Poly[μ3-aqua-aqua-μ5-(4-nitro­benzoato)-caesium]

Smith, G.

doi:10.1107/S1600536813030638

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Pages m664-m665

doi:10.1107/S1600536813030638

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Poly[μ₃-aqua-aqua-μ₅-(4-nitrobenzoato)-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 3 November 2013; accepted 7 November 2013; online 16 November 2013)

In the structure of the title complex, [Cs(C₇H₄NO₂)(H₂O)₂]_n, the caesium salt of 4-nitrobenzoic acid, the irregular CsO₉ coordination sphere comprises three bridging nitro O-atom donors, a bidentate carboxylate O,O′-chelate interaction, a triple-bridging water molecule and a monodentate water molecule. A three-dimensional framework polymer is generated, within which there are water–carboxylate O—H⋯O and water–water O—H⋯O hydrogen-bonding interactions.

CCDC reference: 970813

Related literature

For structures of alkali metal salts of 4-nitrobenzoic acid, see: Turowska-Tyrk et al. (1988 ) (Na); Srivastava & Speakman (1961 ) (K). For the structures of Na, K and Cs complexes with 4-nitroanthranilic acid, see: Smith & Wermuth (2011 ); Smith (2013 ). For the structures of the 4-nitrobenzoic acid polymorphs, see: Groth (1980 ); Tonogaki et al. (1993 ); Bolte (2009 ).

Experimental

Crystal data

[Cs(C₇H₄NO₂)(H₂O)₂]
M_r = 335.05
Monoclinic, P 2₁ /n
a = 6.0700 (3) Å
b = 7.1073 (4) Å
c = 24.2183 (13) Å
β = 94.035 (5)°
V = 1042.22 (10) Å³
Z = 4
Mo Kα radiation
μ = 3.56 mm⁻¹
T = 200 K
0.28 × 0.18 × 0.05 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.604, T_max = 0.980
6334 measured reflections
2057 independent reflections
1836 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.074
S = 1.15
2057 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Selected bond lengths (Å)

Cs1—O1W	3.126 (3)
Cs1—O2W	3.253 (3)
Cs1—O41	3.244 (4)
Cs1—O2Wⁱ	3.220 (3)
Cs1—O42ⁱ	3.248 (4)
Cs1—O11ⁱⁱ	3.215 (3)
Cs1—O12ⁱⁱ	3.338 (4)
Cs1—O2Wⁱⁱⁱ	3.047 (4)
Cs1—O41ⁱⁱⁱ	3.310 (4)
Symmetry codes: (i) x-1, y, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O12^iv	0.82	1.88	2.694 (5)	174
O1W—H12W⋯O11^v	0.93	1.81	2.728 (4)	173
O2W—H21W⋯O1W^vi	0.79	1.99	2.749 (5)	162
O2W—H22W⋯O11^iv	0.84	1.91	2.753 (5)	174
Symmetry codes: (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) -x+1, -y+1, -z+1.

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.

Supporting information

CCDC reference: 970813

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813030638/lh5666sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030638/lh5666Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813030638/lh5666Isup3.cml

checkCIF report

Comment top

4-Nitrobenzoic acid (PNBA) has proved to be a useful ligand for the preparation of metal complexes, which are mainly monomeric but rarely involve the nitro group in coordination. With the known alkali metal salts of PNBA, the sodium salt (a trihydrate) (Turowska-Tyrk et al., 1988) and the potassium salt (a 1:1 salt-acid adduct) (Srivastava & Speakman, 1961), coordination polymeric structures are formed, but the structures of the rubidium and caesium salts have not been reported. The reaction of 4-nitrobenzoic acid with caesium hydroxide in aqueous ethanol afforded good crystals of the title Cs complex, [Cs(C₇H₄NO₂)(H₂O)₂]_n and the structure is reported herein.

In this structure (Fig. 1), the irregular CsO₉ coordinate polyhedron comprises a bidentate carboxylate O,O'-chelate interaction, three O-donors from an O,O'-bridging nitro group, three O donors from a triple-bridging water molecule (O2W) and a monodentate water molecule (O1W) [Cs—O, 3.047 (4)–3.338 (4) Å] (Table 1). The bridging extensions in the two-dimensional sheet substructures which extend along the (0 0 1) plane include a centrosymmetric water–carboxyl quadruple cage (Fig. 2) (Cs···Csⁱⁱⁱ = 4.2610 (6) Å] [for symmetry code (iii), see Table 2]. The p-related carboxyl and nitro substituent groups of the PNBA ligand link the sheets across c, and generate an overall a three-dimensional coordination polymer (Fig. 3). This type of structure extension through the p-related benzoate carboxyl and nitro functional groups is similar to that found in other alkali metal complexes with the 4-nitroanthranilate salts of sodium (a dihydrate) and potassium (a monohydrate) (Smith, 2013), and caesium (a monohydrate) (Smith & Wermuth, 2011).

The crystal structure of the title complex polymer is stabilized by intra-sheet water O—H···O_carboxyl and O—H···O_water hydrogen-bonding interactions (Table 2). No inter-ring π–π interactions are present [minimun ring centroid separation 4.643 (2) Å]. The PABA ligand in the complex is essentially planar [torsion angles C2—C1—C11—O12 = 177.9 (4)° (carboxyl) and C3—C4—N41—O41 = 177.5 (4)° (nitro)]. This conformation is similar to that found in both monoclinic polymorphs of the parent acid [Tonogaki et al., 1993; Groth, 1980; Bolte, 2009].

Related literature top

For structures of alkali metal salts of 4-nitrobenzoic acid, see: Turowska-Tyrk et al. (1988) (Na); Srivastava & Speakman (1961) (K). For the structures of Na, K and Cs complexes with 4-nitroanthranilic acid, see: Smith & Wermuth (2011); Smith (2013). For the structures of the 4-nitrobenzoic acid polymorphs, see: Groth (1980); Tonogaki et al. (1993); Bolte (2009).

Experimental top

The title compound was synthesized by heating together for 10 minutes, 0.5 mmol of 4-nitrobenzoic acid and 0.5 mmol of CsOH in 15 ml of 10% ethanol–water. Partial room temperature evaporation of the solution gave colourless elongated crystal plates of the title complex from which a specimen was cleaved for the X-ray analysis.

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

	Fig. 1. The molecular configuration and atom-numbering scheme for the coordination polyhedron of title complex, with non-H atoms drawn as 40% probability displacement ellipsoids. For symmetry codes: see Table 1.
	Fig. 2. A partial expansion of the CsO₉ coordination sphere in the polymeric structure. For symmetry codes: (vii) x + 1, y, z; (viii) -x, -y, -z + 1. For other symmetry codes, see Fig. 1 and Table 1.
	Fig. 3. The packing of the structure in the unit cell viewed along a. Hydrogen-bonding associations are shown as dashed lines.

Poly[µ₃-aqua-aqua-µ₅-(4-nitrobenzoato)-caesium] top

Crystal data top

[Cs(C₇H₄NO₂)(H₂O)₂]	F(000) = 640
M_r = 335.05	D_x = 2.135 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2366 reflections
a = 6.0700 (3) Å	θ = 3.5–28.1°
b = 7.1073 (4) Å	µ = 3.56 mm⁻¹
c = 24.2183 (13) Å	T = 200 K
β = 94.035 (5)°	Plate, colourless
V = 1042.22 (10) Å³	0.28 × 0.18 × 0.05 mm
Z = 4

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	2057 independent reflections
Radiation source: Enhance (Mo) X-ray source	1836 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −8→8
T_min = 0.604, T_max = 0.980	l = −22→29
6334 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0285P)² + 0.878P] where P = (F_o² + 2F_c²)/3
2057 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.56 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Cs(C₇H₄NO₂)(H₂O)₂]	V = 1042.22 (10) Å³
M_r = 335.05	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.0700 (3) Å	µ = 3.56 mm⁻¹
b = 7.1073 (4) Å	T = 200 K
c = 24.2183 (13) Å	0.28 × 0.18 × 0.05 mm
β = 94.035 (5)°

Data collection top

Oxford Diffraction Gemini-S CCD-detector diffractometer	2057 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	1836 reflections with I > 2σ(I)
T_min = 0.604, T_max = 0.980	R_int = 0.036
6334 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.15	Δρ_max = 0.56 e Å⁻³
2057 reflections	Δρ_min = −0.67 e Å⁻³
136 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	0.25378 (4)	0.19824 (4)	0.47189 (1)	0.0259 (1)
O1W	0.2785 (5)	0.5049 (5)	0.56462 (14)	0.0354 (11)
O2W	0.7695 (5)	0.2283 (5)	0.51753 (15)	0.0347 (11)
O11	0.3802 (5)	0.0475 (5)	0.10793 (14)	0.0333 (11)
O12	0.0968 (5)	−0.0945 (5)	0.14338 (15)	0.0400 (11)
O41	0.6184 (7)	−0.0192 (5)	0.40379 (16)	0.0467 (14)
O42	0.9117 (7)	0.0828 (7)	0.36824 (17)	0.0576 (16)
N41	0.7213 (7)	0.0261 (6)	0.36407 (17)	0.0311 (12)
C1	0.4023 (7)	−0.0137 (5)	0.20429 (19)	0.0189 (11)
C2	0.6135 (7)	0.0617 (6)	0.2120 (2)	0.0236 (14)
C3	0.7195 (7)	0.0745 (6)	0.26440 (19)	0.0235 (14)
C4	0.6093 (7)	0.0113 (6)	0.30818 (19)	0.0229 (14)
C5	0.4009 (7)	−0.0646 (6)	0.30250 (19)	0.0250 (14)
C6	0.2985 (7)	−0.0777 (6)	0.25023 (19)	0.0223 (14)
C11	0.2830 (7)	−0.0201 (6)	0.1477 (2)	0.0252 (14)
H2	0.68620	0.10490	0.18090	0.0280*
H3	0.86400	0.12560	0.26980	0.0280*
H5	0.32940	−0.10700	0.33390	0.0300*
H6	0.15490	−0.13100	0.24530	0.0270*
H11W	0.37890	0.53710	0.58680	0.0530*
H12W	0.14960	0.48830	0.58230	0.0530*
H21W	0.72670	0.30190	0.49470	0.0520*
H22W	0.79800	0.29200	0.54650	0.0520*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.0259 (2)	0.0272 (2)	0.0240 (2)	0.0000 (1)	−0.0015 (1)	0.0013 (1)
O1W	0.0348 (18)	0.052 (2)	0.0189 (19)	−0.0046 (17)	−0.0014 (14)	0.0006 (16)
O2W	0.044 (2)	0.0296 (17)	0.030 (2)	−0.0030 (15)	−0.0003 (16)	−0.0028 (15)
O11	0.0334 (18)	0.049 (2)	0.0173 (19)	−0.0022 (16)	0.0010 (14)	0.0089 (16)
O12	0.0335 (19)	0.055 (2)	0.030 (2)	−0.0104 (18)	−0.0092 (15)	0.0061 (18)
O41	0.065 (3)	0.056 (2)	0.018 (2)	0.002 (2)	−0.0040 (18)	0.0036 (18)
O42	0.049 (2)	0.085 (3)	0.036 (3)	−0.015 (2)	−0.0171 (19)	−0.007 (2)
N41	0.042 (2)	0.033 (2)	0.017 (2)	0.0051 (19)	−0.0076 (19)	−0.0057 (18)
C1	0.020 (2)	0.0163 (19)	0.020 (2)	0.0015 (17)	−0.0021 (18)	−0.0017 (18)
C2	0.027 (2)	0.021 (2)	0.023 (3)	−0.0022 (18)	0.0028 (19)	0.0012 (19)
C3	0.023 (2)	0.024 (2)	0.023 (3)	−0.0029 (19)	−0.0008 (19)	−0.0037 (19)
C4	0.028 (2)	0.020 (2)	0.020 (3)	0.0046 (19)	−0.0041 (19)	−0.0051 (18)
C5	0.034 (2)	0.024 (2)	0.018 (3)	0.001 (2)	0.008 (2)	0.0026 (19)
C6	0.023 (2)	0.021 (2)	0.023 (3)	−0.0010 (18)	0.0028 (18)	0.0009 (19)
C11	0.028 (2)	0.025 (2)	0.022 (3)	0.005 (2)	−0.003 (2)	0.002 (2)

Geometric parameters (Å, º) top

Cs1—O1W	3.126 (3)	O2W—H21W	0.7900
Cs1—O2W	3.253 (3)	O2W—H22W	0.8400
Cs1—O41	3.244 (4)	N41—C4	1.475 (6)
Cs1—O2Wⁱ	3.220 (3)	C1—C2	1.390 (6)
Cs1—O42ⁱ	3.248 (4)	C1—C6	1.393 (6)
Cs1—O11ⁱⁱ	3.215 (3)	C1—C11	1.505 (7)
Cs1—O12ⁱⁱ	3.338 (4)	C2—C3	1.385 (7)
Cs1—O2Wⁱⁱⁱ	3.047 (4)	C3—C4	1.369 (6)
Cs1—O41ⁱⁱⁱ	3.310 (4)	C4—C5	1.373 (6)
O11—C11	1.260 (6)	C5—C6	1.374 (6)
O12—C11	1.246 (5)	C2—H2	0.9500
O41—N41	1.226 (6)	C3—H3	0.9500
O42—N41	1.221 (6)	C5—H5	0.9500
O1W—H11W	0.8200	C6—H6	0.9500
O1W—H12W	0.9300

O1W—Cs1—O2W	73.36 (8)	Cs1^v—O12—C11	87.7 (3)
O1W—Cs1—O41	134.24 (9)	Cs1—O41—N41	132.6 (3)
O1W—Cs1—O2Wⁱ	72.89 (8)	Cs1—O41—Cs1ⁱⁱⁱ	81.10 (9)
O1W—Cs1—O42ⁱ	136.65 (10)	Cs1ⁱⁱⁱ—O41—N41	135.6 (3)
O1W—Cs1—O11ⁱⁱ	83.74 (9)	Cs1^iv—O42—N41	134.2 (3)
O1W—Cs1—O12ⁱⁱ	106.92 (9)	H11W—O1W—H12W	110.00
O1W—Cs1—O2Wⁱⁱⁱ	129.32 (9)	Cs1—O1W—H11W	132.00
O1W—Cs1—O41ⁱⁱⁱ	67.55 (9)	Cs1—O1W—H12W	104.00
O2W—Cs1—O41	61.92 (9)	Cs1^iv—O2W—H21W	94.00
O2W—Cs1—O2Wⁱ	139.38 (9)	Cs1—O2W—H21W	63.00
O2W—Cs1—O42ⁱ	145.77 (10)	Cs1—O2W—H22W	117.00
O2W—Cs1—O11ⁱⁱ	110.50 (8)	H21W—O2W—H22W	105.00
O2W—Cs1—O12ⁱⁱ	86.77 (8)	Cs1ⁱⁱⁱ—O2W—H22W	118.00
O2W—Cs1—O2Wⁱⁱⁱ	94.93 (9)	Cs1ⁱⁱⁱ—O2W—H21W	135.00
O2W—Cs1—O41ⁱⁱⁱ	63.75 (10)	Cs1^iv—O2W—H22W	101.00
O2Wⁱ—Cs1—O41	151.44 (9)	O41—N41—O42	123.6 (4)
O41—Cs1—O42ⁱ	84.76 (11)	O42—N41—C4	118.2 (4)
O11ⁱⁱ—Cs1—O41	102.41 (9)	O41—N41—C4	118.3 (4)
O12ⁱⁱ—Cs1—O41	63.24 (9)	C2—C1—C11	120.9 (4)
O2Wⁱⁱⁱ—Cs1—O41	66.80 (9)	C2—C1—C6	118.9 (4)
O41—Cs1—O41ⁱⁱⁱ	98.90 (10)	C6—C1—C11	120.1 (4)
O2Wⁱ—Cs1—O42ⁱ	74.49 (10)	C1—C2—C3	120.9 (4)
O2Wⁱ—Cs1—O11ⁱⁱ	87.52 (8)	C2—C3—C4	117.9 (4)
O2Wⁱ—Cs1—O12ⁱⁱ	124.49 (8)	C3—C4—C5	123.3 (4)
O2Wⁱ—Cs1—O2Wⁱⁱⁱ	89.33 (9)	N41—C4—C3	118.0 (4)
O2Wⁱ—Cs1—O41ⁱⁱⁱ	82.79 (10)	N41—C4—C5	118.8 (4)
O11ⁱⁱ—Cs1—O42ⁱ	67.02 (11)	C4—C5—C6	118.2 (4)
O12ⁱⁱ—Cs1—O42ⁱ	70.23 (10)	C1—C6—C5	120.9 (4)
O2Wⁱⁱⁱ—Cs1—O42ⁱ	77.45 (11)	O11—C11—O12	124.7 (4)
O41ⁱⁱⁱ—Cs1—O42ⁱ	134.58 (11)	O11—C11—C1	117.6 (4)
O11ⁱⁱ—Cs1—O12ⁱⁱ	39.52 (8)	O12—C11—C1	117.7 (4)
O2Wⁱⁱⁱ—Cs1—O11ⁱⁱ	143.86 (9)	C1—C2—H2	120.00
O11ⁱⁱ—Cs1—O41ⁱⁱⁱ	151.25 (9)	C3—C2—H2	120.00
O2Wⁱⁱⁱ—Cs1—O12ⁱⁱ	121.77 (9)	C2—C3—H3	121.00
O12ⁱⁱ—Cs1—O41ⁱⁱⁱ	150.49 (9)	C4—C3—H3	121.00
O2Wⁱⁱⁱ—Cs1—O41ⁱⁱⁱ	63.27 (9)	C4—C5—H5	121.00
Cs1—O2W—Cs1^iv	139.38 (12)	C6—C5—H5	121.00
Cs1—O2W—Cs1ⁱⁱⁱ	85.07 (8)	C1—C6—H6	119.00
Cs1^iv—O2W—Cs1ⁱⁱⁱ	90.67 (9)	C5—C6—H6	120.00
Cs1^v—O11—C11	93.0 (3)

O1W—Cs1—O2W—Cs1^iv	−145.1 (2)	O1W—Cs1—O12ⁱⁱ—C11ⁱⁱ	−76.3 (3)
O1W—Cs1—O2W—Cs1ⁱⁱⁱ	129.64 (10)	O2W—Cs1—O12ⁱⁱ—C11ⁱⁱ	−147.8 (3)
O41—Cs1—O2W—Cs1^iv	24.89 (16)	O41—Cs1—O12ⁱⁱ—C11ⁱⁱ	152.2 (3)
O41—Cs1—O2W—Cs1ⁱⁱⁱ	−60.38 (9)	O1W—Cs1—O2Wⁱⁱⁱ—Cs1ⁱⁱⁱ	−72.49 (11)
O2Wⁱ—Cs1—O2W—Cs1^iv	−179.98 (15)	O2W—Cs1—O2Wⁱⁱⁱ—Cs1ⁱⁱⁱ	−0.03 (11)
O2Wⁱ—Cs1—O2W—Cs1ⁱⁱⁱ	94.74 (13)	O41—Cs1—O2Wⁱⁱⁱ—Cs1ⁱⁱⁱ	56.56 (9)
O42ⁱ—Cs1—O2W—Cs1^iv	10.4 (3)	O1W—Cs1—O41ⁱⁱⁱ—Cs1ⁱⁱⁱ	−134.37 (10)
O42ⁱ—Cs1—O2W—Cs1ⁱⁱⁱ	−74.9 (2)	O1W—Cs1—O41ⁱⁱⁱ—N41ⁱⁱⁱ	80.5 (4)
O11ⁱⁱ—Cs1—O2W—Cs1^iv	−68.59 (19)	O2W—Cs1—O41ⁱⁱⁱ—Cs1ⁱⁱⁱ	−52.52 (9)
O11ⁱⁱ—Cs1—O2W—Cs1ⁱⁱⁱ	−153.85 (8)	O2W—Cs1—O41ⁱⁱⁱ—N41ⁱⁱⁱ	162.4 (4)
O12ⁱⁱ—Cs1—O2W—Cs1^iv	−36.36 (18)	O41—Cs1—O41ⁱⁱⁱ—Cs1ⁱⁱⁱ	0.00 (10)
O12ⁱⁱ—Cs1—O2W—Cs1ⁱⁱⁱ	−121.63 (9)	O41—Cs1—O41ⁱⁱⁱ—N41ⁱⁱⁱ	−145.1 (4)
O2Wⁱⁱⁱ—Cs1—O2W—Cs1^iv	85.26 (18)	Cs1^v—O11—C11—C1	135.5 (3)
O2Wⁱⁱⁱ—Cs1—O2W—Cs1ⁱⁱⁱ	0.00 (9)	Cs1^v—O11—C11—O12	−43.3 (5)
O41ⁱⁱⁱ—Cs1—O2W—Cs1^iv	142.2 (2)	Cs1^v—O12—C11—O11	41.3 (4)
O41ⁱⁱⁱ—Cs1—O2W—Cs1ⁱⁱⁱ	56.92 (9)	Cs1^v—O12—C11—C1	−137.5 (3)
O1W—Cs1—O41—N41	−79.8 (4)	Cs1—O41—N41—O42	99.6 (6)
O1W—Cs1—O41—Cs1ⁱⁱⁱ	67.23 (13)	Cs1—O41—N41—C4	−80.5 (5)
O2W—Cs1—O41—N41	−93.3 (4)	Cs1ⁱⁱⁱ—O41—N41—O42	−30.2 (7)
O2W—Cs1—O41—Cs1ⁱⁱⁱ	53.78 (9)	Cs1ⁱⁱⁱ—O41—N41—C4	149.7 (3)
O2Wⁱ—Cs1—O41—N41	121.7 (4)	Cs1^iv—O42—N41—O41	−7.8 (8)
O2Wⁱ—Cs1—O41—Cs1ⁱⁱⁱ	−91.25 (19)	Cs1^iv—O42—N41—C4	172.3 (3)
O42ⁱ—Cs1—O41—N41	78.6 (4)	O41—N41—C4—C5	−4.5 (6)
O42ⁱ—Cs1—O41—Cs1ⁱⁱⁱ	−134.36 (10)	O41—N41—C4—C3	175.5 (4)
O11ⁱⁱ—Cs1—O41—N41	13.5 (4)	O42—N41—C4—C5	175.5 (4)
O11ⁱⁱ—Cs1—O41—Cs1ⁱⁱⁱ	160.58 (7)	O42—N41—C4—C3	−4.5 (6)
O12ⁱⁱ—Cs1—O41—N41	8.1 (4)	C11—C1—C2—C3	177.4 (4)
O12ⁱⁱ—Cs1—O41—Cs1ⁱⁱⁱ	155.17 (11)	C2—C1—C6—C5	0.9 (6)
O2Wⁱⁱⁱ—Cs1—O41—N41	157.2 (4)	C6—C1—C2—C3	−0.4 (6)
O2Wⁱⁱⁱ—Cs1—O41—Cs1ⁱⁱⁱ	−55.78 (8)	C6—C1—C11—O12	−4.4 (6)
O41ⁱⁱⁱ—Cs1—O41—N41	−147.1 (4)	C11—C1—C6—C5	−176.9 (4)
O41ⁱⁱⁱ—Cs1—O41—Cs1ⁱⁱⁱ	0.00 (11)	C2—C1—C11—O11	−1.0 (6)
O1W—Cs1—O2Wⁱ—Cs1ⁱ	145.0 (2)	C2—C1—C11—O12	177.9 (4)
O2W—Cs1—O2Wⁱ—Cs1ⁱ	179.97 (17)	C6—C1—C11—O11	176.8 (4)
O41—Cs1—O2Wⁱ—Cs1ⁱ	−51.0 (3)	C1—C2—C3—C4	−0.3 (6)
O1W—Cs1—O42ⁱ—N41ⁱ	−63.5 (5)	C2—C3—C4—C5	0.4 (7)
O2W—Cs1—O42ⁱ—N41ⁱ	151.9 (4)	C2—C3—C4—N41	−179.6 (4)
O41—Cs1—O42ⁱ—N41ⁱ	139.1 (5)	C3—C4—C5—C6	0.1 (7)
O1W—Cs1—O11ⁱⁱ—C11ⁱⁱ	145.7 (3)	N41—C4—C5—C6	−180.0 (4)
O2W—Cs1—O11ⁱⁱ—C11ⁱⁱ	76.1 (3)	C4—C5—C6—C1	−0.7 (6)
O41—Cs1—O11ⁱⁱ—C11ⁱⁱ	11.7 (3)

Symmetry codes: (i) x−1, y, z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y, −z+1; (iv) x+1, y, z; (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···O12^vi	0.82	1.88	2.694 (5)	174
O1W—H12W···O11^vii	0.93	1.81	2.728 (4)	173
O2W—H21W···O1W^viii	0.79	1.99	2.749 (5)	162
O2W—H22W···O11^vi	0.84	1.91	2.753 (5)	174

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

Selected bond lengths (Å) top

Cs1—O1W	3.126 (3)	Cs1—O11ⁱⁱ	3.215 (3)
Cs1—O2W	3.253 (3)	Cs1—O12ⁱⁱ	3.338 (4)
Cs1—O41	3.244 (4)	Cs1—O2Wⁱⁱⁱ	3.047 (4)
Cs1—O2Wⁱ	3.220 (3)	Cs1—O41ⁱⁱⁱ	3.310 (4)
Cs1—O42ⁱ	3.248 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O12^iv	0.82	1.88	2.694 (5)	174
O1W—H12W···O11^v	0.93	1.81	2.728 (4)	173
O2W—H21W···O1W^vi	0.79	1.99	2.749 (5)	162
O2W—H22W···O11^iv	0.84	1.91	2.753 (5)	174

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

Acknowledgements

The author acknowledges financial support from the Science and Engineering Faculty and the University Library, Queensland University of Technology.

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