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

Jin, S.; Huang, Y.; Fang, H.; Wang, T.; Ding, L.

doi:10.1107/S1600536812037920

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2896

https://doi.org/10.1107/S1600536812037920

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

Shouwen Jin,^a ^* Yanfei Huang,^a Hao Fang,^a Tianyi Wang ^a and Liangliang Ding ^a

^aTianmu College of ZheJiang A & F University, Lin'An 311300, People's Republic of China
^*Correspondence e-mail: shouwenjin@yahoo.cn

(Received 21 August 2012; accepted 4 September 2012; online 8 September 2012)

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, I 4₁ /a c d
a = 24.9060 (4) Å
c = 14.9684 (2) Å
V = 9285.0 (2) Å³
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[F² > 2σ(F²)] = 0.053
wR(F²) = 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

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) $[-y+{\script{7\over 4}}, x+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (ii) $[y+{\script{1\over 4}}, x-{\script{1\over 4}}, -z+{\script{7\over 4}}]$ ; (iii) $[-x+2, -y+{\script{3\over 2}}, z]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812037920/ng5290sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037920/ng5290Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812037920/ng5290Isup3.cml

checkCIF report

Comment top

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

Related literature top

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 top

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).

Structure description top

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).

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).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 (Sheldrick, 2008).

Figures top

	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.

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

Crystal data top

C₁₀H₁₄N₄·0.5H₂O	D_x = 1.140 Mg m⁻³
M_r = 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 top

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

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) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0974P)² + 1.819P] where P = (F_o² + 2F_c²)/3
2050 reflections	(Δ/σ)_max = 0.001
144 parameters	Δρ_max = 0.23 e Å⁻³
1 restraint	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₀H₁₄N₄·0.5H₂O	Z = 32
M_r = 199.26	Mo Kα radiation
Tetragonal, I4₁/acd	µ = 0.08 mm⁻¹
a = 24.9060 (4) Å	T = 293 K
c = 14.9684 (2) Å	0.40 × 0.38 × 0.37 mm
V = 9285.0 (2) Å³

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2050 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1480 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.973	R_int = 0.070
27495 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	1 restraint
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.23 e Å⁻³
2050 reflections	Δρ_min = −0.15 e Å⁻³
144 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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) top

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) top

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.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄N₄·0.5H₂O
M_r	199.26
Crystal system, space group	Tetragonal, I4₁/acd
Temperature (K)	293
a, c (Å)	24.9060 (4), 14.9684 (2)
V (Å³)	9285.0 (2)
Z	32
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.38 × 0.37

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.970, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	27495, 2050, 1480
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.169, 1.10
No. of reflections	2050
No. of parameters	144
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.15

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1D···N4	0.844 (9)	1.948 (10)	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.

Acknowledgements

We gratefully acknowledge the financial support of the Education Office Foundation of Zhejiang Province (project No. Y201017321) and the Innovation Project of Zhejiang A & F University.

References

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