Poly[[μ10-2,3-bis(carboxymethyl)butanedioato]disodium]

Wu, J.; Zhu, H.

doi:10.1107/S1600536810040857

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1419

https://doi.org/10.1107/S1600536810040857

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Poly[[μ₁₀-2,3-bis(carboxymethyl)butanedioato]disodium]

Jiang Wu ^a and Hong-lin Zhu ^a ^*

^aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Center of Applied Solid State Chemistry Research, Ningbo University, Ningbo, Zhejiang, 315211, People's Republic of China
^*Correspondence e-mail: Zhuhonglin1@nbu.edu.cn

(Received 8 October 2010; accepted 12 October 2010; online 20 October 2010)

The asymmetric unit of the title compound, [Na₂(C₈H₈O₈)]_n, contains one Na⁺ ion and half of a 2,3-bis(carboxymethyl)butanedioate (H₂BTC²⁻) dianion, which lies on a center of symmetry. The dianion exhibits a μ₁₀-bridging mode. Each Na atom lies in a NaO₆ octahedron defined by six O atoms from five dianions. Adjacent NaO₆ octahedra share a common O—O edge, generating a bioctahedron; adjacent bioctahedra are O—O edge-connected to one another, building up a chain along [001]. The chains are connected by adjacent H₂BTC²⁻ anions into a three-dimensional framework. The structure is further stabilized by O—H⋯O hydrogen bonds.

Related literature

For related structures, see: Delgado et al. (2007 ); Liu et al. (2008 ); Wang et al. (2005 ); Zheng et al. (2004 ); Zhu & Zheng (2010 ).

Experimental

Crystal data

[Na₂(C₈H₈O₈)]
M_r = 278.12
Orthorhombic, P b c n
a = 8.9053 (18) Å
b = 8.6395 (17) Å
c = 12.527 (3) Å
V = 963.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.44 × 0.36 × 0.32 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.900, T_max = 0.925
8610 measured reflections
1097 independent reflections
1000 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.111
S = 1.10
1097 reflections
86 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2C⋯O4ⁱ	0.85 (2)	1.67 (3)	2.5097 (18)	177 (2)
Symmetry code: (i) $[-x+{\script{5\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks ptcLa, I. DOI: https://doi.org/10.1107/S1600536810040857/ng5044sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040857/ng5044Isup2.hkl

checkCIF report

Comment top

Recently, the aliphatic multi-carboxylic acids have attractived considerable attention due to both its conformational flexibility and a variety of coordination fashions (Wang et al., 2005; Zheng et al., 2004).The butane-1,2,3,4-tetracarboxylic acid (H₄BTC) ligand possesses four ionizable protons that can be removed gradually to form a series of deprotonated anions such as H₃BTC^-, H₂BTC^2-, HBTC^3-, BTC^4-, which have allowed the preparation of a variety of complexes with differents metals (Delgado et al., 2007; Liu et al., 2008; Zhu et al., 2010). In this contribution, we report the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound contains one Na⁺ ion and half a H₂BTC^2- anion(Figure 1). The H₂BTC^2-ligand is diprotonated, which is crystallographically imposed by symmetry of center with inversion centers at the midpoints of the central C3—C3ⁱ bond with the Wyckoff 4b site. Each H₂BTC^2- anions coordinate ten sodium ions through eight carboxyl oxygen atoms. The carboxylate group and carboxylic group all coordinates to two metal atoms in a syn/anti µ₂η² bridging fashion, and two seven-membered chelating rings are concomitantly formed. Each Na atom is in a distorted octahedra NaO₆ gemetry defined by six O atoms from five H₂BTC^2- ligands, the Na—O contact distances are all within the normal ranges. The adjacent two NaO₆ octahedra are fused via common edge O1—O1 and O3—O3, generating a one-dimensional sodium-oxide chains (Figure 2), and the resulting chains are further interlinked by H₂BTC^2- anions into three-dimensional frameworks (Figure 3).

Related literature top

For related structures, see: Delgado et al. (2007); Liu et al. (2008); Wang et al. (2005); Zheng et al. (2004); Zhu & Zheng (2010).

Experimental top

All chemicals were obtained from commerical sources and were used as obtained. NaOH (0.079 g, 1.98 mmol) was added to a stirred mixture solution of butane-1,2,3,4-tetracarboxylic acid (0.1173 g, 0.50 mmol) in 10 ml H₂O and 10 ml me thanol, and the resulting mixture was stirred for 5 min. Colorless crystals were obtained from the solution (pH = 7.13) after standing at room temperature for five weeks.

Structure description top

For related structures, see: Delgado et al. (2007); Liu et al. (2008); Wang et al. (2005); Zheng et al. (2004); Zhu & Zheng (2010).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The content of asymmetric unit showing the atomic numbering and 45% probability dispalcement ellipsoids.[Symmetry codes: (i) -x + 2, -y + 1, -z + 1. (ii) -x + 2, -y, -z + 1. (iii) -x + 2, y, -z + 1.5. (iv) x - 1/2,y - 1/2, -z + 1.5. (v) x - 1/2, -y + 1/2, -z + 1.]
	Fig. 2. The one-dimensional sodium-oxide chains with the common edges O1—O1 and O3—O3.
	Fig. 3. The three-dimensional metal-organic framework in the title compound.

Poly[[µ₁₀-2,3-bis(carboxymethyl)butanedioato]disodium] top

Crystal data top

[Na₂(C₈H₈O₈)]	F(000) = 568
M_r = 278.12	D_x = 1.917 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 7116 reflections
a = 8.9053 (18) Å	θ = 3.3–27.4°
b = 8.6395 (17) Å	µ = 0.24 mm⁻¹
c = 12.527 (3) Å	T = 293 K
V = 963.8 (3) Å³	Block, colorless
Z = 4	0.44 × 0.36 × 0.32 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1097 independent reflections
Radiation source: fine-focus sealed tube	1000 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 0 pixels mm^-1	θ_max = 27.4°, θ_min = 3.3°
ω scan	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
T_min = 0.900, T_max = 0.925	l = −16→16
8610 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0658P)² + 0.5154P] where P = (F_o² + 2F_c²)/3
1097 reflections	(Δ/σ)_max < 0.001
86 parameters	Δρ_max = 0.43 e Å⁻³
1 restraint	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Na₂(C₈H₈O₈)]	V = 963.8 (3) Å³
M_r = 278.12	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 8.9053 (18) Å	µ = 0.24 mm⁻¹
b = 8.6395 (17) Å	T = 293 K
c = 12.527 (3) Å	0.44 × 0.36 × 0.32 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1097 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1000 reflections with I > 2σ(I)
T_min = 0.900, T_max = 0.925	R_int = 0.021
8610 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.43 e Å⁻³
1097 reflections	Δρ_min = −0.22 e Å⁻³
86 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
Na	0.91916 (8)	0.06655 (8)	0.62976 (5)	0.0292 (2)
O1	1.12521 (17)	0.21959 (14)	0.69249 (10)	0.0391 (4)
O2	1.30500 (16)	0.37558 (13)	0.75029 (10)	0.0325 (3)
C1	1.19167 (19)	0.34236 (18)	0.68752 (12)	0.0243 (3)
C2	1.15019 (18)	0.46906 (17)	0.61037 (11)	0.0219 (3)
H2A	1.2386	0.4963	0.5692	0.026*
H2B	1.1207	0.5598	0.6508	0.026*
C3	1.02287 (16)	0.42768 (14)	0.53277 (10)	0.0161 (3)
H3A	0.9358	0.3927	0.5741	0.019*
C4	1.07185 (16)	0.29671 (16)	0.45770 (11)	0.0177 (3)
O3	1.01257 (15)	0.16760 (12)	0.46431 (9)	0.0300 (3)
O4	1.17325 (15)	0.33112 (14)	0.39020 (10)	0.0300 (3)
H2C	1.310 (4)	0.308 (3)	0.7989 (19)	0.088 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na	0.0336 (4)	0.0244 (4)	0.0296 (4)	−0.0038 (3)	0.0023 (3)	−0.0031 (2)
O1	0.0481 (8)	0.0278 (7)	0.0415 (7)	−0.0062 (6)	−0.0172 (6)	0.0104 (5)
O2	0.0432 (7)	0.0262 (6)	0.0282 (6)	0.0011 (5)	−0.0177 (5)	0.0041 (5)
C1	0.0305 (8)	0.0216 (7)	0.0208 (7)	0.0046 (6)	−0.0054 (6)	−0.0007 (5)
C2	0.0278 (7)	0.0185 (7)	0.0194 (7)	0.0020 (6)	−0.0054 (6)	0.0003 (5)
C3	0.0208 (7)	0.0137 (6)	0.0138 (6)	0.0032 (5)	0.0005 (5)	0.0002 (5)
C4	0.0212 (7)	0.0160 (6)	0.0159 (6)	0.0039 (5)	−0.0012 (5)	−0.0008 (5)
O3	0.0448 (7)	0.0166 (5)	0.0286 (6)	−0.0050 (5)	0.0081 (5)	−0.0041 (4)
O4	0.0340 (6)	0.0247 (6)	0.0314 (6)	−0.0026 (5)	0.0148 (5)	−0.0082 (5)

Geometric parameters (Å, º) top

Na—O4ⁱ	2.3748 (15)	O2—H2C	0.843 (10)
Na—O1	2.3943 (15)	C1—C2	1.506 (2)
Na—O3	2.3978 (13)	C2—C3	1.536 (2)
Na—O3ⁱⁱ	2.4188 (13)	C2—H2A	0.9700
Na—O2ⁱⁱⁱ	2.4522 (14)	C2—H2B	0.9700
Na—O1^iv	2.6196 (15)	C3—C4	1.5346 (18)
Na—Na^iv	3.3388 (14)	C3—C3^vi	1.550 (2)
Na—Naⁱⁱ	3.7369 (14)	C3—H3A	0.9800
O1—C1	1.216 (2)	C4—O3	1.2368 (18)
O1—Na^iv	2.6196 (15)	C4—O4	1.2723 (19)
O2—C1	1.311 (2)	O3—Naⁱⁱ	2.4188 (13)
O2—Na^v	2.4522 (14)	O4—Na^vii	2.3748 (15)

O4ⁱ—Na—O1	122.39 (5)	C1—O1—Na	146.90 (11)
O4ⁱ—Na—O3	95.36 (5)	C1—O1—Na^iv	123.86 (11)
O1—Na—O3	79.44 (5)	Na—O1—Na^iv	83.38 (5)
O4ⁱ—Na—O3ⁱⁱ	119.46 (5)	C1—O2—Na^v	146.49 (11)
O1—Na—O3ⁱⁱ	115.41 (6)	C1—O2—H2C	109 (2)
O3—Na—O3ⁱⁱ	78.24 (5)	Na^v—O2—H2C	90 (2)
O4ⁱ—Na—O2ⁱⁱⁱ	86.14 (5)	O1—C1—O2	122.32 (14)
O1—Na—O2ⁱⁱⁱ	119.22 (5)	O1—C1—C2	123.18 (14)
O3—Na—O2ⁱⁱⁱ	156.69 (5)	O2—C1—C2	114.49 (14)
O3ⁱⁱ—Na—O2ⁱⁱⁱ	80.80 (5)	C1—C2—C3	114.71 (13)
O4ⁱ—Na—O1^iv	76.26 (5)	C1—C2—H2A	108.6
O1—Na—O1^iv	63.76 (7)	C3—C2—H2A	108.6
O3—Na—O1^iv	127.10 (5)	C1—C2—H2B	108.6
O3ⁱⁱ—Na—O1^iv	150.95 (5)	C3—C2—H2B	108.6
O2ⁱⁱⁱ—Na—O1^iv	75.89 (5)	H2A—C2—H2B	107.6
O4ⁱ—Na—Na^iv	119.52 (4)	C4—C3—C2	110.47 (11)
O1—Na—Na^iv	51.20 (4)	C4—C3—C3^vi	110.16 (13)
O3—Na—Na^iv	129.07 (5)	C2—C3—C3^vi	109.98 (14)
O3ⁱⁱ—Na—Na^iv	109.34 (4)	C4—C3—H3A	108.7
O2ⁱⁱⁱ—Na—Na^iv	68.03 (4)	C2—C3—H3A	108.7
O1^iv—Na—Na^iv	45.42 (3)	C3^vi—C3—H3A	108.7
O4ⁱ—Na—Naⁱⁱ	112.22 (4)	O3—C4—O4	123.93 (13)
O1—Na—Naⁱⁱ	99.22 (5)	O3—C4—C3	120.17 (12)
O3—Na—Naⁱⁱ	39.32 (3)	O4—C4—C3	115.89 (12)
O3ⁱⁱ—Na—Naⁱⁱ	38.92 (3)	C4—O3—Na	122.30 (9)
O2ⁱⁱⁱ—Na—Naⁱⁱ	119.06 (4)	C4—O3—Naⁱⁱ	127.90 (10)
O1^iv—Na—Naⁱⁱ	162.35 (5)	Na—O3—Naⁱⁱ	101.76 (5)
Na^iv—Na—Naⁱⁱ	128.23 (4)	C4—O4—Na^vii	144.24 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2C···O4^viii	0.85 (2)	1.67 (3)	2.5097 (18)	177 (2)

Symmetry code: (viii) −x+5/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Na₂(C₈H₈O₈)]
M_r	278.12
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	8.9053 (18), 8.6395 (17), 12.527 (3)
V (Å³)	963.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.44 × 0.36 × 0.32

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.900, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	8610, 1097, 1000
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 1.10
No. of reflections	1097
No. of parameters	86
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.22

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), 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
O2—H2C···O4ⁱ	0.85 (2)	1.67 (3)	2.5097 (18)	177 (2)

Symmetry code: (i) −x+5/2, −y+1/2, z+1/2.

Acknowledgements

This project was supported by the National Natural Science Foundation of China (grant No. 20072022), the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Science and Technology Department of Zhejiang Province (grant No. 2006 C21105) and the Education Department of Zhejiang Province. Thanks are also extended to the K. C. Wong Magna Fund of Ningbo University.

References

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