Acta Cryst. (2009). E65, m1126 [ doi:10.1107/S1600536809033078 ]
In the title compound, [Mn(C11H8N3O2S)2(H2O)4]·2H2O, the MnII ion lies on an inversion centre and is coordinated by four water molecules in equatorial positions and two N atoms from two 2-[4-(3-pyridyl)pyrimidin-2-ylsulfanyl]acetate ligands in the axial positions. The water molecules, including the uncoordinated water molecules, and the acetate O atoms are involved in O-H
O and O-HN hydrogen-bonding interactions, which link the components into layers parallel to the a (b + c) plane.
The mixture of Mn(OAc)2 (0.1 mmol), 2-(4-(pyridine-3-yl)pyrimidin-2-ylthio)acetic acid (0.2 mmol) and NaOH (0.2 mmol) in 6 ml of H2O was stirred for 20 min at room temperature. After filtration, the mother liquid was stood for one week to give the colorless crystals suitable for X-raydiffraction analysis.
C-bound H atoms were positioned geometrically (C—H =0.93 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2 Ueq(C). The positions of the water H atoms were found from a difference Fourier map, but placed in idealized positions (O—H = 0.85 Å), and refined as riding with Uiso(H) = 1.2 Ueq(O5).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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).
![[Figure 1]](./cv2600fig1thm.gif)
| Fig. 1. The coordination environment around Mn(II) in the title complex with the atom-labeling scheme [symmetry code: (A) -x, 2-y, 1-z]. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level. |
| [Mn(C11H8N3O2S)2(H2O)4]·2H2O | Z = 1 |
| Mr = 655.58 | F(000) = 339 |
| Triclinic, P1 | Dx = 1.559 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.459 (3) Å | Cell parameters from 3181 reflections |
| b = 9.240 (3) Å | θ = 2.2–28.1° |
| c = 9.360 (4) Å | µ = 0.69 mm−1 |
| α = 87.396 (6)° | T = 298 K |
| β = 75.862 (5)° | Block, colourless |
| γ = 79.872 (5)° | 0.14 × 0.12 × 0.10 mm |
| V = 698.4 (4) Å3 |
| Bruker APEXII CCD area-detector diffractometer | 3181 independent reflections |
| Radiation source: fine-focus sealed tube | 2443 reflections with I > 2σ(I) |
| graphite | Rint = 0.031 |
| φ and ω scans | θmax = 28.1°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→10 |
| Tmin = 0.884, Tmax = 0.920 | k = −6→12 |
| 4518 measured reflections | l = −11→10 |
| 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.094 | H-atom parameters constrained |
| S = 0.98 | w = 1/[σ2(Fo2) + (0.0441P)2] where P = (Fo2 + 2Fc2)/3 |
| 3181 reflections | (Δ/σ)max < 0.001 |
| 187 parameters | Δρmax = 0.49 e Å−3 |
| 0 restraints | Δρmin = −0.55 e Å−3 |
| [Mn(C11H8N3O2S)2(H2O)4]·2H2O | γ = 79.872 (5)° |
| Mr = 655.58 | V = 698.4 (4) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 8.459 (3) Å | Mo Kα radiation |
| b = 9.240 (3) Å | µ = 0.69 mm−1 |
| c = 9.360 (4) Å | T = 298 K |
| α = 87.396 (6)° | 0.14 × 0.12 × 0.10 mm |
| β = 75.862 (5)° |
| Bruker APEXII CCD area-detector diffractometer | 3181 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2443 reflections with I > 2σ(I) |
| Tmin = 0.884, Tmax = 0.920 | Rint = 0.031 |
| 4518 measured reflections | θmax = 28.1° |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.094 | Δρmax = 0.49 e Å−3 |
| S = 0.98 | Δρmin = −0.55 e Å−3 |
| 3181 reflections | Absolute structure: ? |
| 187 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| Mn1 | 0.0000 | 1.0000 | 0.5000 | 0.02786 (13) | |
| S1 | 0.71353 (7) | 0.62719 (6) | 0.00440 (6) | 0.03937 (16) | |
| O1 | 0.12141 (17) | 0.98576 (16) | 0.26485 (16) | 0.0383 (4) | |
| O2 | 0.24139 (17) | 1.03191 (17) | 0.52792 (17) | 0.0447 (4) | |
| N2 | 0.49123 (19) | 0.56249 (17) | 0.24128 (18) | 0.0291 (4) | |
| O4 | 0.44775 (17) | 0.95387 (16) | 0.25780 (16) | 0.0412 (4) | |
| N1 | 0.6987 (2) | 0.36606 (19) | 0.1238 (2) | 0.0379 (4) | |
| C1 | 0.6227 (2) | 0.5074 (2) | 0.1385 (2) | 0.0310 (4) | |
| O3 | 0.71010 (18) | 0.85073 (17) | 0.23595 (17) | 0.0455 (4) | |
| C5 | 0.2749 (2) | 0.5349 (2) | 0.4544 (2) | 0.0279 (4) | |
| N3 | 0.0768 (2) | 0.75451 (18) | 0.53326 (19) | 0.0335 (4) | |
| C11 | 0.5782 (2) | 0.8717 (2) | 0.1953 (2) | 0.0302 (4) | |
| C4 | 0.4233 (2) | 0.4687 (2) | 0.3417 (2) | 0.0295 (4) | |
| C9 | 0.2097 (2) | 0.6826 (2) | 0.4396 (2) | 0.0323 (5) | |
| H9A | 0.2621 | 0.7342 | 0.3595 | 0.039* | |
| C10 | 0.5730 (3) | 0.7975 (2) | 0.0536 (2) | 0.0342 (5) | |
| H10A | 0.5956 | 0.8662 | −0.0272 | 0.041* | |
| H10B | 0.4614 | 0.7793 | 0.0633 | 0.041* | |
| C6 | 0.1962 (3) | 0.4588 (2) | 0.5742 (2) | 0.0354 (5) | |
| H6A | 0.2354 | 0.3600 | 0.5882 | 0.042* | |
| C8 | 0.0031 (3) | 0.6779 (2) | 0.6484 (2) | 0.0364 (5) | |
| H8A | −0.0899 | 0.7256 | 0.7149 | 0.044* | |
| C7 | 0.0596 (3) | 0.5315 (2) | 0.6721 (2) | 0.0394 (5) | |
| H7A | 0.0058 | 0.4824 | 0.7534 | 0.047* | |
| C2 | 0.6305 (3) | 0.2757 (2) | 0.2252 (3) | 0.0415 (5) | |
| H2C | 0.6786 | 0.1769 | 0.2209 | 0.050* | |
| C3 | 0.4920 (3) | 0.3206 (2) | 0.3369 (3) | 0.0402 (5) | |
| H3A | 0.4466 | 0.2544 | 0.4060 | 0.048* | |
| O5 | 1.0477 (2) | 0.7838 (2) | 0.1129 (2) | 0.0871 (8) | |
| H1 | 0.2712 | 1.0656 | 0.5985 | 0.105* | |
| H2 | 0.2259 | 0.9808 | 0.2469 | 0.105* | |
| H3 | 0.3309 | 1.0079 | 0.4625 | 0.105* | |
| H4 | 0.0999 | 0.9300 | 0.2053 | 0.105* | |
| H5 | 1.0980 | 0.7268 | 0.0413 | 0.105* | |
| H6 | 0.9449 | 0.7871 | 0.1208 | 0.105* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.0239 (2) | 0.0266 (2) | 0.0312 (3) | −0.00261 (17) | −0.00359 (17) | −0.00345 (17) |
| S1 | 0.0421 (3) | 0.0381 (3) | 0.0316 (3) | −0.0063 (2) | 0.0042 (2) | −0.0080 (2) |
| O1 | 0.0354 (8) | 0.0416 (9) | 0.0347 (8) | −0.0006 (7) | −0.0053 (6) | −0.0082 (6) |
| O2 | 0.0289 (8) | 0.0619 (11) | 0.0447 (10) | −0.0092 (7) | −0.0080 (7) | −0.0149 (8) |
| N2 | 0.0291 (9) | 0.0264 (9) | 0.0310 (9) | −0.0038 (7) | −0.0055 (7) | −0.0033 (7) |
| O4 | 0.0305 (8) | 0.0442 (9) | 0.0447 (9) | −0.0013 (7) | −0.0023 (7) | −0.0141 (7) |
| N1 | 0.0360 (10) | 0.0308 (10) | 0.0452 (11) | 0.0008 (8) | −0.0091 (8) | −0.0125 (8) |
| C1 | 0.0313 (11) | 0.0301 (11) | 0.0339 (12) | −0.0060 (8) | −0.0105 (9) | −0.0066 (8) |
| O3 | 0.0342 (8) | 0.0558 (10) | 0.0482 (10) | −0.0005 (7) | −0.0147 (7) | −0.0200 (8) |
| C5 | 0.0274 (10) | 0.0260 (10) | 0.0319 (11) | −0.0056 (8) | −0.0095 (8) | 0.0004 (8) |
| N3 | 0.0293 (9) | 0.0303 (9) | 0.0371 (10) | −0.0036 (7) | −0.0019 (7) | −0.0008 (7) |
| C11 | 0.0309 (11) | 0.0293 (11) | 0.0301 (11) | −0.0086 (8) | −0.0039 (8) | −0.0006 (8) |
| C4 | 0.0304 (10) | 0.0259 (10) | 0.0344 (11) | −0.0039 (8) | −0.0125 (9) | −0.0017 (8) |
| C9 | 0.0314 (11) | 0.0267 (10) | 0.0361 (12) | −0.0048 (8) | −0.0035 (9) | 0.0027 (8) |
| C10 | 0.0415 (12) | 0.0325 (11) | 0.0283 (11) | −0.0068 (9) | −0.0075 (9) | 0.0003 (8) |
| C6 | 0.0428 (12) | 0.0274 (11) | 0.0374 (12) | −0.0076 (9) | −0.0121 (10) | 0.0045 (9) |
| C8 | 0.0324 (11) | 0.0390 (12) | 0.0342 (12) | −0.0070 (9) | −0.0003 (9) | −0.0015 (9) |
| C7 | 0.0427 (13) | 0.0403 (13) | 0.0335 (12) | −0.0119 (10) | −0.0036 (10) | 0.0084 (9) |
| C2 | 0.0462 (13) | 0.0246 (11) | 0.0512 (14) | 0.0041 (10) | −0.0130 (11) | −0.0077 (10) |
| C3 | 0.0456 (13) | 0.0253 (11) | 0.0470 (14) | −0.0031 (9) | −0.0081 (11) | 0.0008 (9) |
| O5 | 0.0420 (10) | 0.1175 (19) | 0.0989 (17) | −0.0176 (11) | 0.0041 (11) | −0.0692 (14) |
| Mn1—O1 | 2.1889 (16) | C5—C9 | 1.393 (3) |
| Mn1—O1i | 2.1889 (16) | C5—C4 | 1.485 (3) |
| Mn1—O2i | 2.1919 (15) | N3—C9 | 1.335 (2) |
| Mn1—O2 | 2.1919 (15) | N3—C8 | 1.345 (3) |
| Mn1—N3i | 2.2761 (18) | C11—C10 | 1.534 (3) |
| Mn1—N3 | 2.2761 (18) | C4—C3 | 1.388 (3) |
| S1—C1 | 1.759 (2) | C9—H9A | 0.9300 |
| S1—C10 | 1.800 (2) | C10—H10A | 0.9700 |
| O1—H2 | 0.8520 | C10—H10B | 0.9700 |
| O1—H4 | 0.8477 | C6—C7 | 1.375 (3) |
| O2—H1 | 0.8510 | C6—H6A | 0.9300 |
| O2—H3 | 0.8511 | C8—C7 | 1.380 (3) |
| N2—C1 | 1.320 (2) | C8—H8A | 0.9300 |
| N2—C4 | 1.342 (3) | C7—H7A | 0.9300 |
| O4—C11 | 1.252 (2) | C2—C3 | 1.382 (3) |
| N1—C2 | 1.327 (3) | C2—H2C | 0.9300 |
| N1—C1 | 1.347 (2) | C3—H3A | 0.9300 |
| O3—C11 | 1.246 (2) | O5—H5 | 0.8500 |
| C5—C6 | 1.386 (3) | O5—H6 | 0.8501 |
| O1—Mn1—O1i | 180.000 (1) | C8—N3—Mn1 | 123.89 (14) |
| O1—Mn1—O2i | 95.09 (6) | O3—C11—O4 | 125.43 (18) |
| O1i—Mn1—O2i | 84.91 (6) | O3—C11—C10 | 118.76 (18) |
| O1—Mn1—O2 | 84.91 (6) | O4—C11—C10 | 115.76 (18) |
| O1i—Mn1—O2 | 95.09 (6) | N2—C4—C3 | 120.38 (18) |
| O2i—Mn1—O2 | 180.00 (8) | N2—C4—C5 | 115.60 (16) |
| O1—Mn1—N3i | 87.81 (6) | C3—C4—C5 | 124.02 (18) |
| O1i—Mn1—N3i | 92.19 (6) | N3—C9—C5 | 124.01 (18) |
| O2i—Mn1—N3i | 88.48 (6) | N3—C9—H9A | 118.0 |
| O2—Mn1—N3i | 91.52 (6) | C5—C9—H9A | 118.0 |
| O1—Mn1—N3 | 92.19 (6) | C11—C10—S1 | 116.57 (14) |
| O1i—Mn1—N3 | 87.81 (6) | C11—C10—H10A | 108.1 |
| O2i—Mn1—N3 | 91.52 (6) | S1—C10—H10A | 108.1 |
| O2—Mn1—N3 | 88.48 (6) | C11—C10—H10B | 108.1 |
| N3i—Mn1—N3 | 180.000 (1) | S1—C10—H10B | 108.1 |
| C1—S1—C10 | 101.21 (10) | H10A—C10—H10B | 107.3 |
| Mn1—O1—H2 | 113.5 | C7—C6—C5 | 119.14 (19) |
| Mn1—O1—H4 | 123.8 | C7—C6—H6A | 120.4 |
| H2—O1—H4 | 108.6 | C5—C6—H6A | 120.4 |
| Mn1—O2—H1 | 132.6 | N3—C8—C7 | 122.84 (19) |
| Mn1—O2—H3 | 122.8 | N3—C8—H8A | 118.6 |
| H1—O2—H3 | 104.6 | C7—C8—H8A | 118.6 |
| C1—N2—C4 | 117.31 (17) | C6—C7—C8 | 119.36 (19) |
| C2—N1—C1 | 114.58 (18) | C6—C7—H7A | 120.3 |
| N2—C1—N1 | 127.05 (19) | C8—C7—H7A | 120.3 |
| N2—C1—S1 | 118.41 (15) | N1—C2—C3 | 123.44 (19) |
| N1—C1—S1 | 114.55 (15) | N1—C2—H2C | 118.3 |
| C6—C5—C9 | 117.58 (18) | C3—C2—H2C | 118.3 |
| C6—C5—C4 | 124.11 (18) | C2—C3—C4 | 117.2 (2) |
| C9—C5—C4 | 118.31 (17) | C2—C3—H3A | 121.4 |
| C9—N3—C8 | 117.06 (18) | C4—C3—H3A | 121.4 |
| C9—N3—Mn1 | 118.88 (13) | H5—O5—H6 | 106.5 |
| C4—N2—C1—N1 | −0.9 (3) | C9—C5—C4—C3 | −174.50 (19) |
| C4—N2—C1—S1 | 179.48 (14) | C8—N3—C9—C5 | 0.1 (3) |
| C2—N1—C1—N2 | 0.1 (3) | Mn1—N3—C9—C5 | 175.57 (15) |
| C2—N1—C1—S1 | 179.79 (15) | C6—C5—C9—N3 | −0.1 (3) |
| C10—S1—C1—N2 | −3.72 (17) | C4—C5—C9—N3 | 179.86 (18) |
| C10—S1—C1—N1 | 176.59 (14) | O3—C11—C10—S1 | 28.1 (3) |
| O1—Mn1—N3—C9 | 24.51 (15) | O4—C11—C10—S1 | −154.45 (16) |
| O1i—Mn1—N3—C9 | −155.49 (15) | C1—S1—C10—C11 | 71.70 (17) |
| O2i—Mn1—N3—C9 | 119.67 (15) | C9—C5—C6—C7 | −0.2 (3) |
| O2—Mn1—N3—C9 | −60.33 (15) | C4—C5—C6—C7 | 179.86 (19) |
| O1—Mn1—N3—C8 | −160.35 (16) | C9—N3—C8—C7 | 0.2 (3) |
| O1i—Mn1—N3—C8 | 19.65 (16) | Mn1—N3—C8—C7 | −175.02 (15) |
| O2i—Mn1—N3—C8 | −65.20 (17) | C5—C6—C7—C8 | 0.5 (3) |
| O2—Mn1—N3—C8 | 114.80 (17) | N3—C8—C7—C6 | −0.5 (3) |
| C1—N2—C4—C3 | 0.9 (3) | C1—N1—C2—C3 | 0.6 (3) |
| C1—N2—C4—C5 | −179.45 (16) | N1—C2—C3—C4 | −0.5 (3) |
| C6—C5—C4—N2 | −174.15 (19) | N2—C4—C3—C2 | −0.3 (3) |
| C9—C5—C4—N2 | 5.9 (3) | C5—C4—C3—C2 | −179.9 (2) |
| C6—C5—C4—C3 | 5.5 (3) |
| Symmetry codes: (i) −x, −y+2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H1···O3ii | 0.85 | 1.82 | 2.655 (2) | 168 |
| O1—H2···O4 | 0.85 | 1.88 | 2.709 (2) | 165 |
| O2—H3···O4 | 0.85 | 1.97 | 2.743 (2) | 150 |
| O1—H4···O5iii | 0.85 | 1.81 | 2.642 (3) | 167 |
| O5—H5···N1iv | 0.85 | 2.09 | 2.888 (3) | 155 |
| O5—H6···O3 | 0.85 | 2.01 | 2.775 (3) | 149 |
| Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x−1, y, z; (iv) −x+2, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H1···O3i | 0.85 | 1.82 | 2.655 (2) | 168 |
| O1—H2···O4 | 0.85 | 1.88 | 2.709 (2) | 165 |
| O2—H3···O4 | 0.85 | 1.97 | 2.743 (2) | 150 |
| O1—H4···O5ii | 0.85 | 1.81 | 2.642 (3) | 167 |
| O5—H5···N1iii | 0.85 | 2.09 | 2.888 (3) | 155 |
| O5—H6···O3 | 0.85 | 2.01 | 2.775 (3) | 149 |
| Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z; (iii) −x+2, −y+1, −z. |
The authors acknowledge financial support from the China Postdoctoral Research Fund (grant No. 20070411010) and the Young Teachers' Starting Fund of Southeast University.
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Hydro(solvo)thermal reactions of (heterocyclicthio)acetic acid with both transition metal ions and lanthanide ions have been investigated in several reports (Zhu et al., 2009; Hao et al., 2008; He et al., 2007), wherein in situ C—S cleavage has taken place under these situations. Herein, we report a manganese (II) coordination complex with a newly synthesized (heterocyclicthio)acetic acid, namely 2-(4-(pyridine-3-yl)pyrimidin-2-ylthio)acetic acid.
As shown in Fig. 1, the coordination arrangement around Mn(II) center is similar to our previously reported Cu(II) compound with the ligand of 4-(pyridin-4-yl)pyrimidine-2-sulfonate (Li et al., 2009). The Mn(II) center also adopts an octahedral coordination geometry completed by four water O atoms in equatorial positions and two N atoms in apical positions. In the title complex, the MnII atom sits on an inversion centre with the asymmetric unit containing half of the complex and one free water molecule. The Mn—O bond lengths vary from 2.189 (2) to 2.192 (2) Å and the Mn—N bond distance is 2.276 (2) Å. Intra- and intermolecular hydrogen bonding interactions, such as O—H···O and O—H···N are observed in the crystal structure (Table 1).