3,5,3′,5′-Tetra­methyl-4,4′-bi(1H-pyrazol­yl) hemihydrate

Abstract

In the title compound, C₁₀H₁₄N₄·0.5H₂O, the amino H atom of one of the two pyrazole rings is disordered over its two N atoms in a 1:1 ratio. The pyrazole rings are aligned at 60.1 (1)°. In the crystal, two bipyrazolyl mol­ecules are linked by an N—H⋯N hydrogen bond, generating a dimer; the dimer is connected to the water mol­ecule, which lies on a twofold rotation axis, resulting in the formation of a chain that makes an angle of ca 45.3 (1)° with the ab plane. The chains are cross-linked by N—H⋯O and O—H⋯N inter­actions, forming a three-dimensional network.

Related literature  

For general background to coordination compounds based on 3,5,3′,5′-tetra­methyl-1H,1′H-[4,4′]bipyrazolyl, see: Boldog et al. (2001 ▶); Zhang & Kitagawa (2008 ▶).

Experimental  

Crystal data  

• C₁₀H₁₄N₄·0.5H₂O

• M _r = 199.26

• Tetragonal,

• a = 24.9060 (4) Å

• c = 14.9684 (2) Å

• V = 9285.0 (2) ų

• Z = 32

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 293 K

• 0.40 × 0.38 × 0.37 mm

Data collection  

• Bruker SMART 1K CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.970, T _max = 0.973

• 27495 measured reflections

• 2050 independent reflections

• 1480 reflections with I > 2σ(I)

• R _int = 0.070

Refinement  

• R[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 0.169

• S = 1.10

• 2050 reflections

• 144 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812037920/ng5290Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1D⋯N4	0.84 (1)	1.95 (1)	2.791 (2)	175 (2)
N3—H3⋯O1i	0.88 (3)	1.96 (3)	2.827 (2)	169 (2)
N2—H2⋯N2ii	0.91 (5)	2.23 (5)	3.015 (4)	144 (5)
N1—H1⋯N1iii	0.91 (5)	1.98 (5)	2.862 (4)	164 (5)

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

supplementary crystallographic information

Comment

The use of 3,5,3',5'-tetramethyl-1H,1'H-[4,4']bipyrazolyl has drawn strong interest in coordination chemistry (Zhang et al., 2008, Boldog et al., 2001).

In the crystal structure of C₁₀H₁₄N₄^.0.5H₂O, the amino H atom of one of the two pyrazole rings is disordered over its two N atoms in a 1:1 ratio. The two pyrazole rings are aligned at 60.1 (1)°. Two C₁₀H₁₄N₄ molecules are linked by an N–H···N hydrogen bond to generate a dimer; the dimer is connected to the water molecule, which lies on a twofold rotation axis to chain that makes an angle of ca 45.3 (1)° with the ab plane. The chains were crosslinked together by N—H···O, and O—H···N associations to form a three-dimensional network structure

Experimental

3,5,3',5'-Tetramethyl-1H,1'H-[4,4']bipyrazolyl was prepared according to the literature and crystals were grown from its solution in ethanol. (Boldog et al. 2001).

Refinement

H atoms bonded to N, and O atoms were located in a difference Fourier map and refined isotropically.

Other H atoms were positioned geometrically with C—H = 0.96 Å, and constrained to ride on their parent atoms with U_iso(H) = 1.2Ueq(C).

Figures

Fig. 1.

The structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

The chain structure formed through the nonbonding interactions.

Crystal data

C10H14N4·0.5H2O	Dx = 1.140 Mg m−3
Mr = 199.26	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/acd	Cell parameters from 3432 reflections
Hall symbol: -I 4bd 2c	θ = 2.6–28.4°
a = 24.9060 (4) Å	µ = 0.08 mm−1
c = 14.9684 (2) Å	T = 293 K
V = 9285.0 (2) Å3	Block, colorless
Z = 32	0.40 × 0.38 × 0.37 mm
F(000) = 3424

Data collection

Bruker SMART 1K CCD area-detector diffractometer	2050 independent reflections
Radiation source: fine-focus sealed tube	1480 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
φ and ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −29→29
Tmin = 0.970, Tmax = 0.973	k = −24→29
27495 measured reflections	l = −17→16

Refinement

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) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0974P)2 + 1.819P] where P = (Fo2 + 2Fc2)/3
2050 reflections	(Δ/σ)max = 0.001
144 parameters	Δρmax = 0.23 e Å−3
1 restraint	Δρmin = −0.15 e Å−3

Special details

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 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.94307 (8)	0.75779 (9)	0.78322 (15)	0.0541 (6)
H1	0.9776 (18)	0.747 (2)	0.788 (3)	0.065*	0.50
N2	0.90490 (9)	0.72523 (9)	0.81759 (15)	0.0553 (6)
H2	0.915 (2)	0.694 (2)	0.843 (4)	0.066*	0.50
N3	0.77810 (8)	0.89553 (8)	0.65442 (13)	0.0456 (5)
H3	0.7666 (10)	0.9167 (10)	0.6112 (17)	0.055*
N4	0.76044 (8)	0.90310 (8)	0.73926 (12)	0.0466 (5)
O1	0.70458 (8)	1.0000	0.7500	0.0384 (5)
H1D	0.7224 (8)	0.9711 (6)	0.7496 (15)	0.046*
C1	0.95234 (11)	0.84574 (12)	0.7094 (2)	0.0661 (8)
H1A	0.9842	0.8510	0.7444	0.099*
H1B	0.9317	0.8783	0.7087	0.099*
H1C	0.9621	0.8363	0.6495	0.099*
C2	0.91976 (9)	0.80188 (9)	0.74928 (16)	0.0437 (6)
C3	0.86404 (8)	0.79798 (9)	0.76267 (14)	0.0371 (5)
C4	0.85697 (9)	0.74878 (10)	0.80591 (15)	0.0448 (6)
C5	0.80618 (11)	0.72243 (11)	0.8364 (2)	0.0743 (9)
H5A	0.8099	0.6842	0.8321	0.111*
H5B	0.7769	0.7341	0.7995	0.111*
H5C	0.7992	0.7322	0.8974	0.111*
C6	0.84046 (14)	0.84292 (14)	0.56201 (18)	0.0778 (10)
H6A	0.8343	0.8711	0.5195	0.117*
H6B	0.8246	0.8102	0.5406	0.117*
H6C	0.8784	0.8379	0.5697	0.117*
C7	0.81576 (9)	0.85775 (9)	0.64938 (14)	0.0411 (6)
C8	0.82394 (8)	0.83821 (8)	0.73500 (14)	0.0360 (5)
C9	0.78832 (9)	0.86804 (9)	0.78872 (15)	0.0414 (6)
C10	0.77949 (12)	0.86516 (12)	0.88733 (17)	0.0670 (8)
H10A	0.7599	0.8962	0.9066	0.100*
H10B	0.8135	0.8640	0.9173	0.100*
H10C	0.7594	0.8334	0.9014	0.100*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0405 (12)	0.0563 (14)	0.0656 (14)	0.0158 (11)	−0.0071 (10)	−0.0029 (11)
N2	0.0478 (13)	0.0522 (14)	0.0659 (15)	0.0120 (11)	−0.0155 (10)	0.0047 (11)
N3	0.0510 (12)	0.0432 (12)	0.0425 (12)	0.0130 (10)	−0.0015 (9)	0.0093 (9)
N4	0.0458 (12)	0.0496 (12)	0.0444 (11)	0.0139 (9)	0.0023 (9)	0.0035 (9)
O1	0.0378 (13)	0.0342 (12)	0.0433 (12)	0.000	0.000	0.0036 (10)
C1	0.0445 (15)	0.0709 (19)	0.083 (2)	−0.0065 (14)	0.0094 (14)	0.0056 (15)
C2	0.0360 (12)	0.0457 (13)	0.0493 (13)	0.0050 (11)	−0.0013 (10)	−0.0036 (10)
C3	0.0317 (12)	0.0394 (12)	0.0401 (12)	0.0036 (10)	−0.0051 (9)	0.0018 (9)
C4	0.0390 (13)	0.0449 (14)	0.0504 (14)	0.0029 (11)	−0.0118 (10)	0.0088 (10)
C5	0.0577 (18)	0.0673 (19)	0.098 (2)	−0.0160 (15)	−0.0166 (15)	0.0370 (16)
C6	0.094 (2)	0.096 (2)	0.0436 (15)	0.0424 (19)	0.0033 (14)	−0.0021 (14)
C7	0.0452 (14)	0.0388 (12)	0.0394 (13)	0.0080 (11)	0.0003 (10)	0.0028 (9)
C8	0.0333 (12)	0.0347 (11)	0.0399 (12)	0.0011 (10)	−0.0017 (9)	0.0028 (9)
C9	0.0377 (13)	0.0449 (13)	0.0416 (12)	0.0052 (11)	0.0007 (10)	0.0048 (10)
C10	0.073 (2)	0.079 (2)	0.0487 (16)	0.0162 (16)	0.0103 (14)	0.0079 (13)

Geometric parameters (Å, º)

N1—C2	1.342 (3)	C3—C8	1.474 (3)
N1—N2	1.351 (3)	C4—C5	1.497 (3)
N1—H1	0.91 (5)	C5—H5A	0.9600
N2—C4	1.342 (3)	C5—H5B	0.9600
N2—H2	0.91 (5)	C5—H5C	0.9600
N3—C7	1.331 (3)	C6—C7	1.492 (3)
N3—N4	1.357 (3)	C6—H6A	0.9600
N3—H3	0.88 (3)	C6—H6B	0.9600
N4—C9	1.339 (3)	C6—H6C	0.9600
O1—H1D	0.844 (9)	C7—C8	1.386 (3)
C1—C2	1.486 (3)	C8—C9	1.409 (3)
C1—H1A	0.9600	C9—C10	1.494 (3)
C1—H1B	0.9600	C10—H10A	0.9600
C1—H1C	0.9600	C10—H10B	0.9600
C2—C3	1.406 (3)	C10—H10C	0.9600
C3—C4	1.397 (3)
C2—N1—N2	109.32 (19)	C4—C5—H5B	109.5
C2—N1—H1	134 (4)	H5A—C5—H5B	109.5
N2—N1—H1	117 (4)	C4—C5—H5C	109.5
C4—N2—N1	108.3 (2)	H5A—C5—H5C	109.5
C4—N2—H2	132 (4)	H5B—C5—H5C	109.5
N1—N2—H2	119 (4)	C7—C6—H6A	109.5
C7—N3—N4	112.30 (18)	C7—C6—H6B	109.5
C7—N3—H3	127.5 (17)	H6A—C6—H6B	109.5
N4—N3—H3	119.9 (17)	C7—C6—H6C	109.5
C9—N4—N3	105.01 (18)	H6A—C6—H6C	109.5
C2—C1—H1A	109.5	H6B—C6—H6C	109.5
C2—C1—H1B	109.5	N3—C7—C8	107.43 (19)
H1A—C1—H1B	109.5	N3—C7—C6	121.0 (2)
C2—C1—H1C	109.5	C8—C7—C6	131.5 (2)
H1A—C1—H1C	109.5	C7—C8—C9	104.47 (19)
H1B—C1—H1C	109.5	C7—C8—C3	126.7 (2)
N1—C2—C3	108.5 (2)	C9—C8—C3	128.66 (19)
N1—C2—C1	121.2 (2)	N4—C9—C8	110.78 (19)
C3—C2—C1	130.3 (2)	N4—C9—C10	120.1 (2)
C4—C3—C2	104.54 (19)	C8—C9—C10	129.1 (2)
C4—C3—C8	129.9 (2)	C9—C10—H10A	109.5
C2—C3—C8	125.59 (19)	C9—C10—H10B	109.5
N2—C4—C3	109.4 (2)	H10A—C10—H10B	109.5
N2—C4—C5	121.4 (2)	C9—C10—H10C	109.5
C3—C4—C5	129.2 (2)	H10A—C10—H10C	109.5
C4—C5—H5A	109.5	H10B—C10—H10C	109.5
C2—N1—N2—C4	−0.3 (3)	N4—N3—C7—C6	179.7 (2)
C7—N3—N4—C9	−0.4 (3)	N3—C7—C8—C9	−0.4 (2)
N2—N1—C2—C3	0.4 (3)	C6—C7—C8—C9	−179.4 (3)
N2—N1—C2—C1	178.0 (2)	N3—C7—C8—C3	−176.4 (2)
N1—C2—C3—C4	−0.3 (3)	C6—C7—C8—C3	4.5 (4)
C1—C2—C3—C4	−177.7 (3)	C4—C3—C8—C7	−122.9 (3)
N1—C2—C3—C8	−179.9 (2)	C2—C3—C8—C7	56.6 (3)
C1—C2—C3—C8	2.7 (4)	C4—C3—C8—C9	62.0 (3)
N1—N2—C4—C3	0.1 (3)	C2—C3—C8—C9	−118.5 (3)
N1—N2—C4—C5	179.5 (2)	N3—N4—C9—C8	0.2 (3)
C2—C3—C4—N2	0.2 (3)	N3—N4—C9—C10	179.7 (2)
C8—C3—C4—N2	179.7 (2)	C7—C8—C9—N4	0.1 (3)
C2—C3—C4—C5	−179.3 (3)	C3—C8—C9—N4	176.0 (2)
C8—C3—C4—C5	0.3 (4)	C7—C8—C9—C10	−179.3 (3)
N4—N3—C7—C8	0.5 (3)	C3—C8—C9—C10	−3.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1D···N4	0.84 (1)	1.95 (1)	2.791 (2)	175 (2)
N3—H3···O1i	0.88 (3)	1.96 (3)	2.827 (2)	169 (2)
N2—H2···N2ii	0.91 (5)	2.23 (5)	3.015 (4)	144 (5)
N1—H1···N1iii	0.91 (5)	1.98 (5)	2.862 (4)	164 (5)

Symmetry codes: (i) −y+7/4, x+1/4, z−1/4; (ii) y+1/4, x−1/4, −z+7/4; (iii) −x+2, −y+3/2, z.