-methyl-1H-pyrazol-1-yl)methane.

The title mol-ecule, C13H16N6, crystallizes from hexane as a mol-ecular crystal with no strong inter-molecular inter-actions (the shortest C-H⋯N contact is longer than 3.38 Å). A relatively short intra-molecular contact (3.09 Å) has a C-H⋯N angle of 118° which is quite small to be still considered a hydrogen bond. The three pyrazole rings form a propeller-like motif, with one methylpyrazole unit almost perpendicular to the mean plane of the three rings [82.20 (6)°]. The other two methylpyrazole units, with nitrogen donor atoms oriented in opposite directions, are oriented at 67.26 (6) and 72.53 (6)° to the mean plane.

Related literature

For syntheses and reactions of tris­pyrazolyl­methanes and their complexes with transition metals, see: Goodman et al. (2012 ▸); Jameson & Castellano (1998 ▸); Reger et al. (2000 ▸).

Experimental

Crystal data

C13H16N6

M = 256.32

Monoclinic,

a = 12.0881 (8) Å

b = 13.4178 (10) Å

c = 9.0985 (6) Å

β = 111.630 (2)°

V = 1371.82 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 173 K

0.60 × 0.48 × 0.29 mm

Data collection

Bruker Photon-100 CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T min = 0.706, T max = 0.747

22036 measured reflections

2612 independent reflections

2171 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.099

S = 1.05

2612 reflections

225 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2013 ▸); cell refinement: SAINT (Bruker, 2013 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015017247/zl2643sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017247/zl2643Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015017247/zl2643Isup3.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015017247/zl2643Isup4.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015017247/zl2643fig1.tif

The mol­ecular structure of the title compound. Displacement elipsoids are drawn at the 50% probability level. Disorder of H atoms bonded to C5 are omitted for clarity.

Click here for additional data file.

c . DOI: 10.1107/S2056989015017247/zl2643fig2.tif

Packing diagram of the title mol­ecule. View along the c axis.

CCDC reference: 1424633

Additional supporting information: crystallographic information; 3D view; checkCIF report

C13H16N6	F(000) = 544
Mr = 256.32	Dx = 1.241 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.0881 (8) Å	Cell parameters from 9433 reflections
b = 13.4178 (10) Å	θ = 2.9–25.7°
c = 9.0985 (6) Å	µ = 0.08 mm−1
β = 111.630 (2)°	T = 173 K
V = 1371.82 (16) Å3	Block, colourless
Z = 4	0.60 × 0.48 × 0.29 mm

Bruker Photon-100 CMOS diffractometer	2171 reflections with I > 2σ(I)
Radiation source: sealedtube	Rint = 0.029
φ and ω scans	θmax = 25.7°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −14→14
Tmin = 0.706, Tmax = 0.747	k = −16→16
22036 measured reflections	l = −10→11
2612 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099	w = 1/[σ2(Fo2) + (0.0457P)2 + 0.5131P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2612 reflections	Δρmax = 0.28 e Å−3
225 parameters	Δρmin = −0.19 e Å−3

Experimental. SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0499 before and 0.0468 after correction. The ratio of minimum to maximum transmission is 0.9453. The λ/2 correction factor is 0.00150.

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. 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H,H,H,H,H) groups 2. Others Sof(H5D)=Sof(H5E)=Sof(H5F)=1-FVAR(1) Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(1) 3.a Disordered Me refined with riding coordinates and stretchable bonds: C5(H5A,H5B,H5C,H5D,H5E,H5F)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.75721 (10)	0.58635 (9)	0.89470 (13)	0.0257 (3)
C1	0.81554 (12)	0.51681 (10)	0.82664 (15)	0.0231 (3)
H1	0.8972 (14)	0.5366 (11)	0.8603 (18)	0.028*
N2	0.64449 (11)	0.57102 (10)	0.88717 (14)	0.0322 (3)
C2	0.80352 (15)	0.67251 (12)	0.96750 (19)	0.0379 (4)
H2	0.8860 (18)	0.6925 (14)	0.984 (2)	0.051 (5)*
N3	0.76487 (10)	0.52045 (9)	0.65612 (13)	0.0247 (3)
C3	0.71772 (17)	0.71542 (14)	1.0092 (2)	0.0469 (4)
H3	0.7246 (19)	0.7797 (18)	1.066 (3)	0.074 (7)*
N4	0.83993 (11)	0.50592 (9)	0.57737 (14)	0.0288 (3)
C4	0.62038 (14)	0.65090 (12)	0.95767 (18)	0.0358 (4)
N5	0.81296 (9)	0.41679 (8)	0.88404 (12)	0.0224 (3)
C5	0.50296 (17)	0.66100 (16)	0.9753 (2)	0.0547 (5)
H5A	0.50076 (17)	0.7279 (9)	1.0330 (8)	0.066*	0.544 (19)
H5B	0.4350 (9)	0.66087 (16)	0.8637 (14)	0.066*	0.544 (19)
H5C	0.4909 (2)	0.6013 (8)	1.0416 (9)	0.066*	0.544 (19)
H5D	0.4504 (7)	0.5989 (8)	0.9259 (7)	0.066*	0.456 (19)
H5E	0.5161 (2)	0.66585 (18)	1.0952 (15)	0.066*	0.456 (19)
H5F	0.4602 (6)	0.7254 (8)	0.9172 (8)	0.066*	0.456 (19)
N6	0.90717 (10)	0.38708 (9)	1.01297 (12)	0.0249 (3)
C6	0.64987 (13)	0.52449 (12)	0.55706 (17)	0.0310 (3)
H6	0.5895 (15)	0.5348 (12)	0.5961 (19)	0.031 (4)*
C7	0.64953 (14)	0.51349 (12)	0.40812 (17)	0.0332 (4)
H7	0.5830 (16)	0.5140 (13)	0.313 (2)	0.043 (5)*
C8	0.76915 (13)	0.50248 (11)	0.42596 (16)	0.0299 (3)
C9	0.82000 (19)	0.48816 (18)	0.3011 (2)	0.0473 (5)
H9A	0.905 (2)	0.4833 (17)	0.347 (3)	0.072 (7)*
H9B	0.784 (2)	0.433 (2)	0.236 (3)	0.084 (8)*
H9C	0.805 (2)	0.548 (2)	0.234 (3)	0.088 (8)*
C10	0.72423 (13)	0.34908 (11)	0.84262 (18)	0.0311 (3)
H10	0.6507 (15)	0.3624 (12)	0.755 (2)	0.036 (4)*
C11	0.76199 (14)	0.27160 (12)	0.94568 (19)	0.0332 (4)
H11	0.7205 (15)	0.2122 (13)	0.945 (2)	0.039 (5)*
C12	0.87610 (13)	0.29819 (11)	1.04977 (16)	0.0285 (3)
C13	0.95886 (18)	0.24190 (16)	1.1873 (2)	0.0454 (4)
H13A	1.032 (2)	0.2793 (19)	1.244 (3)	0.086 (8)*
H13B	0.921 (2)	0.2225 (19)	1.253 (3)	0.088 (8)*
H13C	0.982 (2)	0.183 (2)	1.150 (3)	0.094 (9)*

	U11	U22	U33	U12	U13	U23
N1	0.0252 (6)	0.0268 (6)	0.0242 (6)	−0.0002 (5)	0.0081 (5)	−0.0029 (5)
C1	0.0219 (7)	0.0251 (7)	0.0210 (7)	−0.0020 (5)	0.0063 (5)	−0.0013 (5)
N2	0.0272 (7)	0.0379 (7)	0.0315 (7)	0.0033 (5)	0.0108 (5)	−0.0050 (5)
C2	0.0404 (10)	0.0334 (9)	0.0411 (9)	−0.0069 (7)	0.0163 (7)	−0.0108 (7)
N3	0.0224 (6)	0.0305 (7)	0.0209 (6)	−0.0011 (5)	0.0077 (5)	−0.0003 (5)
C3	0.0528 (11)	0.0350 (10)	0.0560 (11)	0.0016 (8)	0.0237 (9)	−0.0134 (8)
N4	0.0281 (7)	0.0350 (7)	0.0261 (6)	0.0001 (5)	0.0134 (5)	0.0006 (5)
C4	0.0351 (9)	0.0406 (9)	0.0316 (8)	0.0104 (7)	0.0122 (7)	0.0000 (7)
N5	0.0199 (6)	0.0241 (6)	0.0221 (6)	−0.0007 (4)	0.0064 (4)	−0.0015 (5)
C5	0.0450 (11)	0.0647 (13)	0.0602 (12)	0.0151 (9)	0.0260 (9)	−0.0059 (10)
N6	0.0231 (6)	0.0310 (7)	0.0207 (6)	0.0004 (5)	0.0081 (5)	0.0023 (5)
C6	0.0236 (7)	0.0424 (9)	0.0252 (7)	−0.0006 (6)	0.0070 (6)	−0.0003 (6)
C7	0.0317 (8)	0.0409 (9)	0.0224 (7)	−0.0006 (7)	0.0048 (6)	0.0004 (6)
C8	0.0347 (8)	0.0309 (8)	0.0245 (7)	−0.0015 (6)	0.0115 (6)	0.0007 (6)
C9	0.0467 (11)	0.0697 (14)	0.0302 (9)	−0.0003 (10)	0.0195 (8)	−0.0020 (9)
C10	0.0236 (8)	0.0287 (8)	0.0374 (8)	−0.0033 (6)	0.0069 (7)	−0.0032 (6)
C11	0.0314 (8)	0.0262 (8)	0.0455 (9)	−0.0045 (6)	0.0182 (7)	0.0001 (7)
C12	0.0302 (8)	0.0309 (8)	0.0295 (7)	0.0018 (6)	0.0169 (6)	0.0040 (6)
C13	0.0448 (11)	0.0479 (11)	0.0436 (10)	0.0026 (9)	0.0163 (9)	0.0205 (9)

N1—C1	1.4398 (18)	C5—H5D	1.045 (13)
N1—N2	1.3546 (17)	C5—H5E	1.045 (13)
N1—C2	1.347 (2)	C5—H5F	1.045 (13)
C1—H1	0.956 (16)	N6—C12	1.3298 (19)
C1—N3	1.4436 (17)	C6—H6	0.932 (17)
C1—N5	1.4446 (17)	C6—C7	1.362 (2)
N2—C4	1.3353 (19)	C7—H7	0.939 (18)
C2—H2	0.99 (2)	C7—C8	1.402 (2)
C2—C3	1.357 (2)	C8—C9	1.490 (2)
N3—N4	1.3615 (16)	C9—H9A	0.96 (2)
N3—C6	1.3506 (18)	C9—H9B	0.95 (3)
C3—H3	0.99 (2)	C9—H9C	0.98 (3)
C3—C4	1.395 (2)	C10—H10	0.965 (17)
N4—C8	1.3278 (18)	C10—C11	1.361 (2)
C4—C5	1.492 (2)	C11—H11	0.941 (18)
N5—N6	1.3591 (15)	C11—C12	1.401 (2)
N5—C10	1.3490 (18)	C12—C13	1.488 (2)
C5—H5A	1.045 (13)	C13—H13A	0.98 (3)
C5—H5B	1.045 (13)	C13—H13B	0.92 (3)
C5—H5C	1.045 (13)	C13—H13C	0.95 (3)
N2—N1—C1	121.52 (11)	H5B—C5—H5E	141.1
C2—N1—C1	125.94 (12)	H5B—C5—H5F	56.3
C2—N1—N2	112.52 (12)	H5C—C5—H5D	56.3
N1—C1—H1	107.0 (9)	H5C—C5—H5E	56.3
N1—C1—N3	111.06 (11)	H5C—C5—H5F	141.1
N1—C1—N5	111.55 (11)	H5D—C5—H5E	109.5
N3—C1—H1	108.3 (9)	H5D—C5—H5F	109.5
N3—C1—N5	111.27 (11)	H5E—C5—H5F	109.5
N5—C1—H1	107.4 (9)	C12—N6—N5	104.82 (11)
C4—N2—N1	104.33 (12)	N3—C6—H6	120.6 (10)
N1—C2—H2	121.4 (11)	N3—C6—C7	106.53 (13)
N1—C2—C3	106.24 (15)	C7—C6—H6	132.8 (10)
C3—C2—H2	132.4 (11)	C6—C7—H7	127.0 (11)
N4—N3—C1	117.37 (11)	C6—C7—C8	105.75 (13)
C6—N3—C1	130.02 (12)	C8—C7—H7	127.2 (11)
C6—N3—N4	112.10 (11)	N4—C8—C7	111.04 (13)
C2—C3—H3	126.0 (13)	N4—C8—C9	120.42 (14)
C2—C3—C4	106.23 (15)	C7—C8—C9	128.53 (14)
C4—C3—H3	127.8 (13)	C8—C9—H9A	110.7 (14)
C8—N4—N3	104.56 (11)	C8—C9—H9B	110.7 (15)
N2—C4—C3	110.68 (14)	C8—C9—H9C	109.5 (15)
N2—C4—C5	120.61 (16)	H9A—C9—H9B	113 (2)
C3—C4—C5	128.69 (16)	H9A—C9—H9C	104.5 (19)
N6—N5—C1	117.49 (11)	H9B—C9—H9C	108 (2)
C10—N5—C1	130.21 (12)	N5—C10—H10	120.1 (10)
C10—N5—N6	111.75 (11)	N5—C10—C11	106.96 (13)
C4—C5—H5A	109.5	C11—C10—H10	132.9 (10)
C4—C5—H5B	109.5	C10—C11—H11	127.0 (10)
C4—C5—H5C	109.5	C10—C11—C12	105.53 (13)
C4—C5—H5D	109.5	C12—C11—H11	127.5 (10)
C4—C5—H5E	109.5	N6—C12—C11	110.93 (13)
C4—C5—H5F	109.5	N6—C12—C13	120.15 (14)
H5A—C5—H5B	109.5	C11—C12—C13	128.92 (15)
H5A—C5—H5C	109.5	C12—C13—H13A	112.2 (15)
H5A—C5—H5D	141.1	C12—C13—H13B	110.5 (16)
H5A—C5—H5E	56.3	C12—C13—H13C	108.8 (16)
H5A—C5—H5F	56.3	H13A—C13—H13B	112 (2)
H5B—C5—H5C	109.5	H13A—C13—H13C	107 (2)
H5B—C5—H5D	56.3	H13B—C13—H13C	106 (2)
N1—C1—N3—N4	145.25 (12)	C2—C3—C4—C5	178.91 (17)
N1—C1—N3—C6	−43.68 (19)	N3—C1—N5—N6	142.82 (11)
N1—C1—N5—N6	−92.55 (13)	N3—C1—N5—C10	−46.46 (19)
N1—C1—N5—C10	78.17 (17)	N3—N4—C8—C7	−0.73 (16)
N1—N2—C4—C3	−0.18 (17)	N3—N4—C8—C9	179.43 (15)
N1—N2—C4—C5	−179.06 (15)	N3—C6—C7—C8	0.29 (18)
N1—C2—C3—C4	−0.05 (19)	N4—N3—C6—C7	−0.78 (17)
C1—N1—N2—C4	−178.37 (12)	N5—C1—N3—N4	−89.84 (14)
C1—N1—C2—C3	178.37 (14)	N5—C1—N3—C6	81.22 (18)
C1—N3—N4—C8	173.56 (12)	N5—N6—C12—C11	−0.56 (15)
C1—N3—C6—C7	−172.22 (14)	N5—N6—C12—C13	180.00 (14)
C1—N5—N6—C12	173.41 (11)	N5—C10—C11—C12	0.69 (16)
C1—N5—C10—C11	−172.24 (13)	N6—N5—C10—C11	−1.10 (16)
N2—N1—C1—N3	71.12 (16)	C6—N3—N4—C8	0.94 (16)
N2—N1—C1—N5	−53.63 (16)	C6—C7—C8—N4	0.29 (18)
N2—N1—C2—C3	−0.06 (18)	C6—C7—C8—C9	−179.89 (18)
C2—N1—C1—N3	−107.19 (16)	C10—N5—N6—C12	1.03 (15)
C2—N1—C1—N5	128.06 (15)	C10—C11—C12—N6	−0.07 (17)
C2—N1—N2—C4	0.15 (16)	C10—C11—C12—C13	179.30 (17)
C2—C3—C4—N2	0.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N6i	0.96 (2)	2.44 (2)	3.3796 (19)	167 (1)
C6—H6···N2	0.932 (17)	2.529 (16)	3.0918 (19)	119.2 (13)