Poly[μ3-aqua-aqua(μ3-3,5-dinitro­benzoato-κO1:O3:O5)caesium]

Smith, G.

doi:10.1107/S1600536812037130

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Pages m1241-m1242

https://doi.org/10.1107/S1600536812037130

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Poly[μ₃-aqua-aqua(μ₃-3,5-dinitrobenzoato-κO¹:O³:O⁵)caesium]

Graham Smith ^a ^*

^aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 21 August 2012; accepted 28 August 2012; online 5 September 2012)

In the structure of the title complex, [Cs(C₇H₃N₂O₆)(H₂O)₂]_n, the Cs salt of 3,5-dinitrobenzoic acid, the metal complex centres have have irregular CsO₈ coordination, comprising two water molecules (one triply bridging and the other monodentate) and four O-atom donors from two nitro groups and one bridging carboxylate O-atom donor from the ligand. Intra-unit O—H⋯O hydrogen-bonding interactions involving both water molecules are observed in the three-dimensional polymeric complex structure.

Related literature

For exanples of structures of alkali metal complexes with 3,5-dinitrobenzoic acid, see: Yang & Ng (2007 ) (Li, Na); Tiekink et al. (1990 ); Jones et al. (2005 ); Madej et al. (2007 ) (Na); Miao & Fan (2011 ); Miao et al. (2011 ) (Rb). For examples of Cs complexes with nitrobenzoic acids, see: Smith & Wermuth (2011a ,b ).

Experimental

Crystal data

[Cs(C₇H₃N₂O₆)(H₂O)₂]
M_r = 380.06
Monoclinic, P 2₁ /n
a = 15.1249 (5) Å
b = 4.6223 (1) Å
c = 17.1024 (6) Å
β = 107.782 (4)°
V = 1138.54 (7) Å³
Z = 4
Mo Kα radiation
μ = 3.29 mm⁻¹
T = 200 K
0.28 × 0.15 × 0.06 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.792, T_max = 0.980
7596 measured reflections
2652 independent reflections
2336 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.048
S = 1.05
2652 reflections
179 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Selected bond lengths (Å)

Cs1—O1W	3.087 (2)
Cs1—O2W	3.282 (2)
Cs1—O12	3.1751 (16)
Cs1—O12ⁱ	3.1120 (17)
Cs1—O1Wⁱⁱ	3.261 (2)
Cs1—O32ⁱⁱⁱ	3.244 (2)
Cs1—O1W^iv	3.346 (2)
Cs1—O52^v	3.271 (2)
Symmetry codes: (i) x, y-1, z; (ii) x, y+1, z; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y, -z+2; (v) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O2W	0.80 (4)	1.98 (4)	2.734 (3)	159 (3)
O1W—H12W⋯O12^iv	0.83 (4)	2.25 (4)	3.016 (3)	155 (4)
O2W—H21W⋯O11^vi	0.83 (4)	1.94 (4)	2.764 (3)	174 (3)
O2W—H22W⋯O11^vii	0.85 (4)	1.96 (4)	2.797 (3)	168 (3)
Symmetry codes: (iv) -x+1, -y, -z+2; (vi) -x+1, -y+1, -z+2; (vii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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, 1999 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812037130/ng5289sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037130/ng5289Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812037130/ng5289Isup3.cml

checkCIF report

Comment top

3,5-Dinitrobenzoic acid (DNBA) has been a popular ligand used alone or in mixed-ligand applications for metal complexation and the structures of a large number of its complexes have been reported. With the alkali metals the structures of the complex salts with Li and Na (Yang & Ng, 2007; Jones et al., 2005): the complex salt adduct with Na (Tiekink et al., 1990; Madej et al., 2007) and the Rb complex salt and salt adduct (Miao & Fan, 2011; Miao et al., 2011) are known but the structure of the Cs complex salt has not been reported. The reaction of 3,5-dinitrobenzoic acid with caesium hydroxide in aqueous ethanol gave crystals of the title compound [Cs(C₇H₃N₂O₆)(H₂O)₂]_n and the structure is reported here. In the Rb and Cs complexes with the nitro-substituted aromatic carboxylic acids, expanded metal coordination spheres together with polymeric structures are common, in which ligands are bridging, e.g. anhydrous rubidium 3,5-dinitrobenzoate (8-coordinate) (Miao & Fan, 2011); tetracaesium bis(5-nitroisophthalate) heptahydrate (6- and 8-coordinate) (Smith & Wermuth, 2011a) and caesium bis(2-nitroanthranilate) dihydrate (7- and 9-coordinate) (Smith & Wermuth, 2011b).

In the structure of the title compound the CsO₈ complex unit (Fig. 1) is irregular 8-coordinate [Cs—O range, 3.087 (2)–3.346 (2) Å] (Table 1), comprising two water molecules (one triply bridging, the other monodentate) and four O-donors from two nitro groups and one bridging carboxyl-O donor group from the ligand. In the three-dimensional polymeric complex structure (Fig. 2), the rings of the DNBA ligands layer down the short b axis of the unit cell with a ring centroid separation of 4.6223 (1) Å (the b cell dimension) (Fig. 3). Present also are intra-polymer O—H···O hydrogen-bonding interactions involving both water molecules (Table 2).

Related literature top

For exanples of structures of alkali metal complexes with 3,5-dinitrobenzoic acid, see: Yang & Ng (2007) (Li, Na); Tiekink et al. (1990); Jones et al. (2005); Madej et al. (2007) (Na); Miao & Fan (2011); Miao et al. (2011) (Rb). For examples of Cs complexes with nitrobenzoic acids, see: Smith & Wermuth (2011a,b).

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 3,5-dinitrobenzoic acid in 20 ml of 10% ethanol–water. Room temperature evaporation of the solution to incipient dryness gave yellow needle crystals of the title complex from which a specimen was cleaved for the X-ray analysis.

Structure description top

For exanples of structures of alkali metal complexes with 3,5-dinitrobenzoic acid, see: Yang & Ng (2007) (Li, Na); Tiekink et al. (1990); Jones et al. (2005); Madej et al. (2007) (Na); Miao & Fan (2011); Miao et al. (2011) (Rb). For examples of Cs complexes with nitrobenzoic acids, see: Smith & Wermuth (2011a,b).

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, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	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.
	Fig. 2. A section of the three-dimensional coordination polymer showing inter-unit Cs···Cs associations and 30% probability ellipsoids.
	Fig. 3. The packing in the unit cell viewed down the the b axial direction showing intra-unit hydrogen-bonding associations as dashed lines. Non-interactive H atoms are omitted. For symmetry codes, see Fig. 1 and Table 2.

Poly[µ₃-aqua-aqua(µ₃-3,5-dinitrobenzoato- κO¹:O³:O⁵)caesium] top

Crystal data top

[Cs(C₇H₃N₂O₆)(H₂O)₂]	F(000) = 728
M_r = 380.06	D_x = 2.217 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3275 reflections
a = 15.1249 (5) Å	θ = 3.2–28.8°
b = 4.6223 (1) Å	µ = 3.29 mm⁻¹
c = 17.1024 (6) Å	T = 200 K
β = 107.782 (4)°	Needle, yellow
V = 1138.54 (7) Å³	0.28 × 0.15 × 0.06 mm
Z = 4

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	2652 independent reflections
Radiation source: Enhance (Mo) X-ray source	2336 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 16.077 pixels mm^-1	θ_max = 28.9°, θ_min = 3.2°
ω scans	h = −20→20
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −6→5
T_min = 0.792, T_max = 0.980	l = −22→22
7596 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0172P)²] where P = (F_o² + 2F_c²)/3
2652 reflections	(Δ/σ)_max = 0.001
179 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

[Cs(C₇H₃N₂O₆)(H₂O)₂]	V = 1138.54 (7) Å³
M_r = 380.06	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.1249 (5) Å	µ = 3.29 mm⁻¹
b = 4.6223 (1) Å	T = 200 K
c = 17.1024 (6) Å	0.28 × 0.15 × 0.06 mm
β = 107.782 (4)°

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	2652 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	2336 reflections with I > 2σ(I)
T_min = 0.792, T_max = 0.980	R_int = 0.030
7596 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.47 e Å⁻³
2652 reflections	Δρ_min = −0.56 e Å⁻³
179 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cs1	0.63127 (1)	0.11431 (3)	0.94980 (1)	0.0232 (1)
O1W	0.57824 (16)	−0.3598 (5)	1.05448 (13)	0.0315 (7)
O2W	0.69998 (16)	0.0306 (5)	1.14991 (13)	0.0311 (7)
O11	0.37491 (13)	0.6190 (4)	0.75558 (11)	0.0278 (6)
O12	0.52278 (14)	0.6236 (3)	0.83580 (11)	0.0266 (6)
O31	0.74660 (14)	0.3113 (4)	0.68972 (12)	0.0315 (6)
O32	0.71260 (15)	−0.0756 (4)	0.61600 (12)	0.0351 (7)
O51	0.39421 (16)	−0.3890 (4)	0.51426 (12)	0.0351 (7)
O52	0.28880 (15)	−0.1482 (4)	0.54804 (12)	0.0381 (7)
N3	0.69218 (16)	0.1222 (4)	0.65482 (13)	0.0234 (7)
N5	0.36953 (17)	−0.2001 (5)	0.55368 (12)	0.0246 (7)
C1	0.48439 (18)	0.3386 (5)	0.71545 (14)	0.0169 (7)
C2	0.57543 (18)	0.3203 (5)	0.71383 (14)	0.0177 (7)
C3	0.59685 (18)	0.1317 (5)	0.65956 (15)	0.0186 (7)
C4	0.53156 (19)	−0.0458 (5)	0.60715 (14)	0.0191 (7)
C5	0.44224 (19)	−0.0198 (5)	0.60976 (14)	0.0187 (7)
C6	0.41608 (18)	0.1685 (5)	0.66192 (14)	0.0187 (7)
C11	0.45850 (19)	0.5455 (5)	0.77413 (15)	0.0186 (7)
H2	0.62150	0.43370	0.74890	0.0210*
H4	0.54740	−0.17570	0.57210	0.0230*
H6	0.35450	0.18100	0.66120	0.0220*
H11W	0.616 (3)	−0.280 (7)	1.091 (2)	0.038 (10)*
H12W	0.559 (3)	−0.478 (7)	1.081 (2)	0.055 (12)*
H21W	0.677 (3)	0.124 (6)	1.180 (2)	0.052 (12)*
H22W	0.750 (3)	−0.041 (6)	1.1818 (19)	0.037 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.0226 (1)	0.0231 (1)	0.0235 (1)	−0.0002 (1)	0.0063 (1)	0.0030 (1)
O1W	0.0308 (13)	0.0405 (12)	0.0214 (10)	−0.0117 (10)	0.0053 (9)	0.0000 (10)
O2W	0.0259 (12)	0.0355 (11)	0.0284 (11)	0.0046 (10)	0.0032 (10)	−0.0094 (10)
O11	0.0174 (10)	0.0373 (11)	0.0279 (10)	0.0052 (8)	0.0059 (8)	−0.0072 (8)
O12	0.0229 (11)	0.0330 (10)	0.0210 (9)	−0.0005 (8)	0.0023 (8)	−0.0092 (8)
O31	0.0204 (11)	0.0385 (11)	0.0356 (11)	−0.0040 (9)	0.0084 (9)	−0.0042 (9)
O32	0.0310 (12)	0.0442 (12)	0.0324 (11)	0.0130 (9)	0.0130 (10)	−0.0079 (9)
O51	0.0492 (15)	0.0248 (10)	0.0266 (10)	−0.0040 (9)	0.0045 (10)	−0.0093 (8)
O52	0.0252 (12)	0.0548 (13)	0.0342 (11)	−0.0143 (10)	0.0089 (9)	−0.0132 (10)
N3	0.0223 (13)	0.0294 (12)	0.0180 (11)	0.0075 (10)	0.0055 (9)	0.0042 (9)
N5	0.0304 (15)	0.0246 (11)	0.0169 (11)	−0.0075 (10)	0.0044 (10)	−0.0012 (9)
C1	0.0203 (14)	0.0179 (11)	0.0128 (11)	−0.0002 (10)	0.0055 (10)	0.0013 (9)
C2	0.0171 (13)	0.0182 (11)	0.0161 (12)	−0.0004 (10)	0.0024 (10)	0.0025 (10)
C3	0.0188 (14)	0.0198 (12)	0.0178 (12)	0.0039 (10)	0.0067 (10)	0.0057 (10)
C4	0.0278 (15)	0.0153 (11)	0.0141 (12)	0.0013 (10)	0.0063 (10)	−0.0001 (9)
C5	0.0244 (15)	0.0175 (11)	0.0130 (11)	−0.0039 (11)	0.0039 (10)	−0.0005 (10)
C6	0.0197 (14)	0.0207 (12)	0.0152 (11)	−0.0023 (10)	0.0048 (10)	0.0034 (10)
C11	0.0220 (14)	0.0192 (12)	0.0168 (12)	−0.0014 (10)	0.0091 (10)	0.0022 (10)

Geometric parameters (Å, º) top

Cs1—O1W	3.087 (2)	O1W—H11W	0.80 (4)
Cs1—O2W	3.282 (2)	O2W—H21W	0.83 (4)
Cs1—O12	3.1751 (16)	O2W—H22W	0.85 (4)
Cs1—O12ⁱ	3.1120 (17)	N3—C3	1.469 (4)
Cs1—O1Wⁱⁱ	3.261 (2)	N5—C5	1.476 (3)
Cs1—O32ⁱⁱⁱ	3.244 (2)	C1—C2	1.388 (4)
Cs1—O1W^iv	3.346 (2)	C1—C6	1.395 (3)
Cs1—O52^v	3.271 (2)	C1—C11	1.522 (3)
O11—C11	1.253 (4)	C2—C3	1.382 (3)
O12—C11	1.250 (3)	C3—C4	1.382 (4)
O31—N3	1.224 (3)	C4—C5	1.371 (4)
O32—N3	1.224 (3)	C5—C6	1.388 (3)
O51—N5	1.229 (3)	C2—H2	0.9300
O52—N5	1.219 (4)	C4—H4	0.9300
O1W—H12W	0.82 (4)	C6—H6	0.9300

O1W—Cs1—O2W	50.74 (6)	H11W—O1W—H12W	100 (4)
O1W—Cs1—O12	134.87 (6)	Cs1ⁱ—O1W—H11W	123 (3)
O1W—Cs1—O12ⁱ	70.44 (5)	Cs1^iv—O1W—H11W	108 (3)
O1W—Cs1—O1Wⁱⁱ	93.43 (6)	Cs1ⁱ—O1W—H12W	90 (3)
O1W—Cs1—O32ⁱⁱⁱ	149.39 (6)	Cs1^iv—O1W—H12W	75 (3)
O1W—Cs1—O1W^iv	80.87 (6)	Cs1—O1W—H11W	83 (2)
O1W—Cs1—O52^v	60.79 (6)	H21W—O2W—H22W	105 (3)
O2W—Cs1—O12	131.87 (5)	Cs1—O2W—H22W	131 (2)
O2W—Cs1—O12ⁱ	120.39 (5)	Cs1—O2W—H21W	122 (2)
O1Wⁱⁱ—Cs1—O2W	64.41 (6)	O32—N3—C3	117.8 (2)
O2W—Cs1—O32ⁱⁱⁱ	112.44 (6)	O31—N3—C3	118.5 (2)
O1W^iv—Cs1—O2W	93.38 (6)	O31—N3—O32	123.7 (3)
O2W—Cs1—O52^v	55.78 (6)	O51—N5—O52	124.1 (2)
O12—Cs1—O12ⁱ	94.64 (4)	O51—N5—C5	117.8 (2)
O1Wⁱⁱ—Cs1—O12	67.47 (5)	O52—N5—C5	118.0 (2)
O12—Cs1—O32ⁱⁱⁱ	75.75 (5)	C6—C1—C11	119.9 (2)
O1W^iv—Cs1—O12	55.02 (5)	C2—C1—C6	119.5 (2)
O12—Cs1—O52^v	164.29 (6)	C2—C1—C11	120.5 (2)
O1Wⁱⁱ—Cs1—O12ⁱ	135.75 (6)	C1—C2—C3	119.3 (2)
O12ⁱ—Cs1—O32ⁱⁱⁱ	113.90 (5)	C2—C3—C4	122.8 (3)
O1W^iv—Cs1—O12ⁱ	85.35 (5)	N3—C3—C2	119.4 (2)
O12ⁱ—Cs1—O52^v	90.21 (5)	N3—C3—C4	117.7 (2)
O1Wⁱⁱ—Cs1—O32ⁱⁱⁱ	100.85 (5)	C3—C4—C5	116.3 (2)
O1Wⁱⁱ—Cs1—O1W^iv	50.88 (6)	C4—C5—C6	123.6 (2)
O1Wⁱⁱ—Cs1—O52^v	118.15 (5)	N5—C5—C6	118.0 (3)
O1W^iv—Cs1—O32ⁱⁱⁱ	128.87 (5)	N5—C5—C4	118.4 (2)
O32ⁱⁱⁱ—Cs1—O52^v	88.62 (5)	C1—C6—C5	118.4 (3)
O1W^iv—Cs1—O52^v	140.47 (5)	O11—C11—O12	126.9 (2)
Cs1—O1W—Cs1ⁱ	93.43 (6)	O11—C11—C1	116.5 (2)
Cs1—O1W—Cs1^iv	99.13 (6)	O12—C11—C1	116.6 (2)
Cs1ⁱ—O1W—Cs1^iv	129.12 (7)	C1—C2—H2	120.00
Cs1—O12—C11	115.28 (13)	C3—C2—H2	120.00
Cs1—O12—Cs1ⁱⁱ	94.64 (5)	C3—C4—H4	122.00
Cs1ⁱⁱ—O12—C11	149.86 (14)	C5—C4—H4	122.00
Cs1^vi—O32—N3	148.16 (18)	C1—C6—H6	121.00
Cs1^vii—O52—N5	117.78 (15)	C5—C6—H6	121.00
Cs1—O1W—H12W	174 (3)

O2W—Cs1—O1W—Cs1ⁱ	−127.44 (9)	O1W—Cs1—O1W^iv—Cs1^iv	0.00 (6)
O2W—Cs1—O1W—Cs1^iv	102.04 (8)	O2W—Cs1—O1W^iv—Cs1^iv	−49.33 (6)
O12—Cs1—O1W—Cs1ⁱ	118.81 (6)	O12—Cs1—O1W^iv—Cs1^iv	169.89 (8)
O12—Cs1—O1W—Cs1^iv	−11.71 (9)	O1W—Cs1—O52^v—N5^v	−167.08 (18)
O12ⁱ—Cs1—O1W—Cs1ⁱ	42.25 (5)	O2W—Cs1—O52^v—N5^v	−106.86 (18)
O12ⁱ—Cs1—O1W—Cs1^iv	−88.27 (6)	Cs1—O12—C11—O11	122.9 (2)
O1Wⁱⁱ—Cs1—O1W—Cs1ⁱ	179.98 (9)	Cs1—O12—C11—C1	−57.0 (3)
O1Wⁱⁱ—Cs1—O1W—Cs1^iv	49.48 (6)	Cs1ⁱⁱ—O12—C11—O11	−49.7 (5)
O32ⁱⁱⁱ—Cs1—O1W—Cs1ⁱ	−61.86 (12)	Cs1ⁱⁱ—O12—C11—C1	130.5 (3)
O32ⁱⁱⁱ—Cs1—O1W—Cs1^iv	167.61 (7)	Cs1^vi—O32—N3—O31	−0.6 (4)
O1W^iv—Cs1—O1W—Cs1ⁱ	130.53 (6)	Cs1^vi—O32—N3—C3	179.48 (19)
O1W^iv—Cs1—O1W—Cs1^iv	−0.02 (12)	Cs1^vii—O52—N5—O51	12.2 (3)
O52^v—Cs1—O1W—Cs1ⁱ	−59.47 (6)	Cs1^vii—O52—N5—C5	−169.48 (15)
O52^v—Cs1—O1W—Cs1^iv	170.01 (8)	O31—N3—C3—C2	−11.0 (3)
O1W—Cs1—O12—C11	−63.1 (2)	O31—N3—C3—C4	167.3 (2)
O1W—Cs1—O12—Cs1ⁱⁱ	113.15 (7)	O32—N3—C3—C2	169.0 (2)
O2W—Cs1—O12—C11	−135.23 (18)	O32—N3—C3—C4	−12.7 (3)
O2W—Cs1—O12—Cs1ⁱⁱ	41.03 (9)	O51—N5—C5—C4	8.4 (3)
O12ⁱ—Cs1—O12—C11	3.7 (2)	O51—N5—C5—C6	−172.0 (2)
O12ⁱ—Cs1—O12—Cs1ⁱⁱ	−180.00 (7)	O52—N5—C5—C4	−170.0 (2)
O1Wⁱⁱ—Cs1—O12—C11	−134.4 (2)	O52—N5—C5—C6	9.6 (3)
O1Wⁱⁱ—Cs1—O12—Cs1ⁱⁱ	41.90 (6)	C6—C1—C2—C3	−0.5 (3)
O32ⁱⁱⁱ—Cs1—O12—C11	117.2 (2)	C11—C1—C2—C3	−179.6 (2)
O32ⁱⁱⁱ—Cs1—O12—Cs1ⁱⁱ	−66.50 (5)	C2—C1—C6—C5	1.5 (3)
O1W^iv—Cs1—O12—C11	−77.3 (2)	C11—C1—C6—C5	−179.4 (2)
O1W^iv—Cs1—O12—Cs1ⁱⁱ	98.99 (7)	C2—C1—C11—O11	158.1 (2)
O1W—Cs1—O12ⁱ—Cs1ⁱ	−43.76 (6)	C2—C1—C11—O12	−22.1 (3)
O1W—Cs1—O12ⁱ—C11ⁱ	129.5 (4)	C6—C1—C11—O11	−21.0 (3)
O2W—Cs1—O12ⁱ—Cs1ⁱ	−34.52 (8)	C6—C1—C11—O12	158.9 (2)
O2W—Cs1—O12ⁱ—C11ⁱ	138.7 (4)	C1—C2—C3—N3	177.0 (2)
O12—Cs1—O12ⁱ—Cs1ⁱ	180.00 (7)	C1—C2—C3—C4	−1.2 (4)
O12—Cs1—O12ⁱ—C11ⁱ	−6.8 (4)	N3—C3—C4—C5	−176.4 (2)
O1W—Cs1—O1Wⁱⁱ—Cs1ⁱⁱ	179.98 (9)	C2—C3—C4—C5	1.9 (4)
O2W—Cs1—O1Wⁱⁱ—Cs1ⁱⁱ	137.03 (8)	C3—C4—C5—N5	178.7 (2)
O12—Cs1—O1Wⁱⁱ—Cs1ⁱⁱ	−42.25 (5)	C3—C4—C5—C6	−0.9 (4)
O1W—Cs1—O32ⁱⁱⁱ—N3ⁱⁱⁱ	−174.4 (3)	N5—C5—C6—C1	179.7 (2)
O2W—Cs1—O32ⁱⁱⁱ—N3ⁱⁱⁱ	−124.7 (3)	C4—C5—C6—C1	−0.8 (4)
O12—Cs1—O32ⁱⁱⁱ—N3ⁱⁱⁱ	5.1 (3)

Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+1, −y, −z+2; (v) x+1/2, −y−1/2, z+1/2; (vi) −x+3/2, y−1/2, −z+3/2; (vii) x−1/2, −y−1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O2W	0.80 (4)	1.98 (4)	2.734 (3)	159 (3)
O1W—H12W···O12^iv	0.83 (4)	2.25 (4)	3.016 (3)	155 (4)
O2W—H21W···O11^viii	0.83 (4)	1.94 (4)	2.764 (3)	174 (3)
O2W—H22W···O11^ix	0.85 (4)	1.96 (4)	2.797 (3)	168 (3)

Symmetry codes: (iv) −x+1, −y, −z+2; (viii) −x+1, −y+1, −z+2; (ix) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cs(C₇H₃N₂O₆)(H₂O)₂]
M_r	380.06
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	15.1249 (5), 4.6223 (1), 17.1024 (6)
β (°)	107.782 (4)
V (Å³)	1138.54 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.29
Crystal size (mm)	0.28 × 0.15 × 0.06

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD-detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.792, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	7596, 2652, 2336
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.048, 1.05
No. of reflections	2652
No. of parameters	179
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.56

Computer programs: CrysAlis PRO (Agilent, 2012), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).

Selected bond lengths (Å) top

Cs1—O1W	3.087 (2)	Cs1—O1Wⁱⁱ	3.261 (2)
Cs1—O2W	3.282 (2)	Cs1—O32ⁱⁱⁱ	3.244 (2)
Cs1—O12	3.1751 (16)	Cs1—O1W^iv	3.346 (2)
Cs1—O12ⁱ	3.1120 (17)	Cs1—O52^v	3.271 (2)

Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+1, −y, −z+2; (v) x+1/2, −y−1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O2W	0.80 (4)	1.98 (4)	2.734 (3)	159 (3)
O1W—H12W···O12^iv	0.83 (4)	2.25 (4)	3.016 (3)	155 (4)
O2W—H21W···O11^vi	0.83 (4)	1.94 (4)	2.764 (3)	174 (3)
O2W—H22W···O11^vii	0.85 (4)	1.96 (4)	2.797 (3)	168 (3)

Symmetry codes: (iv) −x+1, −y, −z+2; (vi) −x+1, −y+1, −z+2; (vii) x+1/2, −y+1/2, z+1/2.

References

Agilent (2012). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England. Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Jones, H. P., Gillon, A. L. & Davey, R. J. (2005). Acta Cryst. E61, m1131–m1132. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Madej, A., Oleksin, B. J. & Śliwiński, J. (2007). Pol. J. Chem. 81, 1201–1218. CAS Google Scholar
Miao, Y. & Fan, T. (2011). Acta Cryst. E67, m1040. Web of Science CSD CrossRef IUCr Journals Google Scholar
Miao, Y., Zhang, X. & Liu, C. (2011). Acta Cryst. E67, m1002. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, G. & Wermuth, U. D. (2011a). J. Chem. Crystallogr. 41, 688–692. Web of Science CSD CrossRef CAS Google Scholar
Smith, G. & Wermuth, U. D. (2011b). Acta Cryst. E67, m1047–m1048. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tiekink, E. R. T., Hundal, M. S., Sood, G., Kapoor, P. & Poonia, N. S. (1990). Z. Kristallogr. 192, 103–109. CAS Google Scholar
Yang, G. & Ng, S. W. (2007). Cryst. Res. Technol. 42, 201–206. Web of Science CSD CrossRef CAS Google Scholar

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Volume 68| Part 10| October 2012| Pages m1241-m1242

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