Poly[di-μ-aqua-bis­(μ-2-amino-4-nitro­benzoato)dicaesium]

Smith, G.; Wermuth, U.D.

doi:10.1107/S1600536811026614

Poly[di-μ-aqua-bis(μ-2-amino-4-nitrobenzoato)dicaesium]

In the structure of title compound, [Cs₂(C₇H₅N₂O₄)₂(H₂O)₂]_n, the asymmetric unit contains two independent Cs atoms comprising different coordination polyhedra. One is nine-coordinate, the other seven-coordinate, both having irregular configurations. The CsO₉ coordination polyhedron comprises O-atom donors from three bridging water molecules, one of which is doubly bridging, three from carboxylate groups, and three from nitro groups, of which two are bidentate chelate bridging. The CsO₆N coordination polyhedron comprises the two bridging water molecules, one amine N-atom donor, one carboxylate O-atom donor and four O-atom donors from nitro groups (two from the chelate bridges). The extension of the dimeric unit gives a three-dimensional polymeric structure, which is stabilized by both intra- and intermolecular amine N—H

O and water O—H

O hydrogen bonds to carboxylate O-atom acceptors, as well as inter-ring π–π interactions [minimum ring centroid–centroid separation = 3.4172 (15) Å].

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811026614/wm2509sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811026614/wm2509Isup2.hkl Contains datablock I

CCDC reference: 841009

checkCIF report

Key indicators

Single-crystal X-ray study
T = 200 K
Mean (C-C) = 0.004 Å
R factor = 0.024
wR factor = 0.049
Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        O2W
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          6
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        498

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n

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

   0 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
   1 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

Comment top

The structures of the alkali metal complexes with aromatic carboxylic acids are of interest, particularly with the heavier metals Rb and Cs, because of their expanded coordination spheres and their ability to form polymeric systems. We obtained red crystals of the title compound [Cs₂(C₇H₅N₂O₄)₂(H₂O)₂]_n (I) from the reaction of caesium carbonate with 4-nitroanthranilic acid (4-NAA), and the structure is reported here. Although the structure of the Cs complex with anthranilic acid has been reported (a 1:1 metal complex–acid adduct polymer) (Wiesbrock & Schmidbaur, 2003), no metal complexes of 4-nitroanthranilic are known. We have reported the structures of the 4-NAA salts of the Lewis bases ethylenediamine (a dihydrate) (Smith et al., 2002), dicyclohexamine (anhydrous) (Smith et al., 2004) and guanidine (a monohydrate) (Smith et al., 2007).

In the structure of (I), the asymmetric unit contains two independent Cs atoms, one nine-coordinate, the other seven-coordinate, with both having irregular configurations (Fig. 1). The CsO₉ coordination polyhedron about Cs1 comprises oxygen donors from three bridging water molecules, two of which bridge Cs1 and Cs2, three from carboxylate groups, and two from bidentate bridging nitro groups [Cs—O range, 3.165 (2)–3.414 (3) Å]. The CsO₆N coordination polyhedron about Cs2 comprises the two bridging water atoms, one amine N donor, one carboxyl O donor and four O donors from nitro groups (two bidentate bridging) [Cs—O/(N) range, 3.090 (2)–3.352 (3) Å] (Table 1). The extension of the dimeric unit gives a three-dimensional polymeric structure (Fig. 2) which is stabilized by both intra- and intermolecular amine N—H···O and water O—H···O hydrogen bonds to only carboxyl O acceptors (Table 2). Also, there are inter-ring π–π interactions involving both ring 1 (C1A–C6A) and ring 2 (ring 1B–C6B): minimum centroid separation: rings 1–1^vii, 3.4172 (15) Å; rings 2–2^v, 3.6081 (16) Å (for symmetry codes, see Tables 1, 2).

These structural features, including expanded coordination spheres, multiple bridging and polymeric extensions are similar to those found in other Cs complexes with nitro-substituted aromatic carboxylates, e.g. cesium 3,5-dinitrosalicylate (Hu et al., 2005) and cesium 5-nitroisophthalate (Smith & Wermuth, 2010).

Related literature top

For the structures of some Cs complexes of aromatic carboxylatic acids, see: Wiesbrock & Schmidbaur (2003); Hu et al. (2005); Smith & Wermuth (2010). For Lewis base salts of 4-nitroanthranilic acid, see: Smith et al. (2002, 2004, 2007).

Experimental top

The title compound was synthesized by heating together under reflux for 15 minutes, 1 mmol of caesium carbonate and 2 mmol of 4-nitroanthranilic acid in 50 ml of 1:4 ethanol–water. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave flat red prisms of (I) from which a suitable specimen was cleaved for the X-ray analysis.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); 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 dimeric repeat unit of (I), with non-H atoms drawn as 50% probability ellipsoids. For symmetry codes, see Table 1.
	Fig. 2. The polymeric structure of (I) in the unit cell viewed down b. Non-associative H atoms are omitted and hydrogen bonds are shown as dashed lines.

Poly[di-µ-aqua-bis(µ-2-amino-4-nitrobenzoato)dicaesium] top

Crystal data top

[Cs₂(C₇H₅N₂O₄)₂(H₂O)₂]	F(000) = 1264
M_r = 664.12	D_x = 2.268 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8867 reflections
a = 15.3615 (3) Å	θ = 3.2–28.7°
b = 6.9573 (2) Å	µ = 3.81 mm⁻¹
c = 18.3714 (4) Å	T = 200 K
β = 97.903 (2)°	Plate, red
V = 1944.79 (8) Å³	0.40 × 0.30 × 0.10 mm
Z = 4

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	4555 independent reflections
Radiation source: Enhance (Mo) X-ray source	3818 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 16.077 pixels mm^-1	θ_max = 28.8°, θ_min = 3.3°
ω scans	h = −20→20
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −8→9
T_min = 0.411, T_max = 0.980	l = −23→23
14204 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) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0232P)²] where P = (F_o² + 2F_c²)/3
4555 reflections	(Δ/σ)_max = 0.002
303 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

[Cs₂(C₇H₅N₂O₄)₂(H₂O)₂]	V = 1944.79 (8) Å³
M_r = 664.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.3615 (3) Å	µ = 3.81 mm⁻¹
b = 6.9573 (2) Å	T = 200 K
c = 18.3714 (4) Å	0.40 × 0.30 × 0.10 mm
β = 97.903 (2)°

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	4555 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	3818 reflections with I > 2σ(I)
T_min = 0.411, T_max = 0.980	R_int = 0.026
14204 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.47 e Å⁻³
4555 reflections	Δρ_min = −0.90 e Å⁻³
303 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	0.84171 (1)	−0.10346 (2)	0.72068 (1)	0.0226 (1)
Cs2	0.90529 (1)	0.22312 (3)	0.53616 (1)	0.0262 (1)
O1W	0.83714 (17)	0.3457 (3)	0.68930 (14)	0.0301 (8)
O2W	0.8960 (2)	−0.2190 (4)	0.55795 (16)	0.0418 (9)
O11A	0.26335 (13)	0.4294 (3)	0.47800 (11)	0.0320 (7)
O11B	1.01545 (12)	0.4344 (3)	0.26444 (11)	0.0278 (7)
O12A	0.29653 (13)	0.3889 (3)	0.36507 (11)	0.0274 (6)
O12B	0.97730 (13)	0.4711 (3)	0.37664 (11)	0.0308 (7)
O41A	0.71088 (13)	0.0800 (3)	0.53048 (14)	0.0398 (8)
O41B	0.54158 (14)	0.4375 (4)	0.20587 (13)	0.0476 (9)
O42A	0.66924 (15)	0.1204 (3)	0.63677 (13)	0.0404 (8)
O42B	0.58798 (14)	0.4656 (4)	0.10161 (12)	0.0451 (8)
N2A	0.45730 (19)	0.2618 (4)	0.34723 (15)	0.0282 (8)
N2B	0.8077 (2)	0.4733 (4)	0.39156 (14)	0.0308 (9)
N4A	0.65627 (16)	0.1286 (3)	0.56911 (16)	0.0282 (8)
N4B	0.60057 (15)	0.4527 (3)	0.16866 (14)	0.0254 (7)
C1A	0.40690 (16)	0.3164 (4)	0.46641 (14)	0.0161 (8)
C1B	0.86323 (17)	0.4523 (4)	0.27425 (15)	0.0177 (8)
C2A	0.47163 (18)	0.2593 (3)	0.42261 (15)	0.0183 (8)
C2B	0.79362 (17)	0.4629 (4)	0.31685 (15)	0.0195 (8)
C3A	0.55438 (17)	0.2026 (4)	0.45856 (16)	0.0206 (8)
C3B	0.70712 (18)	0.4587 (4)	0.28022 (15)	0.0208 (8)
C4A	0.56969 (17)	0.1972 (4)	0.53363 (16)	0.0208 (8)
C4B	0.69270 (17)	0.4511 (4)	0.20513 (15)	0.0190 (8)
C5A	0.50738 (18)	0.2486 (3)	0.57821 (16)	0.0210 (8)
C5B	0.75952 (18)	0.4438 (4)	0.16125 (15)	0.0216 (8)
C6A	0.42732 (17)	0.3090 (4)	0.54248 (15)	0.0192 (8)
C6B	0.84406 (17)	0.4416 (4)	0.19793 (15)	0.0200 (8)
C11A	0.31553 (17)	0.3831 (4)	0.43413 (15)	0.0190 (8)
C11B	0.95942 (18)	0.4511 (4)	0.30752 (16)	0.0219 (8)
H3B	0.65990	0.46120	0.30690	0.0250*
H5B	0.74790	0.44050	0.11020	0.0260*
H21B	0.764 (2)	0.501 (4)	0.4175 (17)	0.030 (9)*
H3A	0.59870	0.16870	0.43130	0.0250*
H22B	0.857 (2)	0.507 (4)	0.4101 (17)	0.029 (9)*
H5A	0.51900	0.24270	0.62920	0.0250*
H6A	0.38460	0.34700	0.57080	0.0230*
H6B	0.89050	0.43270	0.17050	0.0240*
H11W	0.888 (3)	0.411 (6)	0.699 (2)	0.084 (16)*
H12W	0.797 (3)	0.425 (5)	0.673 (2)	0.048 (14)*
H21A	0.404 (3)	0.271 (5)	0.326 (2)	0.059 (13)*
H21W	0.849 (3)	−0.282 (5)	0.547 (2)	0.037 (13)*
H22A	0.487 (2)	0.182 (5)	0.3227 (18)	0.039 (10)*
H22W	0.932 (3)	−0.289 (6)	0.581 (2)	0.056 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.0213 (1)	0.0241 (1)	0.0224 (1)	0.0021 (1)	0.0035 (1)	−0.0006 (1)
Cs2	0.0251 (1)	0.0282 (1)	0.0242 (1)	−0.0013 (1)	−0.0008 (1)	−0.0002 (1)
O1W	0.0246 (13)	0.0298 (12)	0.0338 (14)	−0.0002 (11)	−0.0029 (10)	0.0040 (11)
O2W	0.0317 (15)	0.0376 (14)	0.0520 (18)	−0.0006 (13)	−0.0084 (13)	0.0074 (12)
O11A	0.0207 (10)	0.0497 (13)	0.0255 (12)	0.0087 (10)	0.0024 (9)	−0.0078 (10)
O11B	0.0145 (10)	0.0370 (12)	0.0316 (12)	0.0014 (9)	0.0022 (9)	−0.0027 (9)
O12A	0.0236 (10)	0.0377 (12)	0.0198 (11)	0.0084 (9)	−0.0007 (8)	0.0013 (9)
O12B	0.0235 (11)	0.0430 (12)	0.0241 (11)	0.0009 (10)	−0.0035 (9)	−0.0032 (10)
O41A	0.0172 (11)	0.0420 (14)	0.0602 (17)	0.0041 (10)	0.0050 (11)	−0.0026 (12)
O41B	0.0195 (11)	0.0811 (19)	0.0434 (15)	0.0017 (12)	0.0087 (11)	0.0026 (13)
O42A	0.0311 (12)	0.0438 (13)	0.0408 (15)	0.0044 (10)	−0.0141 (11)	−0.0011 (11)
O42B	0.0272 (12)	0.0750 (17)	0.0295 (13)	−0.0086 (12)	−0.0086 (10)	0.0112 (12)
N2A	0.0280 (15)	0.0360 (15)	0.0216 (14)	0.0063 (12)	0.0074 (12)	−0.0002 (12)
N2B	0.0230 (14)	0.0484 (17)	0.0210 (14)	0.0039 (13)	0.0027 (12)	−0.0008 (12)
N4A	0.0173 (12)	0.0200 (12)	0.0448 (17)	−0.0038 (10)	−0.0050 (12)	−0.0019 (12)
N4B	0.0194 (12)	0.0280 (12)	0.0280 (14)	0.0009 (10)	0.0006 (11)	0.0016 (11)
C1A	0.0161 (13)	0.0131 (12)	0.0187 (14)	0.0014 (10)	0.0009 (10)	−0.0018 (10)
C1B	0.0181 (13)	0.0151 (12)	0.0193 (14)	0.0014 (11)	0.0005 (11)	−0.0011 (11)
C2A	0.0211 (14)	0.0120 (13)	0.0223 (15)	−0.0008 (10)	0.0049 (11)	0.0004 (10)
C2B	0.0216 (14)	0.0184 (12)	0.0184 (14)	0.0012 (11)	0.0024 (11)	0.0004 (11)
C3A	0.0170 (14)	0.0163 (13)	0.0300 (16)	−0.0024 (11)	0.0083 (11)	−0.0021 (12)
C3B	0.0181 (14)	0.0212 (13)	0.0241 (15)	−0.0004 (11)	0.0062 (11)	0.0004 (12)
C4A	0.0151 (13)	0.0136 (12)	0.0320 (17)	−0.0027 (11)	−0.0031 (12)	−0.0004 (12)
C4B	0.0140 (13)	0.0173 (12)	0.0247 (15)	−0.0007 (11)	−0.0011 (11)	0.0009 (11)
C5A	0.0238 (15)	0.0182 (14)	0.0197 (15)	−0.0023 (11)	−0.0017 (12)	0.0002 (11)
C5B	0.0222 (14)	0.0246 (14)	0.0176 (14)	−0.0023 (12)	0.0009 (11)	0.0003 (12)
C6A	0.0181 (13)	0.0193 (13)	0.0211 (15)	0.0008 (11)	0.0056 (11)	−0.0017 (11)
C6B	0.0209 (14)	0.0193 (13)	0.0208 (14)	−0.0004 (11)	0.0061 (11)	−0.0025 (11)
C11A	0.0190 (14)	0.0162 (13)	0.0217 (15)	−0.0002 (11)	0.0025 (11)	−0.0016 (11)
C11B	0.0216 (14)	0.0189 (13)	0.0248 (16)	−0.0016 (11)	0.0021 (12)	−0.0001 (12)

Geometric parameters (Å, º) top

Cs1—O1W	3.177 (2)	N2A—C2A	1.372 (4)
Cs1—O2W	3.311 (3)	N2B—C2B	1.362 (4)
Cs1—O42A	3.271 (2)	N4A—C4A	1.478 (4)
Cs1—O1Wⁱ	3.414 (3)	N4B—C4B	1.480 (4)
Cs1—O42Aⁱ	3.271 (2)	N2A—H21A	0.86 (4)
Cs1—O12Aⁱⁱ	3.165 (2)	N2A—H22A	0.88 (3)
Cs1—O11Bⁱⁱⁱ	3.166 (2)	N2B—H21B	0.90 (3)
Cs1—O12A^iv	3.202 (2)	N2B—H22B	0.82 (3)
Cs1—O41B^iv	3.326 (2)	C1A—C2A	1.419 (4)
Cs2—O1W	3.248 (3)	C1A—C6A	1.391 (4)
Cs2—O2W	3.108 (3)	C1A—C11A	1.519 (4)
Cs2—O41A	3.136 (2)	C1B—C2B	1.411 (4)
Cs2—N2B	3.352 (3)	C1B—C6B	1.395 (4)
Cs2—O42B^v	3.114 (2)	C1B—C11B	1.519 (4)
Cs2—O12B^vi	3.090 (2)	C2A—C3A	1.406 (4)
Cs2—O42B^iv	3.181 (2)	C2B—C3B	1.405 (4)
O11A—C11A	1.254 (3)	C3A—C4A	1.367 (4)
O11B—C11B	1.252 (3)	C3B—C4B	1.368 (4)
O12A—C11A	1.263 (3)	C4A—C5A	1.389 (4)
O12B—C11B	1.269 (4)	C4B—C5B	1.391 (4)
O41A—N4A	1.219 (3)	C5A—C6A	1.378 (4)
O41B—N4B	1.212 (3)	C5B—C6B	1.379 (4)
O42A—N4A	1.233 (4)	C3A—H3A	0.9300
O42B—N4B	1.224 (3)	C3B—H3B	0.9300
O1W—H11W	0.90 (5)	C5A—H5A	0.9300
O1W—H12W	0.85 (4)	C5B—H5B	0.9300
O2W—H21W	0.85 (4)	C6A—H6A	0.9300
O2W—H22W	0.81 (4)	C6B—H6B	0.9300

O1W—Cs1—O2W	94.42 (7)	Cs2^viii—O42B—N4B	111.06 (17)
O1W—Cs1—O42A	56.62 (6)	Cs2^ix—O42B—Cs2^viii	93.23 (6)
O1W—Cs1—O1Wⁱ	100.99 (6)	Cs1—O1W—H12W	134 (3)
O1W—Cs1—O42Aⁱ	136.12 (6)	Cs2—O1W—H11W	86 (2)
O1W—Cs1—O12Aⁱⁱ	122.03 (6)	Cs2—O1W—H12W	100 (3)
O1W—Cs1—O11Bⁱⁱⁱ	136.78 (6)	H11W—O1W—H12W	108 (4)
O1W—Cs1—O12A^iv	71.93 (6)	Cs1^vii—O1W—H11W	126 (3)
O1W—Cs1—O41B^iv	68.98 (7)	Cs1^vii—O1W—H12W	61 (3)
O2W—Cs1—O42A	88.76 (7)	Cs1—O1W—H11W	118 (3)
O1Wⁱ—Cs1—O2W	137.01 (7)	Cs2—O2W—H21W	122 (3)
O2W—Cs1—O42Aⁱ	128.85 (6)	Cs2—O2W—H22W	128 (3)
O2W—Cs1—O12Aⁱⁱ	68.49 (6)	H21W—O2W—H22W	108 (4)
O2W—Cs1—O11Bⁱⁱⁱ	69.14 (6)	Cs1—O2W—H21W	92 (3)
O2W—Cs1—O12A^iv	166.24 (6)	Cs1—O2W—H22W	85 (3)
O2W—Cs1—O41B^iv	70.16 (7)	Cs2—N2B—C2B	139.7 (2)
O1Wⁱ—Cs1—O42A	67.92 (6)	O42A—N4A—C4A	118.1 (2)
O42A—Cs1—O42Aⁱ	121.97 (6)	O41A—N4A—C4A	118.9 (3)
O12Aⁱⁱ—Cs1—O42A	67.64 (5)	O41A—N4A—O42A	123.1 (3)
O11Bⁱⁱⁱ—Cs1—O42A	153.35 (5)	O41B—N4B—C4B	119.1 (2)
O12A^iv—Cs1—O42A	85.11 (5)	O41B—N4B—O42B	123.2 (2)
O41B^iv—Cs1—O42A	119.55 (6)	O42B—N4B—C4B	117.7 (2)
O1Wⁱ—Cs1—O42Aⁱ	54.41 (6)	C2A—N2A—H21A	118 (3)
O1Wⁱ—Cs1—O12Aⁱⁱ	69.30 (5)	H21A—N2A—H22A	110 (3)
O1Wⁱ—Cs1—O11Bⁱⁱⁱ	118.49 (5)	C2A—N2A—H22A	119 (2)
O1Wⁱ—Cs1—O12A^iv	50.69 (5)	Cs2—N2B—H21B	88.6 (19)
O1Wⁱ—Cs1—O41B^iv	152.73 (6)	C2B—N2B—H21B	121 (2)
O12Aⁱⁱ—Cs1—O42Aⁱ	85.71 (5)	C2B—N2B—H22B	116 (2)
O11Bⁱⁱⁱ—Cs1—O42Aⁱ	67.36 (5)	H21B—N2B—H22B	116 (3)
O12A^iv—Cs1—O42Aⁱ	64.51 (5)	Cs2—N2B—H22B	62 (2)
O41B^iv—Cs1—O42Aⁱ	114.78 (6)	C6A—C1A—C11A	118.2 (2)
O11Bⁱⁱⁱ—Cs1—O12Aⁱⁱ	89.79 (5)	C2A—C1A—C6A	118.7 (2)
O12Aⁱⁱ—Cs1—O12A^iv	119.86 (5)	C2A—C1A—C11A	123.1 (2)
O12Aⁱⁱ—Cs1—O41B^iv	137.81 (6)	C2B—C1B—C11B	123.1 (2)
O11Bⁱⁱⁱ—Cs1—O12A^iv	119.61 (5)	C6B—C1B—C11B	117.6 (2)
O11Bⁱⁱⁱ—Cs1—O41B^iv	67.85 (6)	C2B—C1B—C6B	119.3 (2)
O12A^iv—Cs1—O41B^iv	102.33 (6)	N2A—C2A—C1A	122.8 (3)
O1W—Cs2—O2W	97.03 (7)	N2A—C2A—C3A	119.1 (3)
O1W—Cs2—O41A	72.14 (6)	C1A—C2A—C3A	118.1 (2)
O1W—Cs2—N2B	112.82 (6)	N2B—C2B—C1B	122.3 (3)
O1W—Cs2—O42B^v	154.92 (6)	C1B—C2B—C3B	118.2 (2)
O1W—Cs2—O12B^vi	66.73 (6)	N2B—C2B—C3B	119.5 (3)
O1W—Cs2—O42B^iv	98.84 (6)	C2A—C3A—C4A	120.0 (3)
O2W—Cs2—O41A	68.26 (7)	C2B—C3B—C4B	119.7 (3)
O2W—Cs2—N2B	126.34 (7)	C3A—C4A—C5A	123.4 (3)
O2W—Cs2—O42B^v	62.78 (7)	N4A—C4A—C3A	118.3 (2)
O2W—Cs2—O12B^vi	130.43 (7)	N4A—C4A—C5A	118.3 (3)
O2W—Cs2—O42B^iv	66.20 (7)	C3B—C4B—C5B	123.8 (3)
O41A—Cs2—N2B	79.54 (7)	N4B—C4B—C5B	118.3 (2)
O41A—Cs2—O42B^v	85.88 (6)	N4B—C4B—C3B	117.9 (2)
O12B^vi—Cs2—O41A	136.14 (6)	C4A—C5A—C6A	116.1 (3)
O41A—Cs2—O42B^iv	131.93 (6)	C4B—C5B—C6B	116.0 (2)
O42B^v—Cs2—N2B	73.49 (7)	C1A—C6A—C5A	123.6 (3)
O12B^vi—Cs2—N2B	102.64 (6)	C1B—C6B—C5B	123.1 (2)
O42B^iv—Cs2—N2B	142.10 (7)	O11A—C11A—O12A	123.9 (3)
O12B^vi—Cs2—O42B^v	137.32 (6)	O11A—C11A—C1A	117.7 (2)
O42B^v—Cs2—O42B^iv	86.77 (6)	O12A—C11A—C1A	118.4 (2)
O12B^vi—Cs2—O42B^iv	70.52 (6)	O11B—C11B—C1B	117.5 (2)
Cs1—O1W—Cs2	84.10 (5)	O12B—C11B—C1B	117.8 (2)
Cs1—O1W—Cs1^vii	90.76 (6)	O11B—C11B—O12B	124.7 (3)
Cs1^vii—O1W—Cs2	145.43 (8)	C2A—C3A—H3A	120.00
Cs1—O2W—Cs2	84.13 (7)	C4A—C3A—H3A	120.00
Cs1ⁱⁱⁱ—O11B—C11B	122.77 (17)	C2B—C3B—H3B	120.00
Cs1ⁱⁱ—O12A—C11A	121.78 (17)	C4B—C3B—H3B	120.00
Cs1^viii—O12A—C11A	143.20 (18)	C4A—C5A—H5A	122.00
Cs1ⁱⁱ—O12A—Cs1^viii	95.00 (5)	C6A—C5A—H5A	122.00
Cs2^vi—O12B—C11B	128.65 (17)	C4B—C5B—H5B	122.00
Cs2—O41A—N4A	128.40 (18)	C6B—C5B—H5B	122.00
Cs1^viii—O41B—N4B	141.79 (19)	C1A—C6A—H6A	118.00
Cs1—O42A—N4A	120.36 (17)	C5A—C6A—H6A	118.00
Cs1—O42A—Cs1^vii	91.71 (6)	C1B—C6B—H6B	118.00
Cs1^vii—O42A—N4A	139.56 (16)	C5B—C6B—H6B	118.00
Cs2^ix—O42B—N4B	147.4 (2)

O2W—Cs1—O1W—Cs2	−4.20 (7)	O1W—Cs2—N2B—C2B	−161.7 (3)
O2W—Cs1—O1W—Cs1^vii	141.55 (7)	O2W—Cs2—N2B—C2B	−43.4 (3)
O42A—Cs1—O1W—Cs2	−89.79 (7)	O41A—Cs2—N2B—C2B	−96.3 (3)
O42A—Cs1—O1W—Cs1^vii	55.96 (6)	O42B^v—Cs2—N2B—C2B	−7.5 (3)
O1Wⁱ—Cs1—O1W—Cs2	−143.87 (6)	O12B^vi—Cs2—N2B—C2B	128.5 (3)
O1Wⁱ—Cs1—O1W—Cs1^vii	1.88 (7)	O42B^iv—Cs2—N2B—C2B	54.0 (4)
O42Aⁱ—Cs1—O1W—Cs2	166.94 (6)	O1W—Cs2—O42B^v—N4B^v	116.9 (3)
O42Aⁱ—Cs1—O1W—Cs1^vii	−47.32 (10)	O1W—Cs2—O42B^v—Cs2ⁱⁱⁱ	−104.03 (13)
O12Aⁱⁱ—Cs1—O1W—Cs2	−71.52 (7)	O2W—Cs2—O42B^v—N4B^v	156.1 (3)
O12Aⁱⁱ—Cs1—O1W—Cs1^vii	74.23 (7)	O2W—Cs2—O42B^v—Cs2ⁱⁱⁱ	−64.82 (8)
O11Bⁱⁱⁱ—Cs1—O1W—Cs2	59.73 (9)	O41A—Cs2—O42B^v—N4B^v	88.5 (3)
O11Bⁱⁱⁱ—Cs1—O1W—Cs1^vii	−154.52 (6)	O41A—Cs2—O42B^v—Cs2ⁱⁱⁱ	−132.46 (7)
O12A^iv—Cs1—O1W—Cs2	174.05 (7)	N2B—Cs2—O42B^v—N4B^v	8.2 (3)
O12A^iv—Cs1—O1W—Cs1^vii	−40.21 (5)	N2B—Cs2—O42B^v—Cs2ⁱⁱⁱ	147.25 (8)
O41B^iv—Cs1—O1W—Cs2	62.57 (6)	O1W—Cs2—O12B^vi—C11B^vi	33.6 (2)
O41B^iv—Cs1—O1W—Cs1^vii	−151.68 (7)	O2W—Cs2—O12B^vi—C11B^vi	−45.3 (2)
O1W—Cs1—O2W—Cs2	4.39 (7)	O41A—Cs2—O12B^vi—C11B^vi	55.3 (2)
O42A—Cs1—O2W—Cs2	60.77 (6)	N2B—Cs2—O12B^vi—C11B^vi	143.3 (2)
O1Wⁱ—Cs1—O2W—Cs2	115.69 (8)	O1W—Cs2—O42B^iv—Cs2ⁱⁱⁱ	155.41 (6)
O42Aⁱ—Cs1—O2W—Cs2	−167.73 (5)	O1W—Cs2—O42B^iv—N4B^iv	−2.3 (2)
O12Aⁱⁱ—Cs1—O2W—Cs2	127.16 (8)	O2W—Cs2—O42B^iv—Cs2ⁱⁱⁱ	61.58 (7)
O11Bⁱⁱⁱ—Cs1—O2W—Cs2	−134.45 (8)	O2W—Cs2—O42B^iv—N4B^iv	−96.2 (2)
O41B^iv—Cs1—O2W—Cs2	−61.39 (7)	O41A—Cs2—O42B^iv—Cs2ⁱⁱⁱ	81.52 (9)
O1W—Cs1—O42A—N4A	94.23 (19)	O41A—Cs2—O42B^iv—N4B^iv	−76.2 (2)
O1W—Cs1—O42A—Cs1^vii	−59.92 (6)	N2B—Cs2—O42B^iv—Cs2ⁱⁱⁱ	−57.61 (13)
O2W—Cs1—O42A—N4A	−1.89 (19)	N2B—Cs2—O42B^iv—N4B^iv	144.65 (17)
O2W—Cs1—O42A—Cs1^vii	−156.03 (6)	Cs1ⁱⁱⁱ—O11B—C11B—O12B	57.9 (3)
O1Wⁱ—Cs1—O42A—N4A	−144.9 (2)	Cs1ⁱⁱⁱ—O11B—C11B—C1B	−123.6 (2)
O1Wⁱ—Cs1—O42A—Cs1^vii	60.99 (5)	Cs1ⁱⁱ—O12A—C11A—O11A	−68.7 (3)
O42Aⁱ—Cs1—O42A—N4A	−138.46 (18)	Cs1ⁱⁱ—O12A—C11A—C1A	111.4 (2)
O42Aⁱ—Cs1—O42A—Cs1^vii	67.40 (7)	Cs1^viii—O12A—C11A—O11A	113.3 (3)
O12Aⁱⁱ—Cs1—O42A—N4A	−69.08 (18)	Cs1^viii—O12A—C11A—C1A	−66.7 (4)
O12Aⁱⁱ—Cs1—O42A—Cs1^vii	136.78 (7)	Cs2^vi—O12B—C11B—O11B	55.1 (4)
O11Bⁱⁱⁱ—Cs1—O42A—N4A	−35.0 (3)	Cs2^vi—O12B—C11B—C1B	−123.3 (2)
O11Bⁱⁱⁱ—Cs1—O42A—Cs1^vii	170.83 (9)	Cs2—O41A—N4A—O42A	−54.8 (3)
O12A^iv—Cs1—O42A—N4A	165.78 (19)	Cs2—O41A—N4A—C4A	126.4 (2)
O12A^iv—Cs1—O42A—Cs1^vii	11.64 (5)	Cs1^viii—O41B—N4B—O42B	−40.7 (4)
O41B^iv—Cs1—O42A—N4A	64.4 (2)	Cs1^viii—O41B—N4B—C4B	140.9 (2)
O41B^iv—Cs1—O42A—Cs1^vii	−89.77 (7)	Cs1—O42A—N4A—O41A	−10.5 (3)
O1W—Cs1—O1Wⁱ—Cs1ⁱ	161.87 (6)	Cs1—O42A—N4A—C4A	168.30 (16)
O1W—Cs1—O1Wⁱ—Cs2ⁱ	−117.46 (12)	Cs1^vii—O42A—N4A—O41A	127.3 (2)
O2W—Cs1—O1Wⁱ—Cs1ⁱ	53.01 (11)	Cs1^vii—O42A—N4A—C4A	−53.9 (4)
O2W—Cs1—O1Wⁱ—Cs2ⁱ	133.68 (12)	Cs2^ix—O42B—N4B—O41B	110.6 (3)
O42A—Cs1—O1Wⁱ—Cs1ⁱ	115.00 (7)	Cs2^ix—O42B—N4B—C4B	−70.9 (4)
O42A—Cs1—O1Wⁱ—Cs2ⁱ	−164.33 (14)	Cs2^viii—O42B—N4B—O41B	−24.9 (3)
O1W—Cs1—O42Aⁱ—Cs1ⁱ	121.80 (8)	Cs2^viii—O42B—N4B—C4B	153.57 (17)
O1W—Cs1—O42Aⁱ—N4Aⁱ	−22.7 (3)	Cs2—N2B—C2B—C1B	−58.5 (4)
O2W—Cs1—O42Aⁱ—Cs1ⁱ	−69.58 (9)	Cs2—N2B—C2B—C3B	120.3 (3)
O2W—Cs1—O42Aⁱ—N4Aⁱ	145.9 (3)	O41A—N4A—C4A—C3A	0.2 (4)
O42A—Cs1—O42Aⁱ—Cs1ⁱ	48.46 (7)	O41A—N4A—C4A—C5A	178.8 (2)
O42A—Cs1—O42Aⁱ—N4Aⁱ	−96.1 (3)	O42A—N4A—C4A—C3A	−178.6 (2)
O1W—Cs1—O12Aⁱⁱ—Cs1ⁱ	−131.61 (6)	O42A—N4A—C4A—C5A	−0.1 (4)
O1W—Cs1—O12Aⁱⁱ—C11Aⁱⁱ	47.2 (2)	O41B—N4B—C4B—C3B	−8.7 (4)
O2W—Cs1—O12Aⁱⁱ—Cs1ⁱ	146.96 (8)	O41B—N4B—C4B—C5B	171.9 (3)
O2W—Cs1—O12Aⁱⁱ—C11Aⁱⁱ	−34.2 (2)	O42B—N4B—C4B—C3B	172.7 (3)
O42A—Cs1—O12Aⁱⁱ—Cs1ⁱ	−115.17 (7)	O42B—N4B—C4B—C5B	−6.7 (4)
O42A—Cs1—O12Aⁱⁱ—C11Aⁱⁱ	63.7 (2)	C6A—C1A—C2A—N2A	180.0 (3)
O1W—Cs1—O11Bⁱⁱⁱ—C11Bⁱⁱⁱ	−43.5 (2)	C6A—C1A—C2A—C3A	−1.6 (4)
O2W—Cs1—O11Bⁱⁱⁱ—C11Bⁱⁱⁱ	30.0 (2)	C11A—C1A—C2A—N2A	0.8 (4)
O42A—Cs1—O11Bⁱⁱⁱ—C11Bⁱⁱⁱ	65.8 (2)	C11A—C1A—C2A—C3A	179.2 (2)
O1W—Cs1—O12A^iv—Cs1^vii	44.36 (6)	C2A—C1A—C6A—C5A	−0.1 (4)
O1W—Cs1—O12A^iv—C11A^iv	−134.0 (3)	C11A—C1A—C6A—C5A	179.1 (2)
O42A—Cs1—O12A^iv—Cs1^vii	−12.08 (5)	C2A—C1A—C11A—O11A	179.7 (2)
O42A—Cs1—O12A^iv—C11A^iv	169.6 (3)	C2A—C1A—C11A—O12A	−0.4 (4)
O1W—Cs1—O41B^iv—N4B^iv	−117.3 (3)	C6A—C1A—C11A—O11A	0.5 (4)
O2W—Cs1—O41B^iv—N4B^iv	−14.2 (3)	C6A—C1A—C11A—O12A	−179.6 (3)
O42A—Cs1—O41B^iv—N4B^iv	−90.9 (3)	C6B—C1B—C2B—N2B	179.9 (3)
O2W—Cs2—O1W—Cs1	4.49 (7)	C6B—C1B—C2B—C3B	1.1 (4)
O2W—Cs2—O1W—Cs1^vii	−78.23 (13)	C11B—C1B—C2B—N2B	0.1 (4)
O41A—Cs2—O1W—Cs1	68.91 (6)	C11B—C1B—C2B—C3B	−178.6 (3)
O41A—Cs2—O1W—Cs1^vii	−13.81 (11)	C2B—C1B—C6B—C5B	1.0 (4)
N2B—Cs2—O1W—Cs1	138.88 (6)	C11B—C1B—C6B—C5B	−179.2 (3)
N2B—Cs2—O1W—Cs1^vii	56.16 (14)	C2B—C1B—C11B—O11B	177.5 (3)
O42B^v—Cs2—O1W—Cs1	38.99 (17)	C2B—C1B—C11B—O12B	−3.9 (4)
O42B^v—Cs2—O1W—Cs1^vii	−43.7 (2)	C6B—C1B—C11B—O11B	−2.2 (4)
O12B^vi—Cs2—O1W—Cs1	−126.67 (7)	C6B—C1B—C11B—O12B	176.3 (3)
O12B^vi—Cs2—O1W—Cs1^vii	150.61 (14)	N2A—C2A—C3A—C4A	−179.3 (3)
O42B^iv—Cs2—O1W—Cs1	−62.41 (7)	C1A—C2A—C3A—C4A	2.2 (4)
O42B^iv—Cs2—O1W—Cs1^vii	−145.14 (12)	N2B—C2B—C3B—C4B	179.1 (3)
O1W—Cs2—O2W—Cs1	−4.31 (7)	C1B—C2B—C3B—C4B	−2.2 (4)
O41A—Cs2—O2W—Cs1	−71.86 (7)	C2A—C3A—C4A—N4A	177.3 (2)
N2B—Cs2—O2W—Cs1	−129.46 (7)	C2A—C3A—C4A—C5A	−1.1 (4)
O42B^v—Cs2—O2W—Cs1	−168.65 (9)	C2B—C3B—C4B—N4B	−178.2 (2)
O12B^vi—Cs2—O2W—Cs1	60.98 (10)	C2B—C3B—C4B—C5B	1.2 (4)
O42B^iv—Cs2—O2W—Cs1	92.29 (7)	N4A—C4A—C5A—C6A	−179.1 (2)
O1W—Cs2—O41A—N4A	16.2 (2)	C3A—C4A—C5A—C6A	−0.7 (4)
O2W—Cs2—O41A—N4A	121.7 (2)	N4B—C4B—C5B—C6B	−179.7 (2)
N2B—Cs2—O41A—N4A	−102.1 (2)	C3B—C4B—C5B—C6B	1.0 (4)
O42B^v—Cs2—O41A—N4A	−176.1 (2)	C4A—C5A—C6A—C1A	1.3 (4)
O12B^vi—Cs2—O41A—N4A	−4.7 (3)	C4B—C5B—C6B—C1B	−2.1 (4)
O42B^iv—Cs2—O41A—N4A	102.0 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H22A···O11B^v	0.88 (3)	2.35 (3)	3.132 (3)	148 (3)
N2A—H21A···O12A	0.86 (4)	2.06 (4)	2.685 (4)	129 (3)
N2B—H21B···O11A^x	0.90 (3)	2.08 (3)	2.848 (3)	143 (3)
N2B—H22B···O12B	0.82 (3)	2.04 (3)	2.657 (4)	131 (3)
O1W—H11W···O11B^vi	0.90 (5)	1.88 (4)	2.768 (3)	169 (3)
O1W—H12W···O12A^x	0.85 (4)	1.99 (4)	2.839 (3)	180 (5)
O2W—H21W···O11Aⁱⁱ	0.85 (4)	2.01 (4)	2.851 (4)	179 (6)
O2W—H22W···O12Bⁱⁱⁱ	0.81 (4)	1.96 (4)	2.769 (4)	172 (4)
C6A—H6A···O11A	0.93	2.41	2.762 (3)	102
C6B—H6B···O11B	0.93	2.40	2.746 (3)	102

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

Experimental details

Crystal data
Chemical formula	[Cs₂(C₇H₅N₂O₄)₂(H₂O)₂]
M_r	664.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	15.3615 (3), 6.9573 (2), 18.3714 (4)
β (°)	97.903 (2)
V (Å³)	1944.79 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.81
Crystal size (mm)	0.40 × 0.30 × 0.10

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.411, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	14204, 4555, 3818
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.678

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.049, 1.02
No. of reflections	4555
No. of parameters	303
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.90

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).

Selected bond lengths (Å) top

Cs1—O1W	3.177 (2)	Cs1—O41B^iv	3.326 (2)
Cs1—O2W	3.311 (3)	Cs2—O1W	3.248 (3)
Cs1—O42A	3.271 (2)	Cs2—O2W	3.108 (3)
Cs1—O1Wⁱ	3.414 (3)	Cs2—O41A	3.136 (2)
Cs1—O42Aⁱ	3.271 (2)	Cs2—N2B	3.352 (3)
Cs1—O12Aⁱⁱ	3.165 (2)	Cs2—O42B^v	3.114 (2)
Cs1—O11Bⁱⁱⁱ	3.166 (2)	Cs2—O12B^vi	3.090 (2)
Cs1—O12A^iv	3.202 (2)	Cs2—O42B^iv	3.181 (2)

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