Poly[(μ6-4-amino-3,5,6-trichloro-pyridine-2-carboxyl-ato)aqua-caesium].

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 mol-ecule and all non-H atoms of the 4-amino-3,5,6-trichloro-picolinate anion except the carboxyl-ate 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 carboxyl-ate group giving sheets extending parallel to (010). A three-dimensional coordination polymer structure is generated through the carboxyl-ate group, which also bridges the sheets down [010]. Within the structure, there are intra-unit water O-H⋯Ocarboxyl-ate and amine N-H⋯Npyridine hydrogen-bonding inter-actions.

Related literature

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

Crystal data

[Cs(C6H2Cl3N2O2)(H2O)]

M = 391.37

Monoclinic,

a = 7.0816 (3) Å

b = 6.6863 (2) Å

c = 11.7382 (5) Å

β = 101.005 (4)°

V = 545.58 (4) Å3

Z = 2

Mo Kα radiation

μ = 4.11 mm−1

T = 200 K

0.25 × 0.20 × 0.08 mm

Data collection

Oxford Diffraction Gemini-S CCD detector diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.67, T max = 0.98

3773 measured reflections

1164 independent reflections

1118 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.053

S = 0.98

1164 reflections

89 parameters

H-atom parameters constrained

Δρmax = 0.55 e Å−3

Δρmin = −0.56 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812049562/wm2705sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049562/wm2705Isup2.hkl

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

[Cs(C6H2Cl3N2O2)(H2O)]	F(000) = 368
Mr = 391.37	Dx = 2.382 Mg m−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 3047 reflections
a = 7.0816 (3) Å	θ = 3.5–28.7°
b = 6.6863 (2) Å	µ = 4.11 mm−1
c = 11.7382 (5) Å	T = 200 K
β = 101.005 (4)°	Plate, colourless
V = 545.58 (4) Å3	0.25 × 0.20 × 0.08 mm
Z = 2

Oxford Diffraction Gemini-S CCD detector diffractometer	1164 independent reflections
Radiation source: Enhance Mo X-ray source	1118 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.5°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −8→8
Tmin = 0.67, Tmax = 0.98	l = −11→14
3773 measured reflections

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)] = 0.021	H-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 reflections	Δρmax = 0.55 e Å−3
89 parameters	Δρmin = −0.56 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0132 (11)

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
Cs1	0.29271 (3)	0.2500	0.885412 (19)	0.02831 (13)
Cl3	−0.06235 (13)	0.2500	0.12344 (9)	0.0326 (2)
Cl5	−0.01008 (14)	0.2500	0.58974 (9)	0.0291 (2)
Cl6	0.44747 (14)	0.2500	0.61009 (9)	0.0335 (2)
O1W	−0.1573 (4)	0.2500	0.8385 (3)	0.0433 (8)
H11W	−0.2387	0.1425	0.8335	0.065*
O21	0.4110 (3)	0.0836 (3)	0.14016 (17)	0.0369 (5)
N1	0.3823 (4)	0.2500	0.3865 (3)	0.0223 (6)
N4	−0.2153 (5)	0.2500	0.3441 (3)	0.0380 (8)
H41	−0.2870	0.2500	0.2908	0.046*
H42	−0.2700	0.2500	0.3968	0.046*
C2	0.2692 (5)	0.2500	0.2807 (3)	0.0211 (7)
C3	0.0719 (5)	0.2500	0.2649 (3)	0.0230 (7)
C4	−0.0239 (5)	0.2500	0.3586 (3)	0.0241 (8)
C5	0.0961 (5)	0.2500	0.4690 (3)	0.0224 (7)
C6	0.2937 (5)	0.2500	0.4763 (3)	0.0221 (7)
C21	0.3725 (5)	0.2500	0.1780 (3)	0.0253 (8)

	U11	U22	U33	U12	U13	U23
Cs1	0.02573 (17)	0.03285 (17)	0.02648 (18)	0.000	0.00536 (11)	0.000
Cl3	0.0204 (5)	0.0427 (5)	0.0316 (5)	0.000	−0.0029 (4)	0.000
Cl5	0.0277 (5)	0.0283 (5)	0.0359 (5)	0.000	0.0172 (4)	0.000
Cl6	0.0263 (5)	0.0492 (6)	0.0243 (5)	0.000	0.0034 (4)	0.000
O1W	0.0298 (16)	0.0423 (17)	0.056 (2)	0.000	0.0042 (15)	0.000
O21	0.0456 (12)	0.0340 (11)	0.0352 (12)	0.0137 (9)	0.0178 (10)	0.0035 (9)
N1	0.0173 (15)	0.0238 (15)	0.0266 (17)	0.000	0.0061 (12)	0.000
N4	0.0158 (16)	0.058 (2)	0.041 (2)	0.000	0.0076 (14)	0.000
C2	0.0187 (17)	0.0181 (16)	0.027 (2)	0.000	0.0048 (14)	0.000
C3	0.0169 (17)	0.0240 (17)	0.027 (2)	0.000	0.0008 (15)	0.000
C4	0.0164 (17)	0.0187 (16)	0.037 (2)	0.000	0.0052 (15)	0.000
C5	0.0198 (17)	0.0196 (16)	0.030 (2)	0.000	0.0116 (15)	0.000
C6	0.0194 (17)	0.0216 (16)	0.0243 (19)	0.000	0.0020 (14)	0.000
C21	0.0149 (16)	0.036 (2)	0.0238 (19)	0.000	0.0002 (14)	0.000

Cs1—Cl5	3.7151 (11)	O1W—H11W	0.9200
Cs1—Cl6	3.6052 (11)	O1W—H11Wvii	0.9200
Cs1—O1W	3.129 (3)	N1—C2	1.343 (5)
Cs1—O21i	3.116 (2)	N1—C6	1.326 (5)
Cs1—O21ii	3.116 (2)	N4—C4	1.333 (5)
Cs1—O21iii	3.150 (2)	N4—H42	0.7900
Cs1—O21iv	3.150 (2)	N4—H41	0.7300
Cs1—Cl3v	3.7127 (4)	C2—C3	1.374 (5)
Cs1—Cl3vi	3.7127 (4)	C2—C21	1.525 (5)
Cl5—C5	1.727 (4)	C3—C4	1.398 (5)
Cl6—C6	1.732 (4)	C3—Cl3	1.749 (4)
C21—O21	1.247 (3)	C4—C5	1.408 (5)
C21—O21vii	1.247 (3)	C5—C6	1.386 (5)
Cl5—Cs1—Cl6	51.87 (2)	Cl3vi—Cs1—O21iii	75.19 (4)
Cl5—Cs1—O1W	56.55 (7)	O21i—Cs1—O21ii	91.43 (5)
Cl5—Cs1—O21iv	152.65 (4)	O21i—Cs1—O21iii	77.10 (5)
Cl3v—Cs1—Cl5	78.56 (2)	O21ii—Cs1—O21iii	106.40 (5)
Cl3vi—Cs1—Cl5	78.56 (2)	Cs1v—Cl3—C3	100.54 (5)
Cl5—Cs1—O21i	100.91 (4)	Cs1vi—Cl3—C3	100.54 (5)
Cl5—Cs1—O21ii	100.91 (4)	Cs1v—Cl3—Cs1vi	128.44 (3)
Cl5—Cs1—O21iii	152.65 (4)	Cs1—Cl5—C5	120.18 (13)
Cl6—Cs1—O1W	108.42 (7)	Cs1—Cl6—C6	124.53 (13)
Cl6—Cs1—O21iv	141.22 (4)	Cs1viii—O21—Cs1ix	102.90 (6)
Cl3v—Cs1—Cl6	100.49 (2)	Cs1—O1W—H11W	128.00
Cl3vi—Cs1—Cl6	100.49 (2)	Cs1—O1W—H11Wvii	128.00
Cl6—Cs1—O21i	65.68 (4)	H11W—O1W—H11Wvii	103.00
Cl6—Cs1—O21ii	65.68 (4)	C2—N1—C6	116.5 (3)
Cl6—Cs1—O21iii	141.22 (4)	C4—N4—H41	130.00
O1W—Cs1—O21iv	104.15 (7)	H41—N4—H42	108.00
Cl3v—Cs1—O1W	64.39 (1)	C4—N4—H42	123.00
Cl3vi—Cs1—O1W	64.39 (1)	N1—C2—C21	116.1 (3)
O1W—Cs1—O21i	131.69 (4)	N1—C2—C3	122.4 (3)
O1W—Cs1—O21ii	131.69 (4)	C3—C2—C21	121.5 (3)
O1W—Cs1—O21iii	104.15 (7)	C2—C3—C4	121.8 (3)
Cl3v—Cs1—O21iv	75.19 (4)	Cl3—C3—C2	118.9 (3)
Cl3vi—Cs1—O21iv	112.36 (4)	Cl3—C3—C4	119.3 (3)
O21iv—Cs1—O21i	106.40 (5)	N4—C4—C5	122.5 (3)
O21iv—Cs1—O21ii	77.10 (5)	C3—C4—C5	115.2 (3)
O21iv—Cs1—O21iii	41.36 (5)	N4—C4—C3	122.3 (3)
Cl3v—Cs1—Cl3vi	128.44 (2)	C4—C5—C6	118.8 (3)
Cl3v—Cs1—O21i	160.44 (4)	Cl5—C5—C4	118.4 (3)
Cl3v—Cs1—O21ii	69.70 (4)	Cl5—C5—C6	122.8 (3)
Cl3v—Cs1—O21iii	112.36 (4)	Cl6—C6—C5	120.6 (3)
Cl3vi—Cs1—O21i	69.70 (4)	Cl6—C6—N1	114.2 (3)
Cl3vi—Cs1—O21ii	160.44 (4)	N1—C6—C5	125.2 (3)
Cl6—Cs1—Cl5—C5	0.00 (1)	C21—C2—C3—C4	180.00 (1)
O1W—Cs1—Cl5—C5	180.00 (1)	N1—C2—C21—O21	89.9 (3)
Cl5—Cs1—Cl6—C6	0.00 (1)	C3—C2—C21—O21	−90.1 (3)
O1W—Cs1—Cl6—C6	0.00 (1)	Cl3—C3—C4—N4	0.00 (1)
Cs1—Cl5—C5—C4	180.00 (1)	Cl3—C3—C4—C5	180.00 (1)
Cs1—Cl5—C5—C6	0.00 (1)	C2—C3—C4—N4	180.00 (1)
Cs1—Cl6—C6—N1	180.00 (1)	C2—C3—C4—C5	0.00 (1)
Cs1—Cl6—C6—C5	0.00 (1)	N4—C4—C5—Cl5	0.00 (1)
C6—N1—C2—C3	0.00 (1)	N4—C4—C5—C6	180.00 (1)
C6—N1—C2—C21	180.00 (1)	C3—C4—C5—Cl5	180.00 (1)
C2—N1—C6—Cl6	180.00 (1)	C3—C4—C5—C6	0.00 (1)
C2—N1—C6—C5	0.00 (1)	Cl5—C5—C6—Cl6	0.00 (1)
N1—C2—C3—Cl3	180.00 (1)	Cl5—C5—C6—N1	180.00 (1)
N1—C2—C3—C4	0.00 (1)	C4—C5—C6—Cl6	180.00 (1)
C21—C2—C3—Cl3	0.00 (1)	C4—C5—C6—N1	0.00 (1)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O21x	0.92	2.00	2.905 (3)	168
N4—H42···N1xi	0.79	2.44	2.985 (5)	127
N4—H42···Cl5	0.79	2.63	2.971 (4)	108
N4—H41···Cl3	0.73	2.75	2.992 (4)	102

Table 1

Selected bond lengths (Å)

Cs1—Cl5	3.7151 (11)
Cs1—Cl6	3.6052 (11)
Cs1—O1W	3.129 (3)
Cs1—O21i	3.116 (2)
Cs1—O21ii	3.116 (2)
Cs1—O21iii	3.150 (2)
Cs1—O21iv	3.150 (2)
Cs1—Cl3v	3.7127 (4)
Cs1—Cl3vi	3.7127 (4)

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

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O21vii	0.92	2.00	2.905 (3)	168
N4—H42⋯N1viii	0.79	2.44	2.985 (5)	127

Symmetry codes: (vii) ; (viii) .