Literature DB >> 21583640

2-(1H-Pyrazol-3-yl)pyridinium chloride monohydrate.

Tatiana R Amarante¹, Isabel S Gonçalves, Filipe A Almeida Paz.

Abstract

The title organic salt, C(8)H(8)N(3) (+)·Cl(-)·H(2)O, exhibits a rich hydrogen-bonding network involving all constituent species. The water mol-ecules are engaged in strong O-H⋯Cl inter-actions with the chloride anions, two neighboring protonated 2-(1H-pyrazol-3-yl)pyridinium species inter-act via N-H⋯N bonds with two pyrazole rings. Further, a short and highly directional C-H⋯O inter-action is observed connecting the pyridinium ring to the water mol-ecule of crystallization. Weak C-H⋯Cl and N-H⋯Cl inter-actions contribute to the stabilization of the crystal structure.

Entities: Chemical Disease Species

Year: 2009 PMID： 21583640 PMCID： PMC2977379 DOI： 10.1107/S1600536809028402

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For related structures with 2-(3-pyrazolyl)pyridine or its derivatives, see: Coelho et al. (2006 ▶, 2007 ▶); Fleming et al. (1998 ▶); Jones et al. (1997 ▶); Lam et al. (1997 ▶); Leita et al. (2004 ▶); Li (2007 ▶); Liu et al. (2006 ▶); Mokuolu et al. (2007 ▶); Hu, Li et al. (2006 ▶); Hu, Wang et al. (2006 ▶); Hu et al. (2008 ▶); Huo et al. (2006 ▶); Ward, Fleming et al. (1998 ▶); Ward, Mann et al. (1998 ▶). For detailed background to the role of hydrogen bonds in the supramolecular organization of organic crystals, see: Nangia & Desiraju (1998 ▶). For general background studies on crystal engineering approaches from our research group, see: Paz & Klinowski (2003 ▶); Paz et al. (2002 ▶). For a description of the graph-set notation for hydrogen-bonded aggregates, see: Bernstein et al. (1995 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C8H8N3 +·Cl−·H2O M = 199.64 Triclinic, a = 6.8487 (2) Å b = 8.3523 (3) Å c = 9.0843 (3) Å α = 114.693 (1)° β = 99.867 (2)° γ = 91.097 (2)° V = 462.75 (3) Å3 Z = 2 Mo Kα radiation μ = 0.38 mm−1 T = 150 K 0.18 × 0.15 × 0.09 mm

Data collection

Bruker X8 Kappa CCD APEXII diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.930, T max = 0.951 26245 measured reflections 4422 independent reflections 3687 reflections with I > 2σ(I) R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.048 wR(F 2) = 0.162 S = 1.07 4422 reflections 124 parameters 3 restraints H atoms treated by a mixture of independent and constrained refinement Δρmax = 1.26 e Å−3 Δρmin = −0.99 e Å−3 Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT-Plus (Bruker, 2005 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028402/tk2502sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028402/tk2502Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report Enhanced figure: interactive version of Fig. 4 Enhanced figure: interactive version of Fig. 5

C₈H₈N₃⁺·Cl⁻·H₂O	Z = 2
M_r = 199.64	F(000) = 208
Triclinic, P1	D_x = 1.433 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8487 (2) Å	Cell parameters from 9894 reflections
b = 8.3523 (3) Å	θ = 2.5–39.6°
c = 9.0843 (3) Å	µ = 0.38 mm⁻¹
α = 114.693 (1)°	T = 150 K
β = 99.867 (2)°	Prism, colourless
γ = 91.097 (2)°	0.18 × 0.15 × 0.09 mm
V = 462.75 (3) Å³

Bruker X8 Kappa CCD APEXII diffractometer	4422 independent reflections
Radiation source: fine-focus sealed tube	3687 reflections with I > 2σ(I)
graphite	R_int = 0.024
ω and φ scans	θ_max = 36.3°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −11→11
T_min = 0.930, T_max = 0.951	k = −13→13
26245 measured reflections	l = −15→15

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0872P)² + 0.3244P] where P = (F_o² + 2F_c²)/3
4422 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 1.26 e Å⁻³
3 restraints	Δρ_min = −0.99 e Å⁻³

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.

	x	y	z	U_iso*/U_eq
N1	0.61184 (17)	0.19217 (15)	0.62050 (15)	0.0183 (2)
H1	0.5010	0.1500	0.6343	0.022*
N2	0.70080 (17)	0.10464 (15)	0.49209 (14)	0.0173 (2)
N3	1.1678 (2)	0.28024 (18)	0.43052 (18)	0.0245 (2)
H3	1.1939	0.3832	0.5176	0.029*
C1	0.7105 (2)	0.35120 (18)	0.72575 (18)	0.0209 (2)
H1C	0.6738	0.4335	0.8239	0.025*
C2	0.8746 (2)	0.37168 (17)	0.66403 (18)	0.0195 (2)
H2	0.9742	0.4694	0.7095	0.023*
C3	0.86126 (18)	0.21518 (16)	0.51834 (16)	0.0153 (2)
C4	0.99968 (18)	0.16869 (16)	0.40505 (16)	0.0155 (2)
C5	0.96578 (17)	0.01058 (15)	0.27103 (14)	0.01290 (18)
H5	0.8509	−0.0658	0.2533	0.015*
C6	1.0876 (2)	−0.04322 (19)	0.16188 (17)	0.0206 (2)
H6	1.0589	−0.1564	0.0705	0.025*
C7	1.2539 (2)	0.0651 (2)	0.18193 (19)	0.0231 (3)
H7	1.3393	0.0285	0.1042	0.028*
C8	1.2942 (2)	0.2287 (2)	0.31810 (19)	0.0220 (2)
H8	1.4081	0.3052	0.3343	0.026*
Cl1	0.67400 (5)	0.34331 (4)	0.14179 (4)	0.02184 (10)
O1W	0.68083 (18)	0.73153 (15)	0.15022 (15)	0.0261 (2)
H1A	0.575 (3)	0.719 (3)	0.064 (2)	0.039*
H1B	0.692 (4)	0.623 (2)	0.159 (3)	0.039*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0160 (4)	0.0180 (5)	0.0194 (5)	−0.0016 (4)	0.0048 (4)	0.0061 (4)
N2	0.0165 (4)	0.0166 (4)	0.0173 (4)	−0.0016 (3)	0.0037 (4)	0.0059 (4)
N3	0.0234 (5)	0.0216 (5)	0.0292 (6)	−0.0003 (4)	0.0076 (5)	0.0107 (5)
C1	0.0206 (6)	0.0170 (5)	0.0217 (6)	0.0001 (4)	0.0062 (5)	0.0042 (4)
C2	0.0182 (5)	0.0147 (5)	0.0228 (6)	−0.0012 (4)	0.0049 (4)	0.0051 (4)
C3	0.0144 (5)	0.0142 (4)	0.0172 (5)	−0.0002 (4)	0.0023 (4)	0.0068 (4)
C4	0.0150 (5)	0.0147 (5)	0.0174 (5)	0.0004 (4)	0.0025 (4)	0.0076 (4)
C5	0.0123 (4)	0.0127 (4)	0.0128 (4)	−0.0003 (3)	0.0011 (3)	0.0052 (3)
C6	0.0219 (6)	0.0208 (5)	0.0184 (5)	0.0033 (4)	0.0051 (4)	0.0073 (4)
C7	0.0219 (6)	0.0259 (6)	0.0249 (6)	0.0042 (5)	0.0096 (5)	0.0123 (5)
C8	0.0190 (5)	0.0227 (6)	0.0276 (6)	0.0003 (4)	0.0077 (5)	0.0129 (5)
Cl1	0.01974 (15)	0.02010 (15)	0.02130 (16)	−0.00223 (11)	0.00433 (11)	0.00468 (11)
O1W	0.0240 (5)	0.0202 (5)	0.0275 (5)	−0.0047 (4)	−0.0012 (4)	0.0065 (4)

N1—N2	1.3471 (16)	C3—C4	1.4572 (18)
N1—C1	1.3485 (18)	C4—C5	1.3521 (17)
N1—H1	0.8800	C5—C6	1.3439 (18)
N2—C3	1.3433 (16)	C5—H5	0.9500
N3—C8	1.389 (2)	C6—C7	1.379 (2)
N3—C4	1.3908 (18)	C6—H6	0.9500
N3—H3	0.8800	C7—C8	1.389 (2)
C1—C2	1.3765 (19)	C7—H7	0.9500
C1—H1C	0.9500	C8—H8	0.9500
C2—C3	1.4061 (18)	O1W—H1A	0.940 (19)
C2—H2	0.9500	O1W—H1B	0.95 (2)

N2—N1—C1	112.87 (11)	C5—C4—N3	118.43 (12)
N2—N1—H1	123.6	C5—C4—C3	119.14 (11)
C1—N1—H1	123.6	N3—C4—C3	122.42 (12)
C3—N2—N1	104.03 (10)	C6—C5—C4	122.82 (12)
C8—N3—C4	119.79 (13)	C6—C5—H5	118.6
C8—N3—H3	120.1	C4—C5—H5	118.6
C4—N3—H3	120.1	C5—C6—C7	120.30 (13)
N1—C1—C2	107.03 (12)	C5—C6—H6	119.8
N1—C1—H1C	126.5	C7—C6—H6	119.8
C2—C1—H1C	126.5	C6—C7—C8	118.69 (13)
C1—C2—C3	104.32 (11)	C6—C7—H7	120.7
C1—C2—H2	127.8	C8—C7—H7	120.7
C3—C2—H2	127.8	N3—C8—C7	119.94 (13)
N2—C3—C2	111.76 (11)	N3—C8—H8	120.0
N2—C3—C4	121.41 (11)	C7—C8—H8	120.0
C2—C3—C4	126.84 (11)	H1A—O1W—H1B	110.2 (14)

C1—N1—N2—C3	−0.48 (15)	C2—C3—C4—C5	179.05 (13)
N2—N1—C1—C2	0.23 (17)	N2—C3—C4—N3	−179.37 (12)
N1—C1—C2—C3	0.12 (16)	C2—C3—C4—N3	−0.1 (2)
N1—N2—C3—C2	0.55 (15)	N3—C4—C5—C6	0.11 (19)
N1—N2—C3—C4	179.90 (11)	C3—C4—C5—C6	−179.10 (12)
C1—C2—C3—N2	−0.43 (16)	C4—C5—C6—C7	−1.1 (2)
C1—C2—C3—C4	−179.74 (13)	C5—C6—C7—C8	1.0 (2)
C8—N3—C4—C5	0.9 (2)	C4—N3—C8—C7	−0.9 (2)
C8—N3—C4—C3	−179.96 (13)	C6—C7—C8—N3	−0.1 (2)
N2—C3—C4—C5	−0.20 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.88	2.25	2.9502 (16)	137
O1W—H1A···Cl1ⁱⁱ	0.94 (2)	2.18 (1)	3.1113 (13)	173 (2)
O1W—H1B···Cl1	0.95 (2)	2.28 (1)	3.2106 (12)	170 (2)
C5—H5···O1Wⁱⁱⁱ	0.95	.	2.7203 (16)	156
C8—H8···Cl1^iv	0.95	.	3.5862 (18)	137
N3—H3···Cl1^v	0.88	2.94	3.7915 (15)	162
C2—H2···Cl1^v	0.95	.	3.5604 (13)	159
C6—H6···Cl1^vi	0.95	.	3.5329 (14)	127
C7—H7···Cl1^vi	0.95	.	3.5649 (14)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.88	2.25	2.9502 (16)	137
O1W—H1A⋯Cl1ⁱⁱ	0.940 (19)	2.176 (10)	3.1113 (13)	173 (2)
O1W—H1B⋯Cl1	0.95 (2)	2.279 (11)	3.2106 (12)	170 (2)
C5—H5⋯O1Wⁱⁱⁱ	0.95		2.7203 (16)	156
C8—H8⋯Cl1^iv	0.95		3.5862 (18)	137
N3—H3⋯Cl1^v	0.88	2.94	3.7915 (15)	162
C2—H2⋯Cl1^v	0.95		3.5604 (13)	159
C6—H6⋯Cl1^vi	0.95		3.5329 (14)	127
C7—H7⋯Cl1^vi	0.95		3.5649 (14)	123

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

8 in total

1. Synthesis and X-ray Crystal Structure of a Triple-Stranded Helical Supramolecular Complex Formed between Tris(3-(pyridin-2-yl)pyrazole)ruthenium(II) and Copper(I).

Authors: Michael H. W. Lam; Samuel T. C. Cheung; Ka-Man Fung; Wing-Tak Wong
Journal: Inorg Chem Date: 1997-10-08 Impact factor: 5.165

2. The Cambridge Structural Database: a quarter of a million crystal structures and rising.

Authors: Frank H Allen
Journal: Acta Crystallogr B Date: 2002-05-29

3. Syntheses, crystal structures, and magneto-structural correlations of novel Cu(II) complexes containing a planar [Cu(mu-L1)]2 (HL1 = 3-(2-pyridyl)pyrazole) unit: from dinuclear to tetranuclear and then to one-dimensional compounds.

Authors: Tong-Liang Hu; Jian-Rong Li; Chun-Sen Liu; Xue-Song Shi; Jiang-Ning Zhou; Xian-He Bu; Joan Ribas
Journal: Inorg Chem Date: 2006-01-09 Impact factor: 5.165

4. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

5. Four copper(II) pyrazolido complexes derived from reactions of 3{5}-substituted pyrazoles with CuF(2) or Cu(OH)(2).

Authors: Q Folshade Mokuolu; Dolos Foguet-Albiol; Leigh F Jones; Joanna Wolowska; Radoslaw M Kowalczyk; Colin A Kilner; George Christou; Patrick C McGowan; Malcolm A Halcrow
Journal: Dalton Trans Date: 2007-03-09 Impact factor: 4.390

6. Structure and magnetism of a new pyrazolate bridged iron(II) spin crossover complex displaying a single HS-HS to LS-LS transition.

Authors: Ben A Leita; Boujemaa Moubaraki; Keith S Murray; Jonathan P Smith; John D Cashion
Journal: Chem Commun (Camb) Date: 2003-11-20 Impact factor: 6.222

7. Microwave assisted synthesis of molybdenum and tungsten tetracarbonyl complexes with a pyrazolylpyridine ligand. Crystal structure of cis-[Mo(CO)4{ethyl[3-(2-pyridyl)-1-pyrazolyl]acetate}].

Authors: Ana C Coelho; Filipe A Almeida Paz; Jacek Klinowski; Martyn Pillinger; Isabel S Gonçalves
Journal: Molecules Date: 2006-12-06 Impact factor: 4.411

8. d(10) Metal complexes assembled from isomeric benzenedicarboxylates and 3-(2-pyridyl)pyrazole showing 1D chain structures: syntheses, structures and luminescent properties.

Authors: Tong-Liang Hu; Ruo-Qiang Zou; Jian-Rong Li; Xian-He Bu
Journal: Dalton Trans Date: 2008-01-21 Impact factor: 4.390