Poly[bis­(μ7-3-sulfonato-l-alaninato)sodiumzinc]

Li, X.; Yu, J.; Liu, L.

doi:10.1107/S160053681202394X

metal-organic compounds

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Volume 68| Part 6| June 2012| Page m849

doi:10.1107/S160053681202394X

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Poly[bis(μ₇-3-sulfonato-L-alaninato)sodiumzinc]

Xiao-lin Li,^a ^* Jing Yu ^a and Li Liu ^a

^aPhysics and Chemistry Department, Jiangxi College of Traditional Chinese Medicine, Fuzhou, Jiangxi 344000, People's Republic of China
^*Correspondence e-mail: caizhou2006@126.com

(Received 9 May 2012; accepted 25 May 2012; online 31 May 2012)

The hydrothermal reaction of Zn(CH₃COO)₂, NaOH and L-cysteic acid produced the title compound, [Na₂Zn(C₃H₅NO₅S)₂]_n. The Zn^II cation is situated on an inversion centre and is in a distorted octahedral environment, being chelated by two deprotoned L-cysteic acid ligands through two amino N atoms and two carboxylic O atoms, with the two axial positions occupied by two carboxylic O atoms from two other L-cysteic acid ligands. Each L-cysteic acid ligand bridges five Na^I ions via its sulfonate group and two Zn^II ions via its carboxyl group, forming a three-dimensional framework. Weak N—H⋯O hydrogen bonding is observed in the crystal structure.

Related literature

For general background to L-cysteic acid complexes, see: Li et al. (2009 , 2011a ,b ); Huang et al. (2009 ).

Experimental

Crystal data

[Na₂Zn(C₃H₅NO₅S)₂]
M_r = 445.67
Monoclinic, P 2₁ /c
a = 13.2432 (6) Å
b = 6.1574 (2) Å
c = 8.5959 (3) Å
β = 98.155 (2)°
V = 693.85 (5) Å³
Z = 2
Mo Kα radiation
μ = 2.19 mm⁻¹
T = 296 K
0.22 × 0.18 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.629, T_max = 0.769
5309 measured reflections
1293 independent reflections
1280 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.075
S = 0.97
1293 reflections
106 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O4ⁱ	2.0588 (18)
Zn1—O4	2.0588 (18)
Zn1—N1	2.116 (2)
Zn1—N1ⁱ	2.116 (2)
Zn1—O5ⁱⁱ	2.195 (2)
Zn1—O5ⁱⁱⁱ	2.195 (2)
Na1—O2^iv	2.309 (2)
Na1—O1	2.347 (2)
Na1—O1^v	2.442 (2)
Na1—O3^vi	2.386 (2)
Na1—O2^vii	2.426 (3)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) x, y-1, z; (v) -x, -y+1, -z+1; (vi) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3	0.90	2.28	3.030 (3)	141
N1—H1A⋯O4ⁱⁱⁱ	0.90	2.28	2.860 (3)	122
Symmetry code: (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); 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/S160053681202394X/zj2077sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202394X/zj2077Isup2.hkl

checkCIF report

Comment top

L-cysteic acid, an amino acid containing containing both sulfur and carboxyl, is indispensable to human beings with important physiologic functions. Recently,Jiang reported many compounds containing L-cysteic acid [Li et al. (2009, 2011a,b);Huang et al. (2009)]. L-cysteic acid, as a multidentate ligand with six coordination sites might be utilized as a versatile linker in the construction of interesting multidimensional complexes with the capability of participating in hydrogen bonding with multiproton acceptor or donor sites, which is a candidate for construction of multidimensional complexes. Herein, we present a new coordination polymer [ZnNa(C₃H₅NO₅S)₂]n (Scheme 1, Fig. 1). Each Zn(II) ion is six-coordinated to four oxygen atoms (O4, O4A, O5B, O5C), which belonging to four different L-cysteic acid ligands, two amino nitrogen atom (N1, N1A) from different ligands to give a distorted octahedron geometries. Each sulfonate group of the taurinate ligand takes part in the formation of a hydrogen bond (Table 2) with the amino group of a neighbouring ligand in the complex. A notable feature of the title complex lies in the coordination modes of the sulfonate group. The most common coordination modes are monodentate and µ₂ or µ₃-bridging, while µ₅-bridging is very rare. The Na atom is surrounded by five O atoms from different ligands, The title complex forms a three-dimensional structure (Fig. 2) through the Na···O linkage. The Na···O distances are in the range 2.309 (2)–2.442 (2) Å, suggesting weak electrostatic interactions.

Related literature top

For general background to L-cysteic acid complexes, see: Li et al. (2009, 2011a,b); Huang et al. (2009).

Experimental top

A mixture of Zn(CH₃COO)₂ (0.5 mmol, 92.5 mg), L-cysteic acid (1.0 mmol 169 mg), NaOH (2.0 mmol, 80 mg) and anhydrous methanol (15.0 ml) was placed in a Teflon-lined stainless steel vessel, and heated directly to 115 °C. After keeping at 115 °C for 5 days, it was cooled to room temperature at a rate for 10 °C/h. block colorless crystals of the complex were obtained.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 molecular structure of the title compound, with 30% probability displacement ellipsoids and the atom-numbering scheme. [Symmetry code: (A) 1 - x, 2 - y, 1 - z; (B) 1 - x, y + 1/2, 3/2 - z; (C) x, -y + 3/2, z - 1/2; (D) x, y - 1, z; (E) -x, -y + 1, 1 - z;(F)x, 3/2 - y, 1/2 + z;(G)-x, -1/2 + y, 3/2 - z.]
	Fig. 2. The crystal packing of the title compound viewed down the a axis.Hydrogen atoms have be omitted for clarity.

Poly[bis(µ₇-3-sulfonato-L-alaninato)sodiumzinc] top

Crystal data top

[Na₂Zn(C₃H₅NO₅S)₂]	Z = 2
M_r = 445.67	F(000) = 448
Monoclinic, P2₁/c	D_x = 2.133 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.2432 (6) Å	µ = 2.19 mm⁻¹
b = 6.1574 (2) Å	T = 296 K
c = 8.5959 (3) Å	Block, colorless
β = 98.155 (2)°	0.22 × 0.18 × 0.12 mm
V = 693.85 (5) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1293 independent reflections
Radiation source: fine-focus sealed tube	1280 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scans	θ_max = 25.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −16→12
T_min = 0.629, T_max = 0.769	k = −7→7
5309 measured reflections	l = −10→10

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0389P)² + 1.860P] where P = (F_o² + 2F_c²)/3
1293 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Na₂Zn(C₃H₅NO₅S)₂]	V = 693.85 (5) Å³
M_r = 445.67	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2432 (6) Å	µ = 2.19 mm⁻¹
b = 6.1574 (2) Å	T = 296 K
c = 8.5959 (3) Å	0.22 × 0.18 × 0.12 mm
β = 98.155 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1293 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1280 reflections with I > 2σ(I)
T_min = 0.629, T_max = 0.769	R_int = 0.018
5309 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 0.97	Δρ_max = 0.40 e Å⁻³
1293 reflections	Δρ_min = −0.45 e Å⁻³
106 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
Zn1	0.5000	1.0000	0.5000	0.02019 (15)
Na1	0.03657 (9)	0.38146 (19)	0.69254 (13)	0.0282 (3)
S1	0.13597 (5)	0.88954 (11)	0.57241 (8)	0.01901 (18)
O1	0.07432 (16)	0.6925 (3)	0.5538 (3)	0.0318 (5)
O2	0.10261 (16)	1.0349 (4)	0.6877 (3)	0.0312 (5)
O3	0.14300 (16)	0.9951 (4)	0.4229 (3)	0.0323 (5)
O4	0.51364 (13)	0.8902 (3)	0.7282 (2)	0.0206 (4)
O5	0.42196 (14)	0.8016 (3)	0.9167 (2)	0.0245 (4)
N1	0.35961 (16)	1.1125 (4)	0.5602 (3)	0.0195 (5)
H1A	0.3642	1.2549	0.5836	0.023*
H1B	0.3098	1.0943	0.4784	0.023*
C1	0.26104 (19)	0.8023 (5)	0.6488 (3)	0.0201 (5)
H1C	0.2573	0.7106	0.7395	0.024*
H1D	0.2877	0.7148	0.5700	0.024*
C2	0.3354 (2)	0.9888 (4)	0.6971 (3)	0.0194 (6)
H2	0.3050	1.0872	0.7672	0.023*
C3	0.4327 (2)	0.8863 (4)	0.7882 (3)	0.0183 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0172 (2)	0.0295 (3)	0.0144 (2)	0.00005 (17)	0.00421 (16)	0.00207 (17)
Na1	0.0300 (6)	0.0232 (6)	0.0301 (6)	0.0004 (5)	0.0000 (5)	−0.0026 (5)
S1	0.0132 (3)	0.0225 (3)	0.0208 (3)	−0.0017 (2)	0.0004 (2)	0.0025 (3)
O1	0.0279 (11)	0.0259 (11)	0.0389 (12)	−0.0079 (9)	−0.0044 (9)	0.0025 (9)
O2	0.0265 (11)	0.0326 (11)	0.0344 (12)	0.0052 (9)	0.0041 (9)	−0.0055 (9)
O3	0.0243 (11)	0.0450 (14)	0.0265 (11)	−0.0006 (9)	−0.0005 (9)	0.0129 (9)
O4	0.0135 (9)	0.0303 (11)	0.0184 (9)	0.0022 (8)	0.0034 (7)	0.0047 (8)
O5	0.0216 (9)	0.0343 (11)	0.0188 (9)	0.0063 (9)	0.0063 (8)	0.0069 (8)
N1	0.0165 (11)	0.0221 (11)	0.0190 (11)	−0.0022 (9)	−0.0003 (8)	0.0044 (9)
C1	0.0149 (12)	0.0230 (13)	0.0225 (13)	0.0006 (11)	0.0030 (10)	0.0023 (11)
C2	0.0146 (12)	0.0248 (14)	0.0188 (13)	0.0008 (10)	0.0027 (10)	0.0028 (10)
C3	0.0171 (12)	0.0205 (13)	0.0170 (12)	0.0012 (10)	0.0013 (10)	−0.0003 (10)

Geometric parameters (Å, º) top

Zn1—O4ⁱ	2.0588 (18)	O1—Na1^v	2.442 (2)
Zn1—O4	2.0588 (18)	O2—Na1^viii	2.309 (2)
Zn1—N1	2.116 (2)	O2—Na1^ix	2.426 (3)
Zn1—N1ⁱ	2.116 (2)	O3—Na1ⁱⁱ	2.386 (2)
Zn1—O5ⁱⁱ	2.195 (2)	O4—C3	1.254 (3)
Zn1—O5ⁱⁱⁱ	2.195 (2)	O5—C3	1.248 (3)
Na1—O2^iv	2.309 (2)	O5—Zn1^x	2.195 (2)
Na1—O1	2.347 (2)	N1—C2	1.474 (3)
Na1—O1^v	2.442 (2)	N1—H1A	0.9000
Na1—O3^vi	2.386 (2)	N1—H1B	0.9000
Na1—O2^vii	2.426 (3)	C1—C2	1.531 (4)
S1—O2	1.450 (2)	C1—H1C	0.9700
S1—O3	1.455 (2)	C1—H1D	0.9700
S1—O1	1.458 (2)	C2—C3	1.545 (4)
S1—C1	1.776 (3)	C2—H2	0.9800

O4ⁱ—Zn1—O4	180.0	Na1—O1—Na1^v	98.23 (8)
O4ⁱ—Zn1—N1	99.45 (8)	S1—O2—Na1^viii	137.36 (15)
O4—Zn1—N1	80.55 (8)	S1—O2—Na1^ix	111.91 (13)
O4ⁱ—Zn1—N1ⁱ	80.55 (8)	Na1^viii—O2—Na1^ix	92.28 (8)
O4—Zn1—N1ⁱ	99.45 (8)	S1—O3—Na1ⁱⁱ	140.46 (14)
N1—Zn1—N1ⁱ	180.0	C3—O4—Zn1	115.68 (16)
O4ⁱ—Zn1—O5ⁱⁱ	89.62 (8)	C3—O5—Zn1^x	122.34 (17)
O4—Zn1—O5ⁱⁱ	90.38 (8)	C2—N1—Zn1	108.92 (16)
N1—Zn1—O5ⁱⁱ	88.13 (8)	C2—N1—H1A	109.9
N1ⁱ—Zn1—O5ⁱⁱ	91.87 (8)	Zn1—N1—H1A	109.9
O4ⁱ—Zn1—O5ⁱⁱⁱ	90.38 (8)	C2—N1—H1B	109.9
O4—Zn1—O5ⁱⁱⁱ	89.62 (8)	Zn1—N1—H1B	109.9
N1—Zn1—O5ⁱⁱⁱ	91.87 (8)	H1A—N1—H1B	108.3
N1ⁱ—Zn1—O5ⁱⁱⁱ	88.13 (8)	C2—C1—S1	113.79 (19)
O5ⁱⁱ—Zn1—O5ⁱⁱⁱ	180.0	C2—C1—H1C	108.8
O2^iv—Na1—O1	129.53 (9)	S1—C1—H1C	108.8
O2^iv—Na1—O3^vi	97.40 (9)	C2—C1—H1D	108.8
O1—Na1—O3^vi	91.05 (9)	S1—C1—H1D	108.8
O2^iv—Na1—O2^vii	132.84 (9)	H1C—C1—H1D	107.7
O1—Na1—O2^vii	97.31 (9)	N1—C2—C1	112.0 (2)
O3^vi—Na1—O2^vii	85.34 (8)	N1—C2—C3	110.8 (2)
O2—S1—O3	113.08 (14)	C1—C2—C3	106.8 (2)
O2—S1—O1	111.61 (13)	N1—C2—H2	109.0
O3—S1—O1	112.31 (13)	C1—C2—H2	109.0
O2—S1—C1	107.02 (13)	C3—C2—H2	109.0
O3—S1—C1	106.76 (13)	O5—C3—O4	125.7 (2)
O1—S1—C1	105.50 (13)	O5—C3—C2	115.4 (2)
S1—O1—Na1	141.19 (13)	O4—C3—C2	119.0 (2)
S1—O1—Na1^v	120.57 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.90	2.28	3.030 (3)	141
N1—H1A···O4ⁱⁱⁱ	0.90	2.28	2.860 (3)	122

Symmetry code: (iii) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Na₂Zn(C₃H₅NO₅S)₂]
M_r	445.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.2432 (6), 6.1574 (2), 8.5959 (3)
β (°)	98.155 (2)
V (Å³)	693.85 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.19
Crystal size (mm)	0.22 × 0.18 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.629, 0.769
No. of measured, independent and observed [I > 2σ(I)] reflections	5309, 1293, 1280
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.075, 0.97
No. of reflections	1293
No. of parameters	106
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.45

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—O4ⁱ	2.0588 (18)	Na1—O2^iv	2.309 (2)
Zn1—O4	2.0588 (18)	Na1—O1	2.347 (2)
Zn1—N1	2.116 (2)	Na1—O1^v	2.442 (2)
Zn1—N1ⁱ	2.116 (2)	Na1—O3^vi	2.386 (2)
Zn1—O5ⁱⁱ	2.195 (2)	Na1—O2^vii	2.426 (3)
Zn1—O5ⁱⁱⁱ	2.195 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.90	2.28	3.030 (3)	141.2
N1—H1A···O4ⁱⁱⁱ	0.90	2.28	2.860 (3)	122.2

Symmetry code: (iii) −x+1, y+1/2, −z+3/2.

Acknowledgements

We are grateful to the Start-up Fundation of Jiangxi College of Traditional Chinese Medicine for funding this study.

References

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