Poly[[diaqua-μ4-tartrato-μ2-tartrato-dimanganese(II)] dihydrate]

Ge, C.; Zhao, Z.; Han, G.; Zhang, X.

doi:10.1107/S1600536807067839

metal-organic compounds

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Volume 64| Part 2| February 2008| Page m360

doi:10.1107/S1600536807067839

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Poly[[diaqua-μ₄-tartrato-μ₂-tartrato-dimanganese(II)] dihydrate]

Chunhua Ge,^a ^* Zhen Zhao,^b Guangxi Han ^a and Xiangdong Zhang ^a

^aCollege of Chemistry, Liaoning University, Shenyang 110036, People's Republic of China, and ^bDepartment of Chemistry, Anshan Normal University, Anshan 114007, People's Republic of China
^*Correspondence e-mail: chhge@lnu.edu.cn

(Received 10 December 2007; accepted 20 December 2007; online 16 January 2008)

In the title compound, {[Mn(C₄H₄O₆)(H₂O)]·H₂O}_n, the Mn²⁺ ion is connected to three different tartrate anions and a water molecule, resulting in a distorted MnO₆ octahedral geometry. There are two tartrate half-anions in the asymmetric unit, both of which are completed by crystallographic twofold rotation symmetry. The tartrate dianions bridge the Mn²⁺ ions to form a wave-like infinite layer. A series of O—H⋯O hydrogen bonds link the layers into a three-dimensional network.

Related literature

For related literature, see: Kam et al. (2007 ).

Experimental

Crystal data

[Mn(C₄H₄O₆)(H₂O)]·H₂O
M_r = 239.04
Monoclinic, P 2/c
a = 11.029 (3) Å
b = 7.3925 (18) Å
c = 10.165 (3) Å
β = 112.149 (3)°
V = 767.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.74 mm⁻¹
T = 293 (2) K
0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.661, T_max = 0.739
3884 measured reflections
1507 independent reflections
1481 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.074
S = 1.10
1507 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O6	2.1036 (15)
Mn1—O1	2.1444 (15)
Mn1—O5ⁱ	2.1695 (15)
Mn1—O1W	2.2018 (16)
Mn1—O3	2.2230 (14)
Mn1—O4ⁱ	2.2518 (14)
Symmetry code: (i) $[x, -y, z-{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2Wⁱⁱ	0.82	1.81	2.628 (2)	175
O3—H3A⋯O2ⁱⁱⁱ	0.82	1.75	2.561 (2)	173
O1W—H1WA⋯O2^iv	0.82	2.04	2.643 (2)	130
O2W—H2WA⋯O5^v	0.82	2.29	2.895 (2)	131
O2W—H2WB⋯O4ⁱ	0.82	2.25	2.919 (3)	140
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-1, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iv) x, y-1, z; (v) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067839/hb2676sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067839/hb2676Isup2.hkl

checkCIF report

Comment top

Researchers have been interested in the study of tartrate-based coordination polymers, which has resulted in the formation of many interesting structures (e.g. Kam et al., 2007). The title compound, (I), is centrosymmetric (Fig. 1). The Mn(II) ion adopts a distorted MnO₆ octahedral geometry (Table 1).

In the crystal, one (R,R) and one (S,S) tartrate ligands coordinate with two metal ions to form a 'tetrameric' A ring (Fig. 2). Then, two (R,R), two (S,S) tartrate ligands and four metal ions form 'hexameric' B ring (Fig. 2). Overal, a layered, two-dimensional, coordination polymer arises. The layers encompass small channels occupied by the uncoordinated water molecules, which interact with the layers by way of O—H···O hydrogen bonds (Table 2).

Related literature top

For related literature, see: Kam et al. (2007).

Experimental top

A mixture of aqueous Mn(NO₃)₂ (2 mmol), racemic tartaric acid (2 mmol) and NaOH (4 mmol) in 20 ml water was stirred for 2 h. The resulting solution was filtered and allowed to stand in air. Slow evaporation at room temperature for several weeks yielded yellow blocks of (I).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a).

Figures top

	Fig. 1. View of (I), showing displacement ellipsoids drawn at 50% probability level (arbitrary spheres for the H atoms). Symmetry codes: (i) -x, y, 1/2 - z; (ii) 1 - x, y, 3/2 - z; (iii) x, -y, z - 1/2.
	Fig. 2. View of the layered network in (I) along [010] direction, with the A and B rings indicated (see text).

Poly[[diaqua-µ₄-tartrato-µ₂-tartrato-dimanganese(II)] dihydrate] top

Crystal data top

[Mn(C₄H₄O₆)(H₂O)]·H₂O	F(000) = 484
M_r = 239.04	D_x = 2.068 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 456 reflections
a = 11.029 (3) Å	θ = 2.8–22.3°
b = 7.3925 (18) Å	µ = 1.74 mm⁻¹
c = 10.165 (3) Å	T = 293 K
β = 112.149 (3)°	Block, yellow
V = 767.6 (3) Å³	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1507 independent reflections
Radiation source: fine-focus sealed tube	1481 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→13
T_min = 0.661, T_max = 0.739	k = −9→5
3884 measured reflections	l = −12→12

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) = 0.074	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0399P)² + 0.6888P] where P = (F_o² + 2F_c²)/3
1507 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Mn(C₄H₄O₆)(H₂O)]·H₂O	V = 767.6 (3) Å³
M_r = 239.04	Z = 4
Monoclinic, P2/c	Mo Kα radiation
a = 11.029 (3) Å	µ = 1.74 mm⁻¹
b = 7.3925 (18) Å	T = 293 K
c = 10.165 (3) Å	0.25 × 0.20 × 0.18 mm
β = 112.149 (3)°

Data collection top

Bruker SMART CCD diffractometer	1507 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1481 reflections with I > 2σ(I)
T_min = 0.661, T_max = 0.739	R_int = 0.012
3884 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.11	Δρ_max = 0.45 e Å⁻³
1507 reflections	Δρ_min = −0.69 e Å⁻³
118 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
Mn1	0.25422 (3)	0.14754 (4)	0.41123 (3)	0.01934 (13)
C1	0.13897 (18)	0.5035 (3)	0.43625 (19)	0.0179 (4)
C2	0.07525 (17)	0.4815 (2)	0.27492 (18)	0.0162 (4)
H2	0.1024	0.5821	0.2294	0.019*
C3	0.42697 (17)	−0.2562 (3)	0.74009 (19)	0.0181 (4)
H3	0.3829	−0.3503	0.6706	0.022*
C4	0.35823 (17)	−0.0765 (3)	0.68319 (19)	0.0200 (4)
O1	0.20895 (14)	0.3801 (2)	0.51027 (14)	0.0251 (3)
O2	0.11465 (16)	0.65022 (18)	0.48441 (15)	0.0242 (3)
O3	0.11895 (14)	0.31700 (19)	0.23691 (14)	0.0212 (3)
H3A	0.1245	0.3256	0.1590	0.032*
O4	0.41270 (13)	−0.30125 (19)	0.87015 (14)	0.0206 (3)
H4	0.4041	−0.4114	0.8703	0.031*
O5	0.28552 (14)	−0.00821 (19)	0.73884 (15)	0.0241 (3)
O6	0.37862 (15)	−0.0127 (2)	0.57879 (16)	0.0315 (4)
O1W	0.08037 (15)	−0.0100 (2)	0.39729 (17)	0.0306 (3)
H1WA	0.0662	−0.1156	0.3707	0.046*
H1WB	0.0915	−0.0298	0.4808	0.046*
O2W	0.6263 (2)	0.3474 (2)	0.6453 (2)	0.0511 (5)
H2WA	0.6577	0.2909	0.7200	0.077*
H2WB	0.5735	0.2819	0.5859	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.02154 (19)	0.01935 (19)	0.01749 (19)	0.00330 (10)	0.00775 (13)	0.00311 (10)
C1	0.0182 (8)	0.0198 (9)	0.0160 (9)	−0.0034 (7)	0.0067 (7)	−0.0012 (7)
C2	0.0180 (9)	0.0170 (9)	0.0139 (8)	0.0015 (7)	0.0064 (7)	0.0005 (7)
C3	0.0175 (9)	0.0200 (9)	0.0165 (8)	−0.0014 (7)	0.0060 (7)	0.0010 (7)
C4	0.0158 (8)	0.0228 (10)	0.0182 (9)	−0.0014 (7)	0.0028 (7)	0.0040 (7)
O1	0.0303 (8)	0.0254 (7)	0.0158 (7)	0.0064 (6)	0.0045 (6)	0.0005 (5)
O2	0.0358 (8)	0.0200 (7)	0.0177 (7)	0.0007 (6)	0.0110 (6)	−0.0020 (5)
O3	0.0274 (7)	0.0235 (7)	0.0143 (6)	0.0079 (6)	0.0095 (5)	0.0012 (5)
O4	0.0242 (7)	0.0193 (7)	0.0208 (7)	0.0014 (5)	0.0112 (5)	0.0051 (5)
O5	0.0274 (7)	0.0215 (7)	0.0261 (7)	0.0038 (6)	0.0131 (6)	0.0038 (5)
O6	0.0261 (7)	0.0416 (9)	0.0294 (8)	0.0111 (6)	0.0136 (6)	0.0194 (7)
O1W	0.0302 (8)	0.0250 (8)	0.0336 (8)	−0.0013 (6)	0.0086 (6)	0.0057 (6)
O2W	0.0643 (13)	0.0254 (9)	0.0473 (12)	0.0007 (8)	0.0024 (10)	0.0043 (7)

Geometric parameters (Å, º) top

Mn1—O6	2.1036 (15)	C3—C4	1.530 (3)
Mn1—O1	2.1444 (15)	C3—C3ⁱⁱⁱ	1.546 (3)
Mn1—O5ⁱ	2.1695 (15)	C3—H3	0.9800
Mn1—O1W	2.2018 (16)	C4—O5	1.249 (2)
Mn1—O3	2.2230 (14)	C4—O6	1.257 (2)
Mn1—O4ⁱ	2.2518 (14)	O3—H3A	0.8199
C1—O1	1.247 (2)	O4—Mn1^iv	2.2518 (14)
C1—O2	1.260 (2)	O4—H4	0.8198
C1—C2	1.530 (2)	O5—Mn1^iv	2.1695 (15)
C2—O3	1.415 (2)	O1W—H1WA	0.8215
C2—C2ⁱⁱ	1.542 (3)	O1W—H1WB	0.8237
C2—H2	0.9800	O2W—H2WA	0.8201
C3—O4	1.429 (2)	O2W—H2WB	0.8201

O6—Mn1—O1	105.52 (6)	C2ⁱⁱ—C2—H2	109.1
O6—Mn1—O5ⁱ	97.63 (6)	O4—C3—C4	109.91 (15)
O1—Mn1—O5ⁱ	153.64 (6)	O4—C3—C3ⁱⁱⁱ	110.62 (18)
O6—Mn1—O1W	92.32 (6)	C4—C3—C3ⁱⁱⁱ	113.12 (11)
O1—Mn1—O1W	95.92 (6)	O4—C3—H3	107.7
O5ⁱ—Mn1—O1W	95.55 (6)	C4—C3—H3	107.7
O6—Mn1—O3	178.49 (5)	C3ⁱⁱⁱ—C3—H3	107.7
O1—Mn1—O3	73.58 (5)	O5—C4—O6	125.50 (19)
O5ⁱ—Mn1—O3	83.51 (5)	O5—C4—C3	119.39 (16)
O1W—Mn1—O3	86.58 (6)	O6—C4—C3	115.08 (17)
O6—Mn1—O4ⁱ	96.86 (6)	C1—O1—Mn1	120.25 (12)
O1—Mn1—O4ⁱ	90.96 (6)	C2—O3—Mn1	117.52 (10)
O5ⁱ—Mn1—O4ⁱ	73.67 (5)	C2—O3—H3A	110.8
O1W—Mn1—O4ⁱ	166.64 (6)	Mn1—O3—H3A	122.8
O3—Mn1—O4ⁱ	84.40 (5)	C3—O4—Mn1^iv	114.70 (10)
O1—C1—O2	124.68 (17)	C3—O4—H4	106.7
O1—C1—C2	119.90 (16)	Mn1^iv—O4—H4	113.7
O2—C1—C2	115.41 (16)	C4—O5—Mn1^iv	119.92 (12)
O3—C2—C1	108.55 (14)	C4—O6—Mn1	128.71 (13)
O3—C2—C2ⁱⁱ	110.22 (11)	Mn1—O1W—H1WA	125.2
C1—C2—C2ⁱⁱ	110.78 (18)	Mn1—O1W—H1WB	103.9
O3—C2—H2	109.1	H1WA—O1W—H1WB	96.1
C1—C2—H2	109.1	H2WA—O2W—H2WB	108.4

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2W^v	0.82	1.81	2.628 (2)	175
O3—H3A···O2^vi	0.82	1.75	2.561 (2)	173
O1W—H1WA···O2^vii	0.82	2.04	2.643 (2)	130
O2W—H2WA···O5ⁱⁱⁱ	0.82	2.29	2.895 (2)	131
O2W—H2WB···O4ⁱ	0.82	2.25	2.919 (3)	140

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

Experimental details

Crystal data
Chemical formula	[Mn(C₄H₄O₆)(H₂O)]·H₂O
M_r	239.04
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	293
a, b, c (Å)	11.029 (3), 7.3925 (18), 10.165 (3)
β (°)	112.149 (3)
V (Å³)	767.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.74
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.661, 0.739
No. of measured, independent and observed [I > 2σ(I)] reflections	3884, 1507, 1481
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.074, 1.11
No. of reflections	1507
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.69

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Selected bond lengths (Å) top

Mn1—O6	2.1036 (15)	Mn1—O1W	2.2018 (16)
Mn1—O1	2.1444 (15)	Mn1—O3	2.2230 (14)
Mn1—O5ⁱ	2.1695 (15)	Mn1—O4ⁱ	2.2518 (14)

Symmetry code: (i) x, −y, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2Wⁱⁱ	0.82	1.81	2.628 (2)	175
O3—H3A···O2ⁱⁱⁱ	0.82	1.75	2.561 (2)	173
O1W—H1WA···O2^iv	0.82	2.04	2.643 (2)	130
O2W—H2WA···O5^v	0.82	2.29	2.895 (2)	131
O2W—H2WB···O4ⁱ	0.82	2.25	2.919 (3)	140

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

Acknowledgements

This project was supported by the Natural Science Foundation of the Education Bureau of Liaoning Province (grant No. 05 L159).

References

Bruker (2001). SMART (Version 5.624), SAINT (Version 6.04) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kam, K. C., Young, K. L. M. & Cheetham, A. K. (2007). Cryst. Growth Des. 7, 1522–1532. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997b). SHELXTL. University of Göttingen, Germany. Google Scholar