supplementary materials


wm2705 scheme

Acta Cryst. (2013). E69, m22-m23    [ doi:10.1107/S1600536812049562 ]

Poly[([mu]6-4-amino-3,5,6-trichloropyridine-2-carboxylato)aquacaesium]

G. Smith

Abstract top

In the structure of the title complex, [Cs(C6H2Cl3N2O2)(H2O)]n, the caesium salt of the commercial herbicide picloram, the Cs+ cation lies on a crystallographic mirror plane, which also contains the coordinating water molecule and all non-H atoms of the 4-amino-3,5,6-trichloropicolinate anion except the carboxylate O-atom donors. The irregular CsCl4O5 coordination polyhedron comprises chlorine donors from the ortho-related ring substituents of the picloramate ligand in a bidentate chelate mode, with a third chlorine bridging [Cs-Cl range 3.6052 (11)-3.7151 (11) Å] as well as a bidentate chelate carboxylate group giving sheets extending parallel to (010). A three-dimensional coordination polymer structure is generated through the carboxylate group, which also bridges the sheets down [010]. Within the structure, there are intra-unit water O-H...Ocarboxylate and amine N-H...Npyridine hydrogen-bonding interactions.

Comment top

4-Amino-3,5,6-trichloropyridine-2-carboxylic acid (picloram) is a commercial herbicide (Mullinson, 1985) introduced by Dow Chemicals as Tordon (O'Neil, 2001). Although it has potential as a metal chelating ligand similar to picolinic acid, there are only five metal complexes with picloramato ligands in the crystallographic literature. Examples include picloram as a bidentate chelate ligand [with MnII (Smith et al., 1981a) and CuII (O'Reilly et al., 1983)], while in the Mg complex (Smith et al., 1981b], picloram acts as a counter-anion. A caesium complex derived from dipicolinic acid has also been reported (Santra et al., 2011).

The reaction of picloram with caesium hydroxide in aqueous ethanol gave crystals of the title compound [Cs(C6H2Cl3N2O2)(H2O)]n and the structure is reported herein. In this structure, the Cs+ cation lies on a crystallographic mirror plane which also contains the coordinating monodentate water molecule and all non-H atoms of the picloramate ligand except the carboxyl O-atom donors (Fig. 1). The irregular CsCl4O5 coordination sphere comprises chlorine donors from the ortho-related ring substituents (Cl5, Cl6) in a bidentate chelate mode [Cs—Cl, 3.6052 (11), 3.7151 (11) Å], with the third chlorine (Cl3) [Cs—Cl, 3.7127 (4) Å] bridging neighbouring Cs+ cations [Cs···Csx, Cs···Csxi = 4.9008 (3) Å] [for (x), -x + 1, y - 1/2, -z + 2; for (xi), -x + 1, y + 1/2, -z + 2], as well as a bidentate chelate and bridging carboxyl group. Although in most structures containing caesium and related ligands, the Cl atom is anionic rather than coordinating, an example of a coordinating carbon-bound Cl is known in which 1,2-dichloroethane acts as a bidentate chelate ligand (Levitskaia et al., 2000). The Cs—Cl bond lengths in that structure are shorter than those in the title complex (3.46–3.56 Å).

In the present complex, sheets are formed parallel to (010) (Fig. 2) and these are extended into a three-dimensional coordination polymer structure through the carboxyl group of the picloram ligand which bridges the sheets down [010] (Fig. 3). The amine group gives weak intramolecular N—H···Cl5 and ···Cl6 interactions and as well forms inter-complex N—H···Npyridine hydrogen bonds which accompany water O—H···Ocarboxyl hydrogen-bonding interactions in the structure (Table 2).

Related literature top

For background information on picloram, see: Mullinson (1985); O'Neil (2001). For examples of structures of metal complexes with picloram, see: Smith et al. (1981a,b); O'Reilly et al. (1983). For another structure with caesium cations involving coordinating carbon-bound Cl, see: Levitskaia et al. (2000). For a caesium complex with dipicolinic acid, see: Santra et al. (2011).

Experimental top

The title compound was synthesized by heating together under reflux for 10 minutes, 0.5 mmol of caesium hydroxide and 0.5 mmol of 4-amino-3,5,6-trichloropicolinic acid in 20 ml of 10% ethanol–water. Room temperature evaporation of the solution to incipient dryness gave colourless crystal plates of the title complex from which a specimen was cleaved for the X-ray analysis.

Refinement top

Hydrogen atoms of the coordinating water molecule and the amine group were located in a difference-Fourier synthesis but were allowed to ride in the refinement with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-numbering scheme for the title compound, with non-H atoms drawn as 50% probability ellipsoids. For symmetry codes: see Table 1.
[Figure 2] Fig. 2. The sheet structure viewed perpendicular to the crystallographic mirror planes, with intermolecular hydrogen bonds and intramolecular N—H···Cl associations shown as dashed lines. For symmetry codes, see Fig. 1 and Table 1.
[Figure 3] Fig. 3. The packing in the unit cell viewed along the the mirror planes showing inter-plane carboxyl bridges and hydrogen-bonding associations (Table 2) as dashed lines.
Poly[(µ6-4-amino-3,5,6-trichloropyridine-2-carboxylato)aquacaesium] top
Crystal data top
[Cs(C6H2Cl3N2O2)(H2O)]F(000) = 368
Mr = 391.37Dx = 2.382 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 3047 reflections
a = 7.0816 (3) Åθ = 3.5–28.7°
b = 6.6863 (2) ŵ = 4.11 mm1
c = 11.7382 (5) ÅT = 200 K
β = 101.005 (4)°Plate, colourless
V = 545.58 (4) Å30.25 × 0.20 × 0.08 mm
Z = 2
Data collection top
Oxford Diffraction Gemini-S CCD detector
diffractometer
1164 independent reflections
Radiation source: Enhance Mo X-ray source1118 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.5°
ω scansh = 87
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 88
Tmin = 0.67, Tmax = 0.98l = 1114
3773 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021H-atom parameters constrained
wR(F2) = 0.053 w = 1/[σ2(Fo2) + (0.0338P)2 + 0.1378P]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max = 0.001
1164 reflectionsΔρmax = 0.55 e Å3
89 parametersΔρmin = 0.56 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0132 (11)
Crystal data top
[Cs(C6H2Cl3N2O2)(H2O)]V = 545.58 (4) Å3
Mr = 391.37Z = 2
Monoclinic, P21/mMo Kα radiation
a = 7.0816 (3) ŵ = 4.11 mm1
b = 6.6863 (2) ÅT = 200 K
c = 11.7382 (5) Å0.25 × 0.20 × 0.08 mm
β = 101.005 (4)°
Data collection top
Oxford Diffraction Gemini-S CCD detector
diffractometer
1164 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
1118 reflections with I > 2σ(I)
Tmin = 0.67, Tmax = 0.98Rint = 0.026
3773 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.021H-atom parameters constrained
wR(F2) = 0.053Δρmax = 0.55 e Å3
S = 0.98Δρmin = 0.56 e Å3
1164 reflectionsAbsolute structure: ?
89 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Cs10.29271 (3)0.25000.885412 (19)0.02831 (13)
Cl30.06235 (13)0.25000.12344 (9)0.0326 (2)
Cl50.01008 (14)0.25000.58974 (9)0.0291 (2)
Cl60.44747 (14)0.25000.61009 (9)0.0335 (2)
O1W0.1573 (4)0.25000.8385 (3)0.0433 (8)
H11W0.23870.14250.83350.065*
O210.4110 (3)0.0836 (3)0.14016 (17)0.0369 (5)
N10.3823 (4)0.25000.3865 (3)0.0223 (6)
N40.2153 (5)0.25000.3441 (3)0.0380 (8)
H410.28700.25000.29080.046*
H420.27000.25000.39680.046*
C20.2692 (5)0.25000.2807 (3)0.0211 (7)
C30.0719 (5)0.25000.2649 (3)0.0230 (7)
C40.0239 (5)0.25000.3586 (3)0.0241 (8)
C50.0961 (5)0.25000.4690 (3)0.0224 (7)
C60.2937 (5)0.25000.4763 (3)0.0221 (7)
C210.3725 (5)0.25000.1780 (3)0.0253 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cs10.02573 (17)0.03285 (17)0.02648 (18)0.0000.00536 (11)0.000
Cl30.0204 (5)0.0427 (5)0.0316 (5)0.0000.0029 (4)0.000
Cl50.0277 (5)0.0283 (5)0.0359 (5)0.0000.0172 (4)0.000
Cl60.0263 (5)0.0492 (6)0.0243 (5)0.0000.0034 (4)0.000
O1W0.0298 (16)0.0423 (17)0.056 (2)0.0000.0042 (15)0.000
O210.0456 (12)0.0340 (11)0.0352 (12)0.0137 (9)0.0178 (10)0.0035 (9)
N10.0173 (15)0.0238 (15)0.0266 (17)0.0000.0061 (12)0.000
N40.0158 (16)0.058 (2)0.041 (2)0.0000.0076 (14)0.000
C20.0187 (17)0.0181 (16)0.027 (2)0.0000.0048 (14)0.000
C30.0169 (17)0.0240 (17)0.027 (2)0.0000.0008 (15)0.000
C40.0164 (17)0.0187 (16)0.037 (2)0.0000.0052 (15)0.000
C50.0198 (17)0.0196 (16)0.030 (2)0.0000.0116 (15)0.000
C60.0194 (17)0.0216 (16)0.0243 (19)0.0000.0020 (14)0.000
C210.0149 (16)0.036 (2)0.0238 (19)0.0000.0002 (14)0.000
Geometric parameters (Å, º) top
Cs1—Cl53.7151 (11)O1W—H11W0.9200
Cs1—Cl63.6052 (11)O1W—H11Wvii0.9200
Cs1—O1W3.129 (3)N1—C21.343 (5)
Cs1—O21i3.116 (2)N1—C61.326 (5)
Cs1—O21ii3.116 (2)N4—C41.333 (5)
Cs1—O21iii3.150 (2)N4—H420.7900
Cs1—O21iv3.150 (2)N4—H410.7300
Cs1—Cl3v3.7127 (4)C2—C31.374 (5)
Cs1—Cl3vi3.7127 (4)C2—C211.525 (5)
Cl5—C51.727 (4)C3—C41.398 (5)
Cl6—C61.732 (4)C3—Cl31.749 (4)
C21—O211.247 (3)C4—C51.408 (5)
C21—O21vii1.247 (3)C5—C61.386 (5)
Cl5—Cs1—Cl651.87 (2)Cl3vi—Cs1—O21iii75.19 (4)
Cl5—Cs1—O1W56.55 (7)O21i—Cs1—O21ii91.43 (5)
Cl5—Cs1—O21iv152.65 (4)O21i—Cs1—O21iii77.10 (5)
Cl3v—Cs1—Cl578.56 (2)O21ii—Cs1—O21iii106.40 (5)
Cl3vi—Cs1—Cl578.56 (2)Cs1v—Cl3—C3100.54 (5)
Cl5—Cs1—O21i100.91 (4)Cs1vi—Cl3—C3100.54 (5)
Cl5—Cs1—O21ii100.91 (4)Cs1v—Cl3—Cs1vi128.44 (3)
Cl5—Cs1—O21iii152.65 (4)Cs1—Cl5—C5120.18 (13)
Cl6—Cs1—O1W108.42 (7)Cs1—Cl6—C6124.53 (13)
Cl6—Cs1—O21iv141.22 (4)Cs1viii—O21—Cs1ix102.90 (6)
Cl3v—Cs1—Cl6100.49 (2)Cs1—O1W—H11W128.00
Cl3vi—Cs1—Cl6100.49 (2)Cs1—O1W—H11Wvii128.00
Cl6—Cs1—O21i65.68 (4)H11W—O1W—H11Wvii103.00
Cl6—Cs1—O21ii65.68 (4)C2—N1—C6116.5 (3)
Cl6—Cs1—O21iii141.22 (4)C4—N4—H41130.00
O1W—Cs1—O21iv104.15 (7)H41—N4—H42108.00
Cl3v—Cs1—O1W64.39 (1)C4—N4—H42123.00
Cl3vi—Cs1—O1W64.39 (1)N1—C2—C21116.1 (3)
O1W—Cs1—O21i131.69 (4)N1—C2—C3122.4 (3)
O1W—Cs1—O21ii131.69 (4)C3—C2—C21121.5 (3)
O1W—Cs1—O21iii104.15 (7)C2—C3—C4121.8 (3)
Cl3v—Cs1—O21iv75.19 (4)Cl3—C3—C2118.9 (3)
Cl3vi—Cs1—O21iv112.36 (4)Cl3—C3—C4119.3 (3)
O21iv—Cs1—O21i106.40 (5)N4—C4—C5122.5 (3)
O21iv—Cs1—O21ii77.10 (5)C3—C4—C5115.2 (3)
O21iv—Cs1—O21iii41.36 (5)N4—C4—C3122.3 (3)
Cl3v—Cs1—Cl3vi128.44 (2)C4—C5—C6118.8 (3)
Cl3v—Cs1—O21i160.44 (4)Cl5—C5—C4118.4 (3)
Cl3v—Cs1—O21ii69.70 (4)Cl5—C5—C6122.8 (3)
Cl3v—Cs1—O21iii112.36 (4)Cl6—C6—C5120.6 (3)
Cl3vi—Cs1—O21i69.70 (4)Cl6—C6—N1114.2 (3)
Cl3vi—Cs1—O21ii160.44 (4)N1—C6—C5125.2 (3)
Cl6—Cs1—Cl5—C50.00 (1)C21—C2—C3—C4180.00 (1)
O1W—Cs1—Cl5—C5180.00 (1)N1—C2—C21—O2189.9 (3)
Cl5—Cs1—Cl6—C60.00 (1)C3—C2—C21—O2190.1 (3)
O1W—Cs1—Cl6—C60.00 (1)Cl3—C3—C4—N40.00 (1)
Cs1—Cl5—C5—C4180.00 (1)Cl3—C3—C4—C5180.00 (1)
Cs1—Cl5—C5—C60.00 (1)C2—C3—C4—N4180.00 (1)
Cs1—Cl6—C6—N1180.00 (1)C2—C3—C4—C50.00 (1)
Cs1—Cl6—C6—C50.00 (1)N4—C4—C5—Cl50.00 (1)
C6—N1—C2—C30.00 (1)N4—C4—C5—C6180.00 (1)
C6—N1—C2—C21180.00 (1)C3—C4—C5—Cl5180.00 (1)
C2—N1—C6—Cl6180.00 (1)C3—C4—C5—C60.00 (1)
C2—N1—C6—C50.00 (1)Cl5—C5—C6—Cl60.00 (1)
N1—C2—C3—Cl3180.00 (1)Cl5—C5—C6—N1180.00 (1)
N1—C2—C3—C40.00 (1)C4—C5—C6—Cl6180.00 (1)
C21—C2—C3—Cl30.00 (1)C4—C5—C6—N10.00 (1)
Symmetry codes: (i) x+1, y+1/2, z+1; (ii) x+1, y, z+1; (iii) x, y+1/2, z+1; (iv) x, y, z+1; (v) x, y1/2, z+1; (vi) x, y+1/2, z+1; (vii) x, y+1/2, z; (viii) x, y, z1; (ix) x+1, y1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H11W···O21x0.922.002.905 (3)168
N4—H42···N1xi0.792.442.985 (5)127
N4—H42···Cl50.792.632.971 (4)108
N4—H41···Cl30.732.752.992 (4)102
Symmetry codes: (x) x, y, z+1; (xi) x1, y, z.
Selected bond lengths (Å) top
Cs1—Cl53.7151 (11)Cs1—O21iii3.150 (2)
Cs1—Cl63.6052 (11)Cs1—O21iv3.150 (2)
Cs1—O1W3.129 (3)Cs1—Cl3v3.7127 (4)
Cs1—O21i3.116 (2)Cs1—Cl3vi3.7127 (4)
Cs1—O21ii3.116 (2)
Symmetry codes: (i) x+1, y+1/2, z+1; (ii) x+1, y, z+1; (iii) x, y+1/2, z+1; (iv) x, y, z+1; (v) x, y1/2, z+1; (vi) x, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H11W···O21vii0.922.002.905 (3)168
N4—H42···N1viii0.792.442.985 (5)127
Symmetry codes: (vii) x, y, z+1; (viii) x1, y, z.
references
References top

Agilent (2012). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Levitskaia, T. G., Bryan, J. C., Sachleben, R. A., Lamb, J. D. & Moyer, B. A. (2000). J. Am. Chem. Soc. 122, 554–562.

Mullinson, W. R. (1985). Proc. West. Soc. Weed Sci. 38, 21–92.

O'Neil, M. J. (2001). Editor. The Merck Index, 13th ed., pp. 1325–1326. Whitehouse Station, NJ, USA: Merck & Co. Inc.

O'Reilly, E. J., Smith, G., Kennard, C. H. L. & White, A. H. (1983). Aust. J. Chem. 36, 183–190.

Santra, S., Das, B. & Baruah, J. B. (2011). J. Chem. Crystallogr. 41, 1981–1987.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Smith, G., O'Reilly, E. J. & Kennard, C. H. L. (1981a). Aust. J. Chem. 34, 891–896.

Smith, G., O'Reilly, E. J. & Kennard, C. H. L. (1981b). Cryst. Struct. Commun. 10, 1277–1282.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.