Crystal structure of poly[[di-μ₂-aqua-aqua­sodium] 4-amino-3,5,6-tri­chloro­pyridine-2-carboxyl­ate trihydrate], the sodium salt of the herbicide picloram

The trihydrated sodium salt of the herbicide picloram comprises a cationic μ₂-aqua-bridged chain structure that is linked to the picloramate anions through amine N—H...O and water O—H...O and O—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.088
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Th(Min) ...          6 Report
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4 Report

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............         14 Report
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00600 Degree
PLAT434_ALERT_2_G Short Inter HL..HL Contact Cl3    ..  Cl5     ..       3.21 Ang.
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          4 Note
              H2 O
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT960_ALERT_3_G Number of Intensities with I  <   - 2*sig(I) ...          1 Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); 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).

Poly[[di-µ₂-aqua-aquasodium] 4-amino-3,5,6-trichloropyridine-2-carboxylate trihydrate]

Crystal data

[Na(H2O)3](C6H2Cl3N2O2)·3H2O	Z = 2
Mr = 371.53	F(000) = 380
Triclinic, P1	Dx = 1.665 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5625 (5) Å	Cell parameters from 2548 reflections
b = 8.4574 (6) Å	θ = 3.8–28.8°
c = 13.8553 (10) Å	µ = 0.68 mm^−1
α = 78.747 (6)°	T = 200 K
β = 79.374 (6)°	Block, colourless
γ = 88.864 (6)°	0.35 × 0.35 × 0.22 mm
V = 741.17 (9) Å^3

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer	2905 independent reflections
Radiation source: Enhance (Mo) X-ray source	2487 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −10→10
Tmin = 0.947, Tmax = 0.980	l = −17→13
6040 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0478P)^2 + 0.2264P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
2905 reflections	Δρmax = 0.30 e Å^−3
182 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.050 (3)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl3	0.73580 (8)	0.09272 (5)	0.52593 (4)	0.0257 (2)
Cl5	0.76678 (8)	0.74102 (5)	0.46993 (4)	0.0240 (2)
Cl6	0.67863 (9)	0.70381 (6)	0.70472 (4)	0.0295 (2)
O21	0.4767 (2)	0.04778 (17)	0.77535 (11)	0.0287 (5)
O22	0.8188 (2)	0.04407 (17)	0.77067 (11)	0.0292 (5)
N1	0.6684 (2)	0.39495 (18)	0.71307 (12)	0.0196 (5)
N4	0.7849 (3)	0.42747 (19)	0.40294 (12)	0.0213 (5)
C2	0.6814 (3)	0.2631 (2)	0.67196 (14)	0.0172 (5)
C3	0.7193 (3)	0.2696 (2)	0.57064 (14)	0.0170 (5)
C4	0.7473 (3)	0.4178 (2)	0.50250 (14)	0.0168 (6)
C5	0.7335 (3)	0.5539 (2)	0.54712 (14)	0.0173 (5)
C6	0.6946 (3)	0.5361 (2)	0.64975 (15)	0.0186 (6)
C21	0.6561 (3)	0.1034 (2)	0.74534 (14)	0.0204 (6)
Na1	0.24455 (12)	0.42819 (9)	1.01558 (6)	0.0268 (3)
O1W	0.0817 (2)	0.53070 (17)	0.87914 (10)	0.0299 (5)
O2W	0.1503 (2)	0.15728 (17)	1.05390 (11)	0.0300 (5)
O3W	0.4202 (2)	0.62279 (17)	1.07140 (10)	0.0272 (5)
O4W	0.1371 (2)	0.27585 (17)	0.77676 (12)	0.0317 (5)
O5W	0.2700 (2)	−0.10534 (18)	0.95986 (11)	0.0325 (5)
O6W	0.1709 (2)	0.82429 (17)	0.73270 (11)	0.0298 (5)
H41	0.80460	0.32820	0.37840	0.0260*
H42	0.80680	0.53330	0.36040	0.0260*
H11W	0.09740	0.45450	0.85000	0.0450*
H12W	0.10510	0.62480	0.83710	0.0450*
H21W	0.15180	0.09520	1.11820	0.0450*
H22W	0.19310	0.08550	1.02150	0.0450*
H31W	0.38250	0.71930	1.04480	0.0410*
H32W	0.40980	0.61800	1.13770	0.0410*
H41W	0.02360	0.20490	0.77150	0.0480*
H42W	0.25100	0.20920	0.77350	0.0480*
H51W	0.34890	−0.07030	0.89970	0.0490*
H52W	0.15590	−0.13130	0.93860	0.18 (2)*
H61W	0.06160	0.89510	0.72480	0.0450*
H62W	0.30130	0.87260	0.72460	0.0450*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl3	0.0359 (3)	0.0159 (2)	0.0269 (3)	0.0007 (2)	−0.0044 (2)	−0.0091 (2)
Cl5	0.0280 (3)	0.0146 (2)	0.0282 (3)	−0.0001 (2)	−0.0049 (2)	−0.0012 (2)
Cl6	0.0412 (3)	0.0196 (3)	0.0309 (3)	0.0023 (2)	−0.0063 (2)	−0.0131 (2)
O21	0.0247 (8)	0.0260 (8)	0.0314 (9)	−0.0065 (6)	−0.0013 (6)	0.0013 (6)
O22	0.0290 (8)	0.0250 (8)	0.0318 (9)	0.0043 (6)	−0.0089 (7)	0.0013 (6)
N1	0.0202 (9)	0.0195 (8)	0.0195 (9)	0.0004 (6)	−0.0025 (7)	−0.0060 (7)
N4	0.0263 (9)	0.0197 (8)	0.0178 (8)	0.0009 (7)	−0.0031 (7)	−0.0042 (6)
C2	0.0128 (9)	0.0164 (9)	0.0220 (10)	0.0008 (7)	−0.0024 (7)	−0.0037 (7)
C3	0.0152 (9)	0.0147 (9)	0.0224 (10)	0.0005 (7)	−0.0038 (7)	−0.0063 (7)
C4	0.0106 (9)	0.0193 (10)	0.0216 (10)	0.0008 (7)	−0.0044 (7)	−0.0053 (8)
C5	0.0141 (9)	0.0144 (9)	0.0228 (10)	0.0002 (7)	−0.0041 (7)	−0.0019 (7)
C6	0.0160 (10)	0.0167 (9)	0.0252 (10)	0.0015 (7)	−0.0040 (8)	−0.0090 (8)
C21	0.0251 (11)	0.0192 (9)	0.0177 (10)	0.0014 (8)	−0.0028 (8)	−0.0068 (7)
Na1	0.0249 (5)	0.0264 (4)	0.0291 (5)	−0.0002 (3)	−0.0031 (3)	−0.0068 (3)
O1W	0.0360 (9)	0.0275 (8)	0.0252 (8)	0.0022 (6)	−0.0021 (7)	−0.0065 (6)
O2W	0.0390 (9)	0.0239 (8)	0.0246 (8)	0.0020 (6)	−0.0008 (7)	−0.0039 (6)
O3W	0.0322 (9)	0.0264 (8)	0.0223 (8)	0.0022 (6)	−0.0020 (6)	−0.0064 (6)
O4W	0.0282 (8)	0.0283 (8)	0.0399 (9)	0.0023 (6)	−0.0067 (7)	−0.0097 (7)
O5W	0.0342 (9)	0.0353 (9)	0.0247 (8)	0.0009 (7)	−0.0010 (7)	−0.0020 (7)
O6W	0.0257 (8)	0.0311 (8)	0.0330 (9)	−0.0003 (6)	−0.0043 (7)	−0.0079 (6)

Geometric parameters (Å, º)

Na1—O1W^i	2.4185 (16)	O4W—H42W	0.9300
Na1—O3W^ii	2.3803 (16)	O4W—H41W	0.9900
Na1—O1W	2.3529 (16)	O5W—H52W	0.9000
Na1—O2W	2.3183 (17)	O5W—H51W	0.9000
Na1—O3W	2.3530 (16)	O6W—H61W	0.9300
Cl3—C3	1.7216 (18)	O6W—H62W	0.9300
Cl5—C5	1.7213 (18)	N1—C2	1.342 (2)
Cl6—C6	1.7289 (19)	N1—C6	1.330 (2)
O21—C21	1.243 (2)	N4—C4	1.342 (2)
O22—C21	1.250 (2)	N4—H41	0.9600
O1W—H12W	0.8900	N4—H42	0.9700
O1W—H11W	0.8200	C2—C3	1.370 (3)
O2W—H21W	0.9400	C2—C21	1.515 (3)
O2W—H22W	0.8400	C3—C4	1.407 (3)
O3W—H31W	0.8800	C4—C5	1.403 (2)
O3W—H32W	0.9000	C5—C6	1.376 (3)
O1W^i—Na1—O3W^ii	173.66 (6)	H41W—O4W—H42W	103.00
O1W—Na1—O3W	114.69 (6)	H51W—O5W—H52W	98.00
O1W—Na1—O1W^i	86.32 (5)	H61W—O6W—H62W	116.00
O1W—Na1—O3W^ii	100.02 (6)	C2—N1—C6	116.35 (16)
O2W—Na1—O3W	141.97 (6)	C4—N4—H41	118.00
O1W^i—Na1—O2W	85.88 (6)	C4—N4—H42	118.00
O2W—Na1—O3W^ii	92.71 (6)	H41—N4—H42	124.00
O1W—Na1—O2W	103.20 (6)	N1—C2—C3	123.14 (17)
O3W—Na1—O3W^ii	84.24 (5)	N1—C2—C21	115.53 (16)
O1W^i—Na1—O3W	93.06 (5)	C3—C2—C21	121.32 (16)
Na1—O1W—Na1^i	93.68 (5)	Cl3—C3—C2	119.28 (14)
Na1—O3W—Na1^ii	95.76 (6)	Cl3—C3—C4	119.39 (14)
Na1—O1W—H11W	100.00	C2—C3—C4	121.32 (16)
Na1^i—O1W—H11W	121.00	N4—C4—C3	122.49 (16)
Na1—O1W—H12W	128.00	N4—C4—C5	122.95 (17)
H11W—O1W—H12W	112.00	C3—C4—C5	114.55 (17)
Na1^i—O1W—H12W	103.00	Cl5—C5—C4	118.07 (14)
Na1—O2W—H22W	128.00	Cl5—C5—C6	121.71 (14)
H21W—O2W—H22W	97.00	C4—C5—C6	120.22 (16)
Na1—O2W—H21W	121.00	Cl6—C6—N1	115.37 (15)
Na1—O3W—H32W	119.00	Cl6—C6—C5	120.21 (14)
H31W—O3W—H32W	108.00	N1—C6—C5	124.42 (17)
Na1—O3W—H31W	109.00	O21—C21—O22	127.24 (18)
Na1^ii—O3W—H32W	115.00	O21—C21—C2	116.83 (17)
Na1^ii—O3W—H31W	109.00	O22—C21—C2	115.91 (17)
O3W^ii—Na1—O3W—Na1^ii	0.00 (6)	N1—C2—C21—O21	89.1 (2)
O1W—Na1—O1W^i—Na1^i	0.00 (6)	N1—C2—C3—Cl3	179.26 (15)
O2W—Na1—O1W^i—Na1^i	−103.53 (6)	N1—C2—C3—C4	0.0 (3)
O3W—Na1—O1W^i—Na1^i	114.57 (6)	C21—C2—C3—Cl3	0.7 (3)
O1W—Na1—O3W^ii—Na1^ii	114.11 (6)	C3—C2—C21—O22	89.4 (2)
O2W—Na1—O3W^ii—Na1^ii	−141.98 (6)	N1—C2—C21—O22	−89.3 (2)
O3W—Na1—O3W^ii—Na1^ii	−0.02 (8)	C3—C2—C21—O21	−92.2 (2)
O2W—Na1—O3W—Na1^ii	87.03 (10)	C2—C3—C4—C5	0.1 (3)
O1W^i—Na1—O3W—Na1^ii	174.25 (5)	Cl3—C3—C4—N4	0.6 (3)
O2W—Na1—O1W—Na1^i	84.89 (6)	Cl3—C3—C4—C5	−179.13 (15)
O3W—Na1—O1W—Na1^i	−91.68 (6)	C2—C3—C4—N4	179.9 (2)
O1W^i—Na1—O1W—Na1^i	0.00 (5)	C3—C4—C5—Cl5	179.71 (15)
O3W^ii—Na1—O1W—Na1^i	−179.91 (5)	N4—C4—C5—Cl5	−0.1 (3)
O1W—Na1—O3W—Na1^ii	−98.40 (6)	N4—C4—C5—C6	−180.0 (2)
C6—N1—C2—C21	178.63 (17)	C3—C4—C5—C6	−0.2 (3)
C2—N1—C6—Cl6	−179.62 (14)	C4—C5—C6—N1	0.2 (3)
C6—N1—C2—C3	0.0 (3)	Cl5—C5—C6—Cl6	−0.2 (3)
C2—N1—C6—C5	−0.1 (3)	Cl5—C5—C6—N1	−179.72 (15)
C21—C2—C3—C4	−178.59 (18)	C4—C5—C6—Cl6	179.74 (16)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O4W	0.82	1.97	2.786 (2)	178
O1W—H12W···O6W	0.89	1.99	2.877 (2)	174
O2W—H21W···O22^iii	0.94	1.79	2.721 (2)	171
O2W—H22W···O5W	0.84	1.98	2.816 (2)	172
O3W—H31W···O5W^iv	0.88	1.93	2.781 (2)	163
O3W—H32W···N1^ii	0.90	2.02	2.910 (2)	170
O4W—H41W···O22^v	0.99	1.93	2.916 (2)	173
O4W—H42W···O21	0.93	1.99	2.918 (2)	174
O5W—H51W···O21	0.90	1.87	2.748 (2)	166
O5W—H52W···O2W^vi	0.90	2.01	2.8481 (19)	155
O6W—H61W···O22^vii	0.93	2.10	2.972 (2)	156
O6W—H62W···Cl6	0.93	2.83	3.4400 (15)	124
O6W—H62W···O21^iv	0.93	2.19	2.996 (2)	144
N4—H41···Cl3	0.96	2.54	2.9956 (17)	109
N4—H41···O6W^viii	0.96	2.18	3.080 (2)	156
N4—H42···Cl5	0.97	2.52	2.9690 (17)	108
N4—H42···O4W^viii	0.97	2.22	3.146 (2)	160

Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y, −z+2; (iv) x, y+1, z; (v) x−1, y, z; (vi) −x, −y, −z+2; (vii) x−1, y+1, z; (viii) −x+1, −y+1, −z+1.