catena-Poly[[[dichlorido(pyridin-1-ium-3-yl)arsenic(III)]-μ-chlorido] mono-hydrate].

The crystal structure of the title compound, {[AsCl3(C5H5N)]·H2O} n , is characterized by polymeric chains consisting of alternating arsenic and chlorine atoms running parallel to the a axis. O-H⋯Cl and N-H⋯O hydrogen bonds mediated by non-coordinating water mol-ecules assemble these chains into a three-dimensional framework. The As(III) atom, the atoms of the pyridinium ring and the water O atom have m site symmetry and the bridging Cl atom has site symmetry 2. This is the first reported organotrichloro-arsenate(III) in which arsenic adopts a ψ-octa-hedral fivefold coordination.

Related literature

For the synthesis, see: Binz & von Schickh (1936 ▶). For mono­meric and oligomeric monon class="Chemical">organohaloarsenates(III) with tetra­coordinate arsenic, see: Grewe et al. (1998 ▶). For homologous monoorganohaloanti­monate(III)/-bis­muth­ate(III) structures, see: Althaus et al. (1999 ▶); Breunig et al. (1992 ▶, 1999 ▶, 2010 ▶); Hall & Sowerby (1988 ▶); James et al. (1999 ▶); Preut et al. (1987 ▶); Sheldrick & Martin (1992 ▶); von Seyerl et al. (1986 ▶). For organoarsenic functionalized metal oxide clusters, see: Breen, Clérac et al. (2012 ▶); Breen, Zhang et al. (2012 ▶); Onet et al. (2011 ▶); Zhang et al. (2012 ▶).

Experimental

Crystal data

[AsCl3(C5H5N)]·H2O

M = 278.39

Orthorhombic,

a = 8.2107 (9) Å

b = 8.5812 (9) Å

c = 13.2046 (14) Å

V = 930.37 (17) Å3

Z = 4

Mo Kα radiation

μ = 4.46 mm−1

T = 200 K

0.5 × 0.2 × 0.2 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.341, T max = 0.469

3423 measured reflections

1184 independent reflections

1167 reflections with I > 2σ(I)

R int = 0.068

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.078

S = 1.10

1184 reflections

66 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.14 e Å−3

Δρmin = −1.28 e Å−3

Absolute structure: Flack (1983 ▶), 529 Friedel pairs

Flack parameter: 0.006 (12)

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Click here for additional data file.

Crystal structure: contains datablock(s) global. DOI: 10.1107/S1600536812042882/nk2180sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042882/nk2180Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812042882/nk2180Isup3.cdx

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

[AsCl3(C5H5N)]·H2O	Dx = 1.987 Mg m−3
Mr = 278.39	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Im2a	Cell parameters from 2911 reflections
a = 8.2107 (9) Å	θ = 2.8–28.2°
b = 8.5812 (9) Å	µ = 4.46 mm−1
c = 13.2046 (14) Å	T = 200 K
V = 930.37 (17) Å3	Block, colourless
Z = 4	0.5 × 0.2 × 0.2 mm
F(000) = 544

Bruker SMART APEX CCD diffractometer	1184 independent reflections
Radiation source: fine-focus sealed tube	1167 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
φ and ω scans	θmax = 28.2°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −10→10
Tmin = 0.341, Tmax = 0.469	k = −11→9
3423 measured reflections	l = −13→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0554P)2] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
1184 reflections	Δρmax = 1.14 e Å−3
66 parameters	Δρmin = −1.28 e Å−3
3 restraints	Absolute structure: Flack (1983), 529 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.006 (12)

Experimental. R(int) was 0.0767 before and 0.0385 after correction. The Ratio of minimum to maximum transmission is 0.7260. The λ/2 correction factor is 0.0015.

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	Uiso*/Ueq
As1	0.7500	0.27357 (4)	0.63175 (3)	0.01702 (14)
Cl1	0.55187 (9)	0.36810 (11)	0.73375 (6)	0.0270 (2)
Cl2	0.5000	0.15046 (13)	0.5000	0.0229 (2)
N3	0.7500	0.5797 (5)	0.3838 (3)	0.0215 (8)
H3	0.7500	0.5690	0.3175	0.026*
C1	0.7500	0.4632 (5)	0.5450 (3)	0.0187 (8)
C2	0.7500	0.4508 (5)	0.4411 (3)	0.0201 (8)
H2	0.7500	0.3509	0.4100	0.024*
C4	0.7500	0.7237 (6)	0.4225 (4)	0.0291 (11)
H4	0.7500	0.8117	0.3788	0.035*
C5	0.7500	0.7435 (6)	0.5249 (4)	0.0402 (14)
H5	0.7500	0.8450	0.5536	0.048*
C6	0.7500	0.6127 (6)	0.5865 (4)	0.0333 (12)
H6	0.7500	0.6250	0.6580	0.040*
O1	0.7500	0.0724 (4)	0.3215 (2)	0.0242 (7)
H1	0.672 (2)	0.093 (6)	0.358 (2)	0.036*

	U11	U22	U33	U12	U13	U23
As1	0.0145 (2)	0.0197 (2)	0.0169 (2)	0.000	0.000	0.00251 (18)
Cl1	0.0210 (3)	0.0386 (5)	0.0213 (4)	0.0061 (3)	0.0042 (3)	0.0002 (3)
Cl2	0.0192 (5)	0.0278 (6)	0.0219 (5)	0.000	0.0024 (4)	0.000
N3	0.0224 (19)	0.025 (2)	0.0172 (15)	0.000	0.000	0.0015 (14)
C1	0.0204 (19)	0.018 (2)	0.0173 (19)	0.000	0.000	−0.0001 (16)
C2	0.0194 (19)	0.017 (2)	0.024 (2)	0.000	0.000	−0.0017 (16)
C4	0.034 (3)	0.021 (2)	0.032 (2)	0.000	0.000	0.0019 (18)
C5	0.072 (4)	0.014 (3)	0.034 (3)	0.000	0.000	−0.003 (2)
C6	0.058 (4)	0.025 (3)	0.017 (2)	0.000	0.000	−0.0035 (18)
O1	0.0180 (15)	0.0329 (19)	0.0218 (15)	0.000	0.000	−0.0053 (14)

As1—C1	1.990 (4)	C2—H2	0.9500
As1—Cl1	2.2624 (8)	C4—C5	1.363 (7)
As1—Cl2	2.8907 (5)	C4—H4	0.9500
N3—C4	1.337 (7)	C5—C6	1.386 (7)
N3—C2	1.340 (6)	C5—H5	0.9500
N3—H3	0.8800	C6—H6	0.9500
C1—C2	1.377 (6)	O1—H1	0.818 (17)
C1—C6	1.395 (7)
C1—As1—Cl1	92.83 (9)	N3—C2—C1	119.9 (4)
C1—As1—Cl2	87.28 (9)	N3—C2—H2	120.0
Cl1—As1—Cl1i	91.95 (4)	C1—C2—H2	120.0
Cl1—As1—Cl2ii	179.25 (3)	N3—C4—C5	119.6 (5)
Cl1—As1—Cl2	88.78 (2)	N3—C4—H4	120.2
Cl2ii—As1—Cl2	90.49 (2)	C5—C4—H4	120.2
As1iii—Cl2—As1	137.13 (5)	C4—C5—C6	118.7 (4)
C4—N3—C2	123.2 (4)	C4—C5—H5	120.6
C4—N3—H3	118.4	C6—C5—H5	120.6
C2—N3—H3	118.4	C5—C6—C1	121.0 (4)
C2—C1—C6	117.5 (4)	C5—C6—H6	119.5
C2—C1—As1	120.7 (3)	C1—C6—H6	119.5
C6—C1—As1	121.8 (3)
C1—As1—Cl2—As1iii	−26.08 (9)	C6—C1—C2—N3	0.000 (2)
Cl1—As1—Cl2—As1iii	66.82 (2)	As1—C1—C2—N3	180.000 (1)
Cl2ii—As1—Cl2—As1iii	−113.33 (2)	C2—N3—C4—C5	0.000 (2)
Cl1—As1—C1—C2	−133.95 (2)	N3—C4—C5—C6	0.000 (2)
Cl2—As1—C1—C2	−45.308 (11)	C4—C5—C6—C1	0.000 (2)
Cl1—As1—C1—C6	46.05 (2)	C2—C1—C6—C5	0.000 (2)
Cl2—As1—C1—C6	134.692 (12)	As1—C1—C6—C5	180.000 (2)
C4—N3—C2—C1	0.000 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl2	0.82 (2)	2.40 (2)	3.197 (2)	165 (3)
N3—H3···O1iv	0.88	1.84	2.711	173

Table 1

Selected bond lengths (Å)

As1—Cl1	2.2624 (8)
As1—Cl2	2.8907 (5)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl2	0.82 (2)	2.40 (2)	3.197 (2)	165 (3)
N3—H3⋯O1i	0.88	1.84	2.711	173

Symmetry code: (i) .