metal-organic compounds
catena-Poly[[[dichlorido(pyridin-1-ium-3-yl)arsenic(III)]-μ-chlorido] monohydrate]
aSchool of Chemistry, Trinity College Dublin, Dublin 2, Ireland
*Correspondence e-mail: schmittw@tcd.ie
The 3(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 molecules assemble these chains into a three-dimensional framework. The AsIII atom, the atoms of the pyridinium ring and the water O atom have m and the bridging Cl atom has 2. This is the first reported organotrichloroarsenate(III) in which arsenic adopts a ψ-octahedral fivefold coordination.
of the title compound, {[AsClRelated literature
For the synthesis, see: Binz & von Schickh (1936). For monomeric and oligomeric monoorganohaloarsenates(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
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536812042882/nk2180sup1.cif
contains datablock global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042882/nk2180Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042882/nk2180Isup3.cdx
The synthesis reported by Binz & von Schickh (1936) was slightly modified as follows: 3-aminopyridine (20 mmol, 1.882 g) was dissolved in conc. HCl (32%, 15 ml) and As2O3 (20 mmol, 3.957 g) and CuCl (2 mmol, 0.198 g) were added to the solution. The solution was cooled in an ice bath to -5 °C. NaNO2 (30 mmol, 2.07 g) was dissolved in water (3 ml) and slowly added to the solution while keeping the temperature below 0 °C. The reaction mixture was then stirred at 35 °C for 8 h. After cooling to r.t. the precipitate was filtered off and washed with 1-molar HCl solution (2 × 20 ml). The filtrate was cooled to -20 °C and after 7 days the product was obtained in the form of large colourless needles.
H atoms on the pyridine aromatic ring were positioned geometrically and refined using a riding model with C—H distances constrained to 0.95 Å and the N—H distance constrained to 0.88 Å. Uiso for these hydrogen atoms was constrained to Uiso(H) = 1.2 Ueq(C or N). Restraints were applied to the O1—H1 distance and the H1—O1—H1 angle and Uiso was constrained to Uiso(H1) = 1.5 Ueq(O1). The anisotropic displacement parameters of the atoms in the aromatic ring indicate a slight disorder around the mirror plane, but refining this disorder did not improve the structural model significantly.
Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[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 | Absolute structure parameter: 0.006 (12) |
[AsCl3(C5H5N)]·H2O | V = 930.37 (17) Å3 |
Mr = 278.39 | Z = 4 |
Orthorhombic, Im2a | Mo Kα radiation |
a = 8.2107 (9) Å | µ = 4.46 mm−1 |
b = 8.5812 (9) Å | T = 200 K |
c = 13.2046 (14) Å | 0.5 × 0.2 × 0.2 mm |
Bruker SMART APEX CCD diffractometer | 1184 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1167 reflections with I > 2σ(I) |
Tmin = 0.341, Tmax = 0.469 | Rint = 0.068 |
3423 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.078 | Δρmax = 1.14 e Å−3 |
S = 1.10 | Δρmin = −1.28 e Å−3 |
1184 reflections | Absolute structure: Flack (1983), 529 Friedel pairs |
66 parameters | Absolute structure parameter: 0.006 (12) |
3 restraints |
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) |
Symmetry codes: (i) −x+3/2, y, z; (ii) x+1/2, y, −z+1; (iii) −x+1, y, −z+1. |
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 |
Symmetry code: (iv) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [AsCl3(C5H5N)]·H2O |
Mr | 278.39 |
Crystal system, space group | Orthorhombic, Im2a |
Temperature (K) | 200 |
a, b, c (Å) | 8.2107 (9), 8.5812 (9), 13.2046 (14) |
V (Å3) | 930.37 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.46 |
Crystal size (mm) | 0.5 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.341, 0.469 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3423, 1184, 1167 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.078, 1.10 |
No. of reflections | 1184 |
No. of parameters | 66 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.14, −1.28 |
Absolute structure | Flack (1983), 529 Friedel pairs |
Absolute structure parameter | 0.006 (12) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS (Sheldrick, 2008), SHELXL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl2 | 0.818 (17) | 2.40 (2) | 3.197 (2) | 165 (3) |
N3—H3···O1i | 0.88 | 1.84 | 2.711 | 173.2 |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
Acknowledgements
The authors thank the Science Foundation Ireland (SFI,06/RFP/CHE173 and 08/IN.1/I2047)for financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In the course of our work on arylarsonate functionalized metal oxide clusters (see Breen, Clérac et al. (2012), Breen, Zhang et al. (2012) and references therein for vanadium oxide clusters, Onet et al. (2011) for molybdenum oxide clusters and Zhang et al. (2012) for manganese oxide clusters) we prepared the title compound, whose crystal structure had until now not been determined. In general, the structural chemistry of organohaloarsenates(III) has not been the object of intense study, the only relevant peer-reviewed publication known to us being the contribution by Grewe et al. (1998), which is summarized below. The homologous organohalobismuthates(III) and organohaloantimonates(III) have been more widely studied.
Organodichloroarsines compounds are known to act as soft Lewis acids and form adducts with chloride anions, e.g. [RAsCl3]- (R = Me, Et, Ph) and [MeAsCl2(µ-Cl)AsCl2Me]-. In these adducts, arsenic occurs in ψ-trigonal bipyramidal fourfold coordination. Pentacoordinate, ψ-octahedral adducts are only known for the bromo analogues on account of their stronger acidity: organotribromoarsenates(III) form doubly bridged dimers [RBr2As(µ-Br2)AsBr2R]2- (R = Me, Et, Ph) (Grewe et al., 1998). The homologous organohaloantimonates(III) and organohalobismuthates(III) form a wider variety of structures based mostly on ψ-octahedral REX4 motifs. These units are found isolated in [PhSbCl4]2- (Hall & Sowerby, 1988), [PhSbBr4]2- (James et al., 1999) and [MeSbI4]2- (Breunig et al., 1992). The ψ-trigonal bipyramidal [PhSbCl3]- does exist (Hall & Sowerby, 1988), but its ψ-octahedral dimer [PhCl2Sb(µ-Cl)2SbCl2Ph]2- is also attested (Preut et al., 1987). [Me2Sb2Cl6]2- (Breunig et al., 2010), [Me2Sb2Br6]2- (Althaus et al., 1999), [Ph2Sb2I6]2- (Breunig et al., 1999) and [Ph2Bi2Br6]2- (James et al., 1999) form analogous structures. Addition of a further halide ion results in structures of the [RX3E(µ-X)EX3R]3- type such as [Ph2Sb2Cl7]3- and [Ph2Sb2Br7]3- (Sheldrick & Martin, 1992). The highest aggregation is found in [{PhSbI(µ2-I)}4(µ4-I)]- (von Seyerl et al., 1986), which features an I4 square with Sb atoms on the edges and another I atom in the centre of the square. In all organohaloarsenate(III), -antimonate(III) and -bismuthate(III) structures, bonds to bridging halide ligands are considerably longer than bonds to terminal halide ligands and bridging halide ligands are coordinated cis to one another.
In the title compound, the acidity of the aryldichloroarsine is enhanced by the electron-withdrawing, positively charged pyridinio substituent, so that a ψ-octahedral structure similar to the one encountered in [RBr2As(µ-Br2)AsBr2R]2- or [PhCl2Sb(µ-Cl)2SbCl2Ph]2- becomes possible: As is coordinated axially to the organic substituent and equatorially to four chloride ligands, two bridging and two terminal. The terminal chloride ligands are located cis to one another and connected to As by short bonds, while the bridging chloride ligands are much more distant from the As centre. In contrast to in the compounds cited above, these bridging chloride ligands do not link to the same organoarsenic unit, but to two different arsenic atoms, thus forming a polymeric chain running along the crystallographic a axis (cf. Figure 1).
The nitrogen atom on the pyridine ring forms an N—H···O hydrogen bond to a co-crystallized water molecule. The two O—H bonds of this water molecule in turn form O—H···Cl hydrogen bonds to two bridging chloride ions on a neighboring polymeric chain. Through the intermediary of the intervening water molecules, each chain thus acts as a hydrogen bond donor towards the neighbouring chains in the [011] and [011] directions and as a hydrogen bond acceptor towards the neighbouring chains in the [011] and [011] directions (cf. Figure 2). It is the lack of centrosymmetry in the hydrogen bonding pattern that accounts for the non-centrosymmetric crystal structure and space group.
The arsenic atom, the pyridinium ring and the oxygen atom of the water molecule all lie in the same mirror plane (Wyckoff position 2 b). The displacement ellipsoids on the pyridinium ring suggest a slight disorder about this mirror plane, but refining this disorder did not improve the quality of the structural model significantly. The bridging chlorine atom (Cl2) lies on a twofold axis (Wyckoff position 2a).