Crystal structure of 1-meth­oxy-2,2,2-tris­(pyrazol-1-yl)ethane

Abstract

The title compound, C₁₂H₁₄N₆O, consists of three pyrazole rings bound via nitro­gen to the distal ethane carbon of meth­oxy ethane. The dihedral angles between the three pyrazole rings are 67.62 (14), 73.74 (14), and 78.92 (12)°. In the crystal, mol­ecules are linked by bifurcated C—H,H⋯N hydrogen bonds, forming double-stranded chains along [001]. The chains are linked via C—H⋯O hydrogen bonds, forming a three-dimensional framework structure. The crystal was refined as a perfect (0.5:0.5) inversion twin.

Related literature  

For properties of pyrazole-based tridentate ligands, see: Paulo et al. (2004 ▶); Bigmore et al. (2005 ▶). For nickel and cobalt complexes of N-donor tridentate scorpionate ligands, see: Lyubartseva et al. (2011 ▶, 2012 ▶, 2013a ▶,b ▶); Lyubartseva & Parkin (2009 ▶). For the synthesis of the title compound, see: Maria et al. (2007 ▶).

Experimental  

Crystal data  

• C₁₂H₁₄N₆O

• M _r = 258.29

• Monoclinic,

• a = 12.5828 (3) Å

• b = 12.3847 (3) Å

• c = 8.4807 (2) Å

• β = 102.5635 (11)°

• V = 1289.94 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 90 K

• 0.28 × 0.20 × 0.16 mm

Data collection  

• Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.749, T _max = 0.942

• 11397 measured reflections

• 2934 independent reflections

• 2386 reflections with I > 2σ(I)

• R _int = 0.032

Refinement  

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.102

• S = 1.10

• 2934 reflections

• 174 parameters

• 2 restraints

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

• Absolute structure: Refined as a perfect (i.e. 50:50) inversion twin

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL2014 and PLATON (Spek, 2009 ▶).

Supplementary Material

CCDC reference: 1019968

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯N2i	0.95	2.51	3.453 (4)	171
C9—H9A⋯N2ii	0.95	2.61	3.433 (4)	145
C4—H4A⋯O1iii	0.95	2.53	3.444 (4)	162

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

S1. Synthesis and crystallization

The title compound was prepared using the published procedure (Maria et al., 2007). Colourless block-like crystals were obtained by slow evaporation of a di­ethyl ether solution of pure product. Spectral and other characterizations are in good accordance with the previously reported data (Maria et al., 2007).

S2. Refinement

H atoms were located in difference Fourier maps, but were subsequently included in the refinement using a riding model approximation: C—H = 0.95 - 0.99 Å with U_iso(H) = 1.5U_eq(C-methyl) and = 1.2U_eq(C) for other H atoms. The crystal was refined as a perfect (0.5:0.5) inversion twin.

Figures

Fig. 1.

View of molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.

Crystal data

C12H14N6O	F(000) = 544
Mr = 258.29	Dx = 1.330 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 12.5828 (3) Å	Cell parameters from 1549 reflections
b = 12.3847 (3) Å	θ = 1.0–27.5°
c = 8.4807 (2) Å	µ = 0.09 mm−1
β = 102.5635 (11)°	T = 90 K
V = 1289.94 (5) Å3	Block, colourless
Z = 4	0.28 × 0.20 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer	2934 independent reflections
Radiation source: fine-focus sealed-tube	2386 reflections with I > 2σ(I)
Detector resolution: 9.1 pixels mm-1	Rint = 0.032
φ and ω scans at fixed χ = 55°	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.749, Tmax = 0.942	k = −16→16
11397 measured reflections	l = −10→11

Refinement

Refinement on F2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.042	w = 1/[σ2(Fo2) + (0.0453P)2 + 0.5917P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.23 e Å−3
2934 reflections	Δρmin = −0.18 e Å−3
174 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraints	Extinction coefficient: 0.0127 (19)
Primary atom site location: structure-invariant direct methods	Absolute structure: Refined as a perfect (i.e. 50:50) inversion twin.
Secondary atom site location: difference Fourier map

Special details

Experimental. The crystal was mounted with polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid nitrogen based cryostat, according to published methods (Hope, 1994; Parkin & Hope, 1998).Diffraction data were collected with the crystal at 90 K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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

Refinement. Refinement progress was checked using PLATON (Spek, 2009) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

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

	x	y	z	Uiso*/Ueq
O1	0.34875 (17)	0.16856 (16)	0.5089 (3)	0.0305 (5)
N1	0.62903 (19)	0.25690 (19)	0.5191 (3)	0.0229 (5)
N2	0.6299 (2)	0.2508 (2)	0.3598 (3)	0.0291 (6)
N3	0.4892 (2)	0.35743 (18)	0.5996 (3)	0.0255 (6)
N4	0.5617 (2)	0.4320 (2)	0.6770 (4)	0.0378 (7)
N5	0.5520 (2)	0.1924 (2)	0.7270 (3)	0.0236 (5)
N6	0.5898 (2)	0.0891 (2)	0.7266 (3)	0.0296 (6)
C1	0.5280 (2)	0.2497 (2)	0.5740 (3)	0.0212 (6)
C2	0.7343 (3)	0.2658 (3)	0.3557 (4)	0.0336 (7)
H2A	0.7610	0.2658	0.2591	0.040*
C3	0.8001 (2)	0.2816 (2)	0.5100 (4)	0.0318 (7)
H3A	0.8765	0.2933	0.5376	0.038*
C4	0.7295 (3)	0.2762 (2)	0.6118 (4)	0.0303 (7)
H4A	0.7475	0.2845	0.7259	0.036*
C5	0.5010 (3)	0.5170 (3)	0.6921 (5)	0.0426 (9)
H5A	0.5290	0.5831	0.7406	0.051*
C6	0.3900 (3)	0.4977 (3)	0.6277 (5)	0.0394 (8)
H6A	0.3311	0.5461	0.6252	0.047*
C7	0.3848 (3)	0.3954 (3)	0.5699 (4)	0.0307 (7)
H7A	0.3210	0.3574	0.5187	0.037*
C8	0.6077 (3)	0.0592 (3)	0.8804 (4)	0.0330 (7)
H8A	0.6344	−0.0098	0.9187	0.040*
C9	0.5825 (3)	0.1410 (3)	0.9791 (4)	0.0379 (8)
H9A	0.5884	0.1385	1.0927	0.045*
C10	0.5474 (2)	0.2258 (3)	0.8775 (4)	0.0324 (7)
H10A	0.5244	0.2946	0.9067	0.039*
C11	0.4437 (2)	0.1869 (2)	0.4498 (4)	0.0252 (6)
H11A	0.4249	0.2284	0.3478	0.030*
H11B	0.4751	0.1169	0.4266	0.030*
C12	0.3184 (3)	0.0580 (3)	0.5101 (5)	0.0384 (8)
H12A	0.2517	0.0515	0.5511	0.058*
H12B	0.3770	0.0171	0.5800	0.058*
H12C	0.3057	0.0291	0.4000	0.058*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0238 (11)	0.0263 (11)	0.0426 (13)	−0.0028 (9)	0.0099 (9)	−0.0036 (9)
N1	0.0226 (13)	0.0254 (12)	0.0214 (13)	0.0009 (10)	0.0062 (10)	0.0004 (10)
N2	0.0335 (15)	0.0325 (14)	0.0239 (13)	0.0045 (11)	0.0115 (11)	0.0029 (11)
N3	0.0233 (12)	0.0213 (12)	0.0324 (13)	−0.0003 (10)	0.0072 (10)	−0.0024 (11)
N4	0.0282 (14)	0.0256 (14)	0.0600 (19)	−0.0051 (12)	0.0103 (13)	−0.0140 (13)
N5	0.0247 (12)	0.0237 (12)	0.0227 (12)	−0.0018 (10)	0.0058 (10)	−0.0001 (10)
N6	0.0359 (15)	0.0213 (13)	0.0294 (14)	0.0003 (10)	0.0025 (11)	0.0033 (10)
C1	0.0197 (14)	0.0219 (14)	0.0233 (15)	0.0004 (10)	0.0074 (12)	−0.0010 (11)
C2	0.0357 (17)	0.0306 (17)	0.0400 (19)	0.0029 (14)	0.0203 (15)	0.0051 (14)
C3	0.0222 (15)	0.0285 (15)	0.048 (2)	0.0000 (12)	0.0143 (15)	0.0000 (14)
C4	0.0257 (16)	0.0316 (17)	0.0334 (17)	0.0020 (13)	0.0057 (13)	−0.0024 (13)
C5	0.0370 (18)	0.0272 (18)	0.064 (2)	−0.0032 (14)	0.0130 (17)	−0.0149 (16)
C6	0.0308 (17)	0.0274 (17)	0.061 (2)	0.0062 (14)	0.0116 (16)	−0.0077 (15)
C7	0.0249 (15)	0.0287 (16)	0.0374 (17)	0.0024 (12)	0.0042 (13)	−0.0008 (13)
C8	0.0248 (16)	0.0364 (18)	0.0353 (18)	−0.0083 (14)	0.0009 (13)	0.0113 (15)
C9	0.0300 (17)	0.060 (2)	0.0246 (16)	−0.0035 (16)	0.0075 (13)	0.0056 (15)
C10	0.0260 (16)	0.0457 (19)	0.0282 (16)	−0.0028 (14)	0.0122 (13)	−0.0058 (14)
C11	0.0214 (15)	0.0256 (14)	0.0280 (15)	0.0008 (11)	0.0041 (12)	−0.0027 (12)
C12	0.038 (2)	0.0282 (17)	0.051 (2)	−0.0059 (14)	0.0126 (17)	0.0031 (16)

Geometric parameters (Å, º)

O1—C11	1.411 (3)	C3—H3A	0.9500
O1—C12	1.423 (4)	C4—H4A	0.9500
N1—N2	1.356 (3)	C5—C6	1.405 (5)
N1—C4	1.357 (4)	C5—H5A	0.9500
N1—C1	1.448 (3)	C6—C7	1.355 (5)
N2—C2	1.335 (4)	C6—H6A	0.9500
N3—N4	1.363 (4)	C7—H7A	0.9500
N3—C7	1.365 (4)	C8—C9	1.394 (5)
N3—C1	1.454 (3)	C8—H8A	0.9500
N4—C5	1.323 (4)	C9—C10	1.369 (5)
N5—C10	1.354 (4)	C9—H9A	0.9500
N5—N6	1.364 (3)	C10—H10A	0.9500
N5—C1	1.452 (4)	C11—H11A	0.9900
N6—C8	1.327 (4)	C11—H11B	0.9900
C1—C11	1.534 (4)	C12—H12A	0.9800
C2—C3	1.402 (5)	C12—H12B	0.9800
C2—H2A	0.9500	C12—H12C	0.9800
C3—C4	1.369 (4)
C11—O1—C12	114.0 (2)	N4—C5—H5A	124.0
N2—N1—C4	112.3 (2)	C6—C5—H5A	124.0
N2—N1—C1	121.0 (2)	C7—C6—C5	105.3 (3)
C4—N1—C1	126.7 (2)	C7—C6—H6A	127.3
C2—N2—N1	103.8 (3)	C5—C6—H6A	127.3
N4—N3—C7	111.9 (2)	C6—C7—N3	106.7 (3)
N4—N3—C1	118.8 (2)	C6—C7—H7A	126.7
C7—N3—C1	129.0 (2)	N3—C7—H7A	126.7
C5—N4—N3	104.2 (3)	N6—C8—C9	112.0 (3)
C10—N5—N6	112.0 (3)	N6—C8—H8A	124.0
C10—N5—C1	130.5 (3)	C9—C8—H8A	124.0
N6—N5—C1	117.4 (2)	C10—C9—C8	105.3 (3)
C8—N6—N5	104.1 (3)	C10—C9—H9A	127.4
N1—C1—N5	106.9 (2)	C8—C9—H9A	127.4
N1—C1—N3	109.8 (2)	N5—C10—C9	106.6 (3)
N5—C1—N3	109.0 (2)	N5—C10—H10A	126.7
N1—C1—C11	109.6 (2)	C9—C10—H10A	126.7
N5—C1—C11	110.1 (2)	O1—C11—C1	110.5 (2)
N3—C1—C11	111.3 (2)	O1—C11—H11A	109.5
N2—C2—C3	112.3 (3)	C1—C11—H11A	109.5
N2—C2—H2A	123.8	O1—C11—H11B	109.5
C3—C2—H2A	123.8	C1—C11—H11B	109.5
C4—C3—C2	104.4 (3)	H11A—C11—H11B	108.1
C4—C3—H3A	127.8	O1—C12—H12A	109.5
C2—C3—H3A	127.8	O1—C12—H12B	109.5
N1—C4—C3	107.1 (3)	H12A—C12—H12B	109.5
N1—C4—H4A	126.4	O1—C12—H12C	109.5
C3—C4—H4A	126.4	H12A—C12—H12C	109.5
N4—C5—C6	112.0 (3)	H12B—C12—H12C	109.5
C4—N1—N2—C2	0.6 (3)	N4—N3—C1—C11	−165.4 (3)
C1—N1—N2—C2	177.0 (3)	C7—N3—C1—C11	21.3 (4)
C7—N3—N4—C5	−1.0 (4)	N1—N2—C2—C3	−0.1 (3)
C1—N3—N4—C5	−175.4 (3)	N2—C2—C3—C4	−0.4 (4)
C10—N5—N6—C8	0.5 (3)	N2—N1—C4—C3	−0.9 (3)
C1—N5—N6—C8	178.0 (2)	C1—N1—C4—C3	−177.1 (3)
N2—N1—C1—N5	144.6 (2)	C2—C3—C4—N1	0.8 (3)
C4—N1—C1—N5	−39.6 (4)	N3—N4—C5—C6	0.9 (4)
N2—N1—C1—N3	−97.3 (3)	N4—C5—C6—C7	−0.5 (5)
C4—N1—C1—N3	78.6 (3)	C5—C6—C7—N3	−0.2 (4)
N2—N1—C1—C11	25.2 (3)	N4—N3—C7—C6	0.8 (4)
C4—N1—C1—C11	−158.9 (3)	C1—N3—C7—C6	174.4 (3)
C10—N5—C1—N1	115.6 (3)	N5—N6—C8—C9	−0.2 (3)
N6—N5—C1—N1	−61.3 (3)	N6—C8—C9—C10	−0.2 (4)
C10—N5—C1—N3	−3.0 (4)	N6—N5—C10—C9	−0.6 (3)
N6—N5—C1—N3	−179.9 (2)	C1—N5—C10—C9	−177.7 (3)
C10—N5—C1—C11	−125.4 (3)	C8—C9—C10—N5	0.4 (3)
N6—N5—C1—C11	57.7 (3)	C12—O1—C11—C1	−124.7 (3)
N4—N3—C1—N1	−43.9 (3)	N1—C1—C11—O1	173.5 (2)
C7—N3—C1—N1	142.8 (3)	N5—C1—C11—O1	56.2 (3)
N4—N3—C1—N5	72.9 (3)	N3—C1—C11—O1	−64.8 (3)
C7—N3—C1—N5	−100.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···N2i	0.95	2.51	3.453 (4)	171
C9—H9A···N2ii	0.95	2.61	3.433 (4)	145
C4—H4A···O1iii	0.95	2.53	3.444 (4)	162

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