Poly[μ3-aqua-aqua-μ5-(4-nitro-benzoato)-caesium].

In the structure of the title complex, [Cs(C7H4NO2)(H2O)2] n , the caesium salt of 4-nitro-benzoic acid, the irregular CsO9 coordination sphere comprises three bridging nitro O-atom donors, a bidentate carboxyl-ate O,O'-chelate inter-action, a triple-bridging water mol-ecule and a monodentate water mol-ecule. A three-dimensional framework polymer is generated, within which there are water-carboxyl-ate O-H⋯O and water-water O-H⋯O hydrogen-bonding inter-actions.

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 = 335.05

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.074

S = 1.15

2057 reflections

136 parameters

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.67 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813030638/lh5666sup1.cif

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

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813030638/lh5666Isup3.cml

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

[Cs(C7H4NO2)(H2O)2]	F(000) = 640
Mr = 335.05	Dx = 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

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	Rint = 0.036
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −8→8
Tmin = 0.604, Tmax = 0.980	l = −22→29
6334 measured reflections

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(Fo2) + (0.0285P)2 + 0.878P] where P = (Fo2 + 2Fc2)/3
2057 reflections	(Δ/σ)max = 0.001
136 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.67 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)	Cs1v—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)	Cs1iv—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)	Cs1iv—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)	Cs1iv—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—Cs1iv	139.38 (12)	C6—C5—H5	121.00
Cs1—O2W—Cs1iii	85.07 (8)	C1—C6—H6	119.00
Cs1iv—O2W—Cs1iii	90.67 (9)	C5—C6—H6	120.00
Cs1v—O11—C11	93.0 (3)
O1W—Cs1—O2W—Cs1iv	−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—Cs1iv	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—Cs1iv	−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—Cs1iv	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—Cs1iv	−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—Cs1iv	−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—Cs1iv	85.26 (18)	Cs1v—O11—C11—C1	135.5 (3)
O2Wiii—Cs1—O2W—Cs1iii	0.00 (9)	Cs1v—O11—C11—O12	−43.3 (5)
O41iii—Cs1—O2W—Cs1iv	142.2 (2)	Cs1v—O12—C11—O11	41.3 (4)
O41iii—Cs1—O2W—Cs1iii	56.92 (9)	Cs1v—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)	Cs1iv—O42—N41—O41	−7.8 (8)
O2Wi—Cs1—O41—Cs1iii	−91.25 (19)	Cs1iv—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)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O12vi	0.82	1.88	2.694 (5)	174
O1W—H12W···O11vii	0.93	1.81	2.728 (4)	173
O2W—H21W···O1Wviii	0.79	1.99	2.749 (5)	162
O2W—H22W···O11vi	0.84	1.91	2.753 (5)	174

Table 1

Selected bond lengths (Å)

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

Symmetry codes: (i) ; (ii) ; (iii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O12iv	0.82	1.88	2.694 (5)	174
O1W—H12W⋯O11v	0.93	1.81	2.728 (4)	173
O2W—H21W⋯O1W vi	0.79	1.99	2.749 (5)	162
O2W—H22W⋯O11iv	0.84	1.91	2.753 (5)	174

Symmetry codes: (iv) ; (v) ; (vi) .