supplementary materials
Poly[[diaqua-![[mu]](/logos/entities/mu_rmgif.gif)
4-tartrato-2-tartrato-dimanganese(II)] dihydrate]
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.
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).
The H atoms were located in a different map, relocated in idealized positions
(C—H = 0.98 Å, O—H = 0.82 Å) and refined as riding with
Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O).
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).
Poly[[diaqua-µ
4-tartrato-µ
2-tartrato-dimanganese(II)] dihydrate]
top
Crystal data top
| [Mn(C4H4O6)(H2O)]·H2O | F000 = 484 |
| Mr = 239.04 | Dx = 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 = 2.8–22.3º |
| b = 7.3925 (18) Å | µ = 1.74 mm−1 |
| c = 10.165 (3) Å | T = 293 (2) K |
| β = 112.149 (3)º | 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) |
| Monochromator: graphite | Rint = 0.012 |
| T = 293(2) K | θmax = 26.0º |
| ω scans | θmin = 2.0º |
Absorption correction: multi-scan
(SADABS; Bruker, 2001) | h = −12→13 |
| Tmin = 0.661, Tmax = 0.739 | k = −9→5 |
| 3884 measured reflections | l = −12→12 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0399P)2 + 0.6888P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.11 | (Δ/σ)max < 0.001 |
| 1507 reflections | Δρmax = 0.45 e Å−3 |
| 118 parameters | Δρmin = −0.69 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
Crystal data top
| [Mn(C4H4O6)(H2O)]·H2O | V = 767.6 (3) Å3 |
| Mr = 239.04 | Z = 4 |
| Monoclinic, P2/c | Mo Kα |
| a = 11.029 (3) Å | µ = 1.74 mm−1 |
| b = 7.3925 (18) Å | T = 293 (2) K |
| c = 10.165 (3) Å | 0.25 × 0.20 × 0.18 mm |
| β = 112.149 (3)º | |
Data collection top
Bruker SMART CCD
diffractometer | 1507 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 2001) | 1481 reflections with I > 2σ(I) |
| Tmin = 0.661, Tmax = 0.739 | Rint = 0.012 |
| 3884 measured reflections | |
Refinement top
| R[F2 > 2σ(F2)] = 0.027 | 118 parameters |
| wR(F2) = 0.074 | H-atom parameters constrained |
| S = 1.11 | Δρmax = 0.45 e Å−3 |
| 1507 reflections | Δρmin = −0.69 e Å−3 |
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 | Uiso*/Ueq | |
| 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, °) 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—Mn1iv | 2.2518 (14) |
| C1—O2 | 1.260 (2) | O4—H4 | 0.8198 |
| C1—C2 | 1.530 (2) | O5—Mn1iv | 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—Mn1iv | 114.70 (10) |
| O1—C1—O2 | 124.68 (17) | C3—O4—H4 | 106.7 |
| O1—C1—C2 | 119.90 (16) | Mn1iv—O4—H4 | 113.7 |
| O2—C1—C2 | 115.41 (16) | C4—O5—Mn1iv | 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, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4···O2Wv | 0.82 | 1.81 | 2.628 (2) | 175 |
| O3—H3A···O2vi | 0.82 | 1.75 | 2.561 (2) | 173 |
| O1W—H1WA···O2vii | 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: (v) −x+1, y−1, −z+3/2; (vi) x, −y+1, z−1/2; (vii) x, y−1, z; (iii) −x+1, y, −z+3/2; (i) x, −y, z−1/2. |
Table 1
Selected geometric parameters (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 codes: (i) x, −y, z−1/2. |
Table 2
Hydrogen-bond geometry (Å, °) 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···O2iv | 0.82 | 2.04 | 2.643 (2) | 130 |
| O2W—H2WA···O5v | 0.82 | 2.29 | 2.895 (2) | 131 |
| O2W—H2WB···O4i | 0.82 | 2.25 | 2.919 (3) | 140 |
| Symmetry codes: (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; (i) x, −y, z−1/2. |
This project was supported by the Natural Science Foundation of the Education
Bureau of Liaoning Province (grant No. 05 L159).
Bruker (2001). SMART (Version 5.624), SAINT (Version 6.04) and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.
Kam, K. C., Young, K. L. M. & Cheetham, A. K. (2007). Cryst. Growth Des. 7, 1522–1532.
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Sheldrick, G. M. (1997b). SHELXTL. University of Göttingen, Germany.
![[Figure 1]](./hb2676fig1thm.gif)
![[Figure 2]](./hb2676fig2thm.gif)
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).