Poly[(μ-2-hy­droxy-3,5-dinitro­benzoato)rubidium]

Meng, Y.

doi:10.1107/S1600536811008476

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m454

doi:10.1107/S1600536811008476

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Poly[(μ-2-hydroxy-3,5-dinitrobenzoato)rubidium]

Yan Meng ^a ^*

^aSchool of Environmental Engineering, Chang'an University, South Second Cycle Road 368#, Xi'an 710064, Shaanxi, People's Republic of China
^*Correspondence e-mail: myancau@163.com

(Received 6 February 2011; accepted 6 March 2011; online 15 March 2011)

The asymmetric unit of the title compound, [Rb(C₇H₃N₂O₇)]_n, comprises an Rb⁺ cation and a 3,5-dinitrosalicylate ligand. The Rb⁺ cation is 10-coordinated by O atoms from eight 3,5-dinitrosalicylate anions and is linked by three μ₂-O atoms, forming a zigzag chain along the b-axis direction, which is further linked by the phenyl groups, giving the three-dimensional framework. The crystal structure involves intra-anionic O—H⋯O hydrogen bonds and strong π–π stacking interactions [centroid-centroid distance = 3.6755 (7) Å].

Related literature

For 3,5-dinitrosalicylate complexes, see: Hu et al. (2005 ); Song et al. (2007 , 2008 ). For Rb–O bond lengths, see: Cametti et al. (2005 ).

Experimental

Crystal data

[Rb(C₇H₃N₂O₇)]
M_r = 312.58
Monoclinic, P 2₁ /c
a = 7.5957 (15) Å
b = 7.2971 (15) Å
c = 17.036 (3) Å
β = 95.10 (3)°
V = 940.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 5.30 mm⁻¹
T = 293 K
0.64 × 0.60 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.219, T_max = 0.548
8781 measured reflections
1715 independent reflections
1548 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.107
S = 1.07
1715 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −1.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O2	0.85	1.67	2.459 (4)	153

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008476/om2407sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008476/om2407Isup2.hkl

checkCIF report

Comment top

In the structural investigation of 3,5-dinitrosalicylate complexes, it has been found that the 3,5-dinitrosalicylate moiety functions as a multidentate ligand (Hu et al., 2005; Song et al., 2007; Song et al., 2008) with versatile bonding and coordination modes. In this paper, we report the crystal structure of the title compound, a new Rb complex obtained by the reaction of 3,5-dinitrosalicylic acid and RbOH in water.

The asymmetric unit of the title compound comprises a Rb cation, and a 3,5-dinitrosalicylate anion. The central cation is coordinated to ten O atoms from eight 3,5-dinitrosalicylate anions (Fig. 1) with the Rb–O distances ranging from 2.821 (3) Å to 3.385 (4) Å, which are well within the range reported in the literature (Cametti et al., 2005). The Rb centre is firstly linked by three µ₂-oygen atoms to form a one-dimensional zigzag-shaped chain along the b-axis direction, which is further linked by the phenyl groups to give the three-dimensional framework of the title compound (Fig. 2). The shortest intra-anionic hydrogen bond is established between O7–H7A···O2 with the bond distances of 2.459 (4) Å. Furthermore, strong aromatic π–π stacking interactions between adjacent phenyl rings with a center-to-center distance of 3.6755 (7) Å help to stabilize the three-dimensional framework.

Related literature top

For 3,5-dinitrosalicylate complexes, see: Hu et al. (2005); Song et al. (2007, 2008). For Rb–O bond lengths, see: Cametti et al. (2005).

Experimental top

Analysis grade 3,5-dinitrosalicylic acid and RbOH (purity > 99.5%, Sinopharm Chemical Reagent Co., Ltd., Shanghai, China) were commercially available and used without further purification. To a solution of 10 mmol 3,5-dinitrosalicylic acid in 50 ml double-distilled water, a solution of an equimolar amount of RbOH in 40 ml double-distilled water was added dropwise at room temperature. After vigorous stirring for 3 h, the resulting solution was evaporated to a volume of about 20 ml in vacuum and filtered hot. The filtrate was then set aside for crystallization at room temperature. One month later, yellow block crystals of the title compound suitable for X-ray determination were isolated.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT(Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids. Symmetry code: (i) -x + 2, -y + 2, -z; (ii) -x + 3, -y + 2, -z; (iii) x + 1, y + 1, z; (iv) -x + 3, y + 1/2, -z + 1/2; (v) x + 1, -y + 3/2, z + 1/2; (vi) -x + 2, y + 1/2, -z + 1/2; (vii) x + 1, y, z.
	Fig. 2. The three-dimensional framework of the title compound viewed along the b-axis direction, and the broken lines represent the π–π stacking interactions. The H atoms were omitted for clarity.

Poly[(µ-2-hydroxy-3,5-dinitrobenzoato)rubidium] top

Crystal data top

[Rb(C₇H₃N₂O₇)]	F(000) = 608
M_r = 312.58	D_x = 2.208 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3447 reflections
a = 7.5957 (15) Å	θ = 3.0–25.4°
b = 7.2971 (15) Å	µ = 5.30 mm⁻¹
c = 17.036 (3) Å	T = 293 K
β = 95.10 (3)°	Block, yellow
V = 940.5 (3) Å³	0.64 × 0.60 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1715 independent reflections
Radiation source: fine-focus sealed tube	1548 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 25.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.219, T_max = 0.548	k = −7→8
8781 measured reflections	l = −18→20

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0621P)²] where P = (F_o² + 2F_c²)/3
1715 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −1.28 e Å⁻³

Crystal data top

[Rb(C₇H₃N₂O₇)]	V = 940.5 (3) Å³
M_r = 312.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5957 (15) Å	µ = 5.30 mm⁻¹
b = 7.2971 (15) Å	T = 293 K
c = 17.036 (3) Å	0.64 × 0.60 × 0.20 mm
β = 95.10 (3)°

Data collection top

Bruker SMART CCD diffractometer	1715 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1548 reflections with I > 2σ(I)
T_min = 0.219, T_max = 0.548	R_int = 0.065
8781 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.07	Δρ_max = 0.59 e Å⁻³
1715 reflections	Δρ_min = −1.28 e Å⁻³
154 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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
Rb1	1.61252 (5)	1.14921 (5)	0.20167 (2)	0.0369 (2)
C1	1.2759 (5)	0.8926 (5)	0.1057 (2)	0.0273 (8)
C2	1.1105 (5)	0.8137 (5)	0.0645 (2)	0.0242 (8)
C3	1.0990 (5)	0.7877 (5)	−0.0199 (2)	0.0241 (8)
C4	0.9370 (5)	0.7063 (5)	−0.0527 (2)	0.0247 (8)
C5	0.8025 (5)	0.6593 (4)	−0.0081 (2)	0.0251 (8)
H5	0.6998	0.6056	−0.0314	0.030*
C6	0.8215 (5)	0.6929 (5)	0.0721 (2)	0.0248 (8)
C7	0.9735 (5)	0.7708 (5)	0.1085 (2)	0.0240 (8)
H7	0.9826	0.7939	0.1624	0.029*
N1	0.9095 (5)	0.6663 (4)	−0.13724 (19)	0.0310 (8)
N2	0.6787 (5)	0.6448 (4)	0.1190 (2)	0.0335 (8)
O1	1.2938 (4)	0.9117 (4)	0.17699 (15)	0.0361 (7)
O2	1.3980 (3)	0.9418 (4)	0.06105 (15)	0.0377 (7)
O3	1.0271 (5)	0.6878 (6)	−0.17888 (19)	0.0680 (11)
O4	0.7641 (5)	0.6080 (5)	−0.16227 (18)	0.0562 (9)
O5	0.5666 (4)	0.5376 (5)	0.09310 (19)	0.0554 (9)
O6	0.6775 (4)	0.7154 (5)	0.18481 (17)	0.0500 (8)
O7	1.2245 (4)	0.8369 (4)	−0.05933 (16)	0.0356 (7)
H7A	1.3073	0.8813	−0.0282	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rb1	0.0346 (3)	0.0485 (3)	0.0288 (3)	−0.01148 (17)	0.0097 (2)	−0.00679 (15)
C1	0.022 (2)	0.0290 (18)	0.031 (2)	−0.0011 (16)	0.0012 (16)	0.0035 (15)
C2	0.023 (2)	0.0228 (17)	0.027 (2)	−0.0013 (15)	0.0019 (16)	0.0008 (14)
C3	0.025 (2)	0.0243 (17)	0.0238 (18)	0.0021 (16)	0.0059 (15)	0.0050 (15)
C4	0.031 (2)	0.0272 (18)	0.0160 (17)	0.0016 (16)	0.0020 (15)	0.0024 (14)
C5	0.020 (2)	0.0239 (18)	0.031 (2)	−0.0034 (14)	−0.0018 (16)	0.0013 (14)
C6	0.021 (2)	0.0265 (17)	0.028 (2)	−0.0020 (15)	0.0036 (15)	0.0017 (15)
C7	0.027 (2)	0.0227 (17)	0.0233 (17)	−0.0006 (15)	0.0049 (15)	0.0017 (14)
N1	0.032 (2)	0.0367 (19)	0.0237 (17)	−0.0022 (14)	0.0004 (16)	0.0025 (13)
N2	0.026 (2)	0.042 (2)	0.033 (2)	−0.0057 (15)	0.0073 (16)	0.0027 (14)
O1	0.0316 (16)	0.0488 (17)	0.0275 (15)	−0.0104 (14)	0.0005 (12)	−0.0017 (12)
O2	0.0226 (14)	0.0557 (18)	0.0351 (15)	−0.0144 (14)	0.0048 (11)	0.0052 (13)
O3	0.042 (2)	0.136 (4)	0.0265 (17)	−0.015 (2)	0.0110 (16)	−0.0129 (18)
O4	0.054 (2)	0.086 (2)	0.0274 (16)	−0.0344 (19)	−0.0043 (15)	−0.0013 (15)
O5	0.0378 (18)	0.070 (2)	0.060 (2)	−0.0309 (17)	0.0149 (15)	−0.0087 (17)
O6	0.0384 (19)	0.086 (2)	0.0284 (16)	−0.0061 (17)	0.0174 (13)	−0.0040 (16)
O7	0.0283 (17)	0.0526 (18)	0.0267 (15)	−0.0122 (12)	0.0067 (12)	0.0018 (11)

Geometric parameters (Å, º) top

Rb1—O7ⁱ	2.821 (3)	C5—C6	1.383 (5)
Rb1—O1ⁱⁱ	2.861 (3)	C5—H5	0.9300
Rb1—O1	2.977 (3)	C6—C7	1.383 (5)
Rb1—O3ⁱ	3.041 (4)	C6—N2	1.447 (5)
Rb1—O6ⁱⁱⁱ	3.096 (3)	C7—H7	0.9300
Rb1—O4^iv	3.122 (3)	N1—O3	1.199 (5)
Rb1—O2	3.161 (3)	N1—O4	1.224 (4)
Rb1—O6^v	3.221 (4)	N2—O5	1.210 (4)
Rb1—O4^vi	3.381 (4)	N2—O6	1.234 (4)
Rb1—O5^vii	3.385 (4)	O1—Rb1^viii	2.861 (3)
C1—O1	1.218 (4)	O3—Rb1ⁱ	3.041 (4)
C1—O2	1.301 (5)	O4—Rb1^ix	3.122 (3)
C1—C2	1.498 (5)	O4—Rb1^vi	3.381 (4)
C2—C7	1.371 (5)	O5—Rb1^x	3.385 (4)
C2—C3	1.446 (5)	O6—Rb1^xi	3.096 (3)
C3—O7	1.266 (5)	O6—Rb1^xii	3.221 (4)
C3—C4	1.434 (5)	O7—Rb1ⁱ	2.821 (3)
C4—C5	1.370 (5)	O7—H7A	0.8500
C4—N1	1.465 (5)

O7ⁱ—Rb1—O1ⁱⁱ	119.80 (8)	O4^vi—Rb1—O5^vii	53.74 (8)
O7ⁱ—Rb1—O1	108.25 (8)	O1—C1—O2	122.0 (3)
O1ⁱⁱ—Rb1—O1	129.70 (4)	O1—C1—C2	121.7 (3)
O7ⁱ—Rb1—O3ⁱ	53.65 (9)	O2—C1—C2	116.4 (3)
O1ⁱⁱ—Rb1—O3ⁱ	70.22 (9)	C7—C2—C3	122.1 (3)
O1—Rb1—O3ⁱ	160.00 (9)	C7—C2—C1	118.5 (3)
O7ⁱ—Rb1—O6ⁱⁱⁱ	157.29 (9)	C3—C2—C1	119.4 (3)
O1ⁱⁱ—Rb1—O6ⁱⁱⁱ	65.76 (9)	O7—C3—C4	124.8 (3)
O1—Rb1—O6ⁱⁱⁱ	64.16 (8)	O7—C3—C2	120.6 (3)
O3ⁱ—Rb1—O6ⁱⁱⁱ	135.84 (10)	C4—C3—C2	114.6 (3)
O7ⁱ—Rb1—O4^iv	119.92 (9)	C5—C4—C3	122.9 (3)
O1ⁱⁱ—Rb1—O4^iv	79.29 (9)	C5—C4—N1	116.5 (3)
O1—Rb1—O4^iv	89.80 (9)	C3—C4—N1	120.6 (3)
O3ⁱ—Rb1—O4^iv	93.04 (11)	C4—C5—C6	119.1 (3)
O6ⁱⁱⁱ—Rb1—O4^iv	82.29 (9)	C4—C5—H5	120.4
O7ⁱ—Rb1—O2	66.53 (7)	C6—C5—H5	120.4
O1ⁱⁱ—Rb1—O2	161.17 (8)	C5—C6—C7	121.7 (4)
O1—Rb1—O2	41.94 (7)	C5—C6—N2	119.0 (3)
O3ⁱ—Rb1—O2	119.98 (8)	C7—C6—N2	119.2 (3)
O6ⁱⁱⁱ—Rb1—O2	101.58 (8)	C2—C7—C6	119.5 (3)
O4^iv—Rb1—O2	113.97 (9)	C2—C7—H7	120.3
O7ⁱ—Rb1—O6^v	82.90 (7)	C6—C7—H7	120.3
O1ⁱⁱ—Rb1—O6^v	133.80 (8)	O3—N1—O4	122.4 (3)
O1—Rb1—O6^v	62.88 (8)	O3—N1—C4	120.4 (3)
O3ⁱ—Rb1—O6^v	103.08 (10)	O4—N1—C4	117.2 (3)
O6ⁱⁱⁱ—Rb1—O6^v	109.40 (9)	O5—N2—O6	122.6 (3)
O4^iv—Rb1—O6^v	54.97 (8)	O5—N2—C6	119.5 (3)
O2—Rb1—O6^v	62.26 (8)	O6—N2—C6	117.9 (3)
O7ⁱ—Rb1—O4^vi	103.81 (8)	C1—O1—Rb1^viii	130.0 (3)
O1ⁱⁱ—Rb1—O4^vi	86.82 (8)	C1—O1—Rb1	103.0 (2)
O1—Rb1—O4^vi	67.29 (9)	Rb1^viii—O1—Rb1	98.09 (8)
O3ⁱ—Rb1—O4^vi	121.68 (10)	C1—O2—Rb1	92.0 (2)
O6ⁱⁱⁱ—Rb1—O4^vi	53.55 (8)	N1—O3—Rb1ⁱ	148.5 (3)
O4^iv—Rb1—O4^vi	135.41 (5)	N1—O4—Rb1^ix	136.8 (3)
O2—Rb1—O4^vi	74.36 (8)	N1—O4—Rb1^vi	127.5 (3)
O6^v—Rb1—O4^vi	129.12 (8)	Rb1^ix—O4—Rb1^vi	85.29 (8)
O7ⁱ—Rb1—O5^vii	62.09 (8)	N2—O5—Rb1^x	107.8 (3)
O1ⁱⁱ—Rb1—O5^vii	80.87 (8)	N2—O6—Rb1^xi	124.4 (2)
O1—Rb1—O5^vii	111.55 (8)	N2—O6—Rb1^xii	120.3 (2)
O3ⁱ—Rb1—O5^vii	69.70 (10)	Rb1^xi—O6—Rb1^xii	88.53 (8)
O6ⁱⁱⁱ—Rb1—O5^vii	99.57 (8)	C3—O7—Rb1ⁱ	151.1 (2)
O4^iv—Rb1—O5^vii	157.25 (9)	C3—O7—H7A	109.0
O2—Rb1—O5^vii	88.03 (8)	Rb1ⁱ—O7—H7A	99.6
O6^v—Rb1—O5^vii	141.57 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O2	0.85	1.67	2.459 (4)	153

Experimental details

Crystal data
Chemical formula	[Rb(C₇H₃N₂O₇)]
M_r	312.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.5957 (15), 7.2971 (15), 17.036 (3)
β (°)	95.10 (3)
V (Å³)	940.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.30
Crystal size (mm)	0.64 × 0.60 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.219, 0.548
No. of measured, independent and observed [I > 2σ(I)] reflections	8781, 1715, 1548
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.107, 1.07
No. of reflections	1715
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −1.28

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT(Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O2	0.85	1.67	2.459 (4)	153

Acknowledgements

This work was supported by two grants from the Scientific Research Plan Projects of Shaanxi Education Department (08 J K414, 09 J K702).

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