Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039773/gg2036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039773/gg2036Isup2.hkl |
CCDC reference: 1283839
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.045
- wR factor = 0.117
- Data-to-parameter ratio = 10.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.97 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Mn1 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.20 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.50 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For studies and reviews of inorganic–organic hybrid materials, see: Chung et al. (1971); Okabe & Oya (2000); Serre et al. (2005); Pocker & Fong (1980); Scapin et al. (1997); Kim et al. (2001). For the isostructural analogues, see: CoII: Delgado et al. (2003); NiII: Liu et al. (2005); ZnII: Zhang et al. (2003 or 2007); Delgado et al. (2003); CdII: Mao et al. (2004).
For related literature, see: Delgado et al. (2004); Zhang et al. (2003).
A mixture of manganese(II) sulfate (0.5 mmol), malonate acid (0.5 mmol), sodium hydroxide (1 mmol), pyrazine (1 mmol) and H2O (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was heated at 443 K for two days, and then cooled to room temperature. block crystals of complex (I) were obtained with a yield of 22%. Anal. Calc. for C5H6NMnO5: C 27.91, H 2.79, N 6.51%; Found: C 27.88, H 2.75, N 6.47%.
All H atoms on C atoms were generated geometrically and treated as riding atoms with C—H= 0.93Å and Uiso(H)= 1.2 times Ueq(C). The H atoms of the water molecule were located from difference density maps and were refined with distance restraints of d(H–H) = 1.38 (2) Å, d(O–H) = 0.82 (1) Å.
In recent years, dicarboxylic acids have been widely used as polydentate ligands, which undergo various metal chelation reactions to form transition or rare earth metal complexes with interesting properties in materials science and in biological systems (Church et al., 1971; Okabe & Oya, 2000; Serre et al., 2005; Pocker & Fong, 1980; Scapin et al., 1997). For example, Kim et al. (2001) focused on the syntheses of transition metal complexes containing benzene dicarboxylate and rigid aromatic pyridine ligands in order to study their electronic conductivity and magnetic properties. The importance of transition metal dicarboxylate complexes in materials science and biological systems prompted us to pursue synthetic strategies for these compounds, using malonate as a polydentate ligand and pyrazine as a rigid aromatic ligand. In this paper, we report the synthesis and X-ray crystal structure analysis of the title compound, [Mn2(C3H2O4)2(C4H4N2)(H2O)2]n.
The MnII atom has sixfold coordination, chelated by two O atoms from one malonate ligand to form a six-membered boat-type ring, and by two O atoms from two neighbouring malonates, one aqua molecule and one N atom from the bridging pyrazine ligand (Fig. 1). The Mn—O(carboxylate) and Mn—N bond lengths are in the range 2.060 (4) to 2.220 (4) and 2.269 (4) Å, respectively.
The packing diagram is shown in Fig. 2. If the pyrazine bridges are neglected, a two-dimensional network is formed by the [Mn(malonate)(H2O)] moieties parallel to the (010) plane. There are hydrogen bonds (Table 2) between the aqua and malonate ligands in this network.
For studies and reviews of inorganic–organic hybrid materials, see: Chung et al. (1971); Okabe & Oya (2000); Serre et al. (2005); Pocker & Fong (1980); Scapin et al. (1997); Kim et al. (2001). For the isostructural analogues, see: CoII: Delgado et al. (2003); NiII: Liu et al. (2005); ZnII: Zhang et al. (2003 or 2007); Delgado et al. (2003); CdII: Mao et al. (2004).
For related literature, see: Delgado et al. (2004); Zhang et al. (2003).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Mn2(C3H2O4)2(C4H4N2)(H2O)2] | F(000) = 432 |
Mr = 430.10 | Dx = 1.908 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1314 reflections |
a = 7.0127 (10) Å | θ = 2.8–25.1° |
b = 14.490 (2) Å | µ = 1.74 mm−1 |
c = 7.3711 (10) Å | T = 293 K |
β = 92.182 (1)° | Block, colorless |
V = 748.45 (18) Å3 | 0.36 × 0.28 × 0.24 mm |
Z = 2 |
Bruker APEX II CCD area-detector diffractometer | 1314 independent reflections |
Radiation source: fine-focus sealed tube | 1103 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
φ and ω scans | θmax = 25.1°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→3 |
Tmin = 0.573, Tmax = 0.680 | k = −13→16 |
2397 measured reflections | l = −8→8 |
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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0636P)2 + 2.2589P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.013 |
1314 reflections | Δρmax = 0.72 e Å−3 |
116 parameters | Δρmin = −0.40 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.051 (5) |
[Mn2(C3H2O4)2(C4H4N2)(H2O)2] | V = 748.45 (18) Å3 |
Mr = 430.10 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.0127 (10) Å | µ = 1.74 mm−1 |
b = 14.490 (2) Å | T = 293 K |
c = 7.3711 (10) Å | 0.36 × 0.28 × 0.24 mm |
β = 92.182 (1)° |
Bruker APEX II CCD area-detector diffractometer | 1314 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1103 reflections with I > 2σ(I) |
Tmin = 0.573, Tmax = 0.680 | Rint = 0.023 |
2397 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 3 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.72 e Å−3 |
1314 reflections | Δρmin = −0.40 e Å−3 |
116 parameters |
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 | ||
C3 | 0.5846 (7) | 0.3318 (3) | 0.7561 (7) | 0.0344 (11) | |
C4 | 0.6125 (8) | 0.3910 (4) | 0.5887 (7) | 0.0432 (12) | |
H4A | 0.7407 | 0.4162 | 0.5951 | 0.052* | |
H4B | 0.5240 | 0.4424 | 0.5904 | 0.052* | |
C5 | 0.5834 (7) | 0.3404 (3) | 0.4123 (7) | 0.0348 (11) | |
C2 | 0.4526 (8) | 0.0744 (4) | 0.5906 (8) | 0.0507 (14) | |
H2 | 0.4135 | 0.1258 | 0.6549 | 0.061* | |
C1 | 0.6785 (7) | −0.0046 (4) | 0.4448 (8) | 0.0468 (13) | |
H1 | 0.8016 | −0.0106 | 0.4036 | 0.056* | |
Mn1 | 0.83760 (8) | 0.19134 (4) | 0.58103 (7) | 0.0172 (3) | |
N1 | 0.6323 (6) | 0.0717 (3) | 0.5372 (6) | 0.0389 (10) | |
O2 | 0.6638 (5) | 0.2528 (3) | 0.7693 (5) | 0.0433 (9) | |
O5 | 0.4862 (5) | 0.3675 (2) | 0.8747 (5) | 0.0435 (9) | |
O3 | 0.6698 (5) | 0.2644 (3) | 0.3903 (5) | 0.0464 (9) | |
O4 | 0.4753 (5) | 0.3775 (2) | 0.2943 (5) | 0.0427 (9) | |
O1 | 1.0317 (6) | 0.3107 (3) | 0.5859 (5) | 0.0473 (9) | |
H2W | 1.087 (8) | 0.313 (5) | 0.489 (4) | 0.080* | |
H1W | 1.104 (7) | 0.303 (5) | 0.675 (5) | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C3 | 0.038 (2) | 0.031 (3) | 0.034 (2) | 0.000 (2) | 0.0003 (19) | −0.005 (2) |
C4 | 0.060 (3) | 0.035 (3) | 0.034 (3) | 0.005 (2) | 0.003 (2) | 0.000 (2) |
C5 | 0.039 (2) | 0.029 (3) | 0.036 (3) | 0.003 (2) | 0.005 (2) | 0.004 (2) |
C2 | 0.048 (3) | 0.042 (3) | 0.063 (4) | −0.006 (3) | 0.018 (3) | −0.014 (3) |
C1 | 0.041 (3) | 0.037 (3) | 0.063 (4) | −0.002 (2) | 0.012 (2) | −0.009 (3) |
Mn1 | 0.0218 (4) | 0.0155 (4) | 0.0144 (4) | 0.0007 (2) | 0.0018 (2) | −0.0006 (2) |
N1 | 0.039 (2) | 0.036 (2) | 0.042 (2) | −0.0017 (18) | 0.0021 (17) | −0.0012 (19) |
O2 | 0.056 (2) | 0.039 (2) | 0.0350 (19) | 0.0076 (17) | 0.0117 (16) | 0.0031 (15) |
O5 | 0.049 (2) | 0.040 (2) | 0.043 (2) | 0.0044 (16) | 0.0172 (16) | −0.0004 (17) |
O3 | 0.058 (2) | 0.045 (2) | 0.0355 (19) | 0.0118 (18) | −0.0044 (16) | −0.0029 (16) |
O4 | 0.053 (2) | 0.0347 (19) | 0.0399 (19) | 0.0032 (17) | −0.0064 (16) | 0.0032 (16) |
O1 | 0.051 (2) | 0.055 (2) | 0.037 (2) | −0.0021 (18) | 0.0019 (16) | 0.0004 (18) |
C3—O5 | 1.246 (6) | C1—C2i | 1.386 (8) |
C3—O2 | 1.275 (6) | C1—H1 | 0.9300 |
C3—C4 | 1.521 (7) | Mn1—O5ii | 2.060 (3) |
C4—C5 | 1.500 (7) | Mn1—O4iii | 2.070 (4) |
C4—H4A | 0.9700 | Mn1—O3 | 2.087 (4) |
C4—H4B | 0.9700 | Mn1—O2 | 2.082 (3) |
C5—O4 | 1.254 (6) | Mn1—O1 | 2.200 (4) |
C5—O3 | 1.270 (7) | Mn1—N1 | 2.269 (4) |
C2—N1 | 1.335 (7) | O5—Mn1iv | 2.060 (3) |
C2—C1i | 1.386 (8) | O4—Mn1v | 2.070 (4) |
C2—H2 | 0.9300 | O1—H2W | 0.83 (4) |
C1—N1 | 1.344 (7) | O1—H1W | 0.82 (4) |
O5—C3—O2 | 124.7 (5) | O4iii—Mn1—O2 | 88.18 (14) |
O5—C3—C4 | 115.3 (4) | O3—Mn1—O2 | 84.41 (14) |
O2—C3—C4 | 119.9 (4) | O5ii—Mn1—O1 | 90.42 (14) |
C3—C4—C5 | 114.2 (4) | O4iii—Mn1—O1 | 95.52 (14) |
C3—C4—H4A | 108.7 | O3—Mn1—O1 | 86.84 (16) |
C5—C4—H4A | 108.7 | O2—Mn1—O1 | 91.75 (15) |
C3—C4—H4B | 108.7 | O5ii—Mn1—N1 | 85.11 (15) |
C5—C4—H4B | 108.7 | O4iii—Mn1—N1 | 90.85 (15) |
H4A—C4—H4B | 107.6 | O3—Mn1—N1 | 87.32 (16) |
O4—C5—O3 | 124.2 (5) | O2—Mn1—N1 | 92.14 (15) |
O4—C5—C4 | 116.8 (4) | O1—Mn1—N1 | 172.65 (15) |
O3—C5—C4 | 119.0 (4) | C2—N1—C1 | 115.0 (4) |
N1—C2—C1i | 123.3 (5) | C2—N1—Mn1 | 122.4 (4) |
N1—C2—H2 | 118.3 | C1—N1—Mn1 | 122.4 (3) |
C1i—C2—H2 | 118.3 | C3—O2—Mn1 | 126.7 (3) |
N1—C1—C2i | 121.7 (5) | C3—O5—Mn1iv | 131.0 (3) |
N1—C1—H1 | 119.2 | C5—O3—Mn1 | 127.8 (3) |
C2i—C1—H1 | 119.2 | C5—O4—Mn1v | 124.9 (3) |
O5ii—Mn1—O4iii | 97.27 (15) | Mn1—O1—H2W | 109 (5) |
O5ii—Mn1—O3 | 90.03 (15) | Mn1—O1—H1W | 105 (5) |
O4iii—Mn1—O3 | 172.30 (14) | H2W—O1—H1W | 114 (3) |
O5ii—Mn1—O2 | 173.92 (15) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x−1/2, −y+1/2, z+1/2; (v) x−1/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H2W···O2ii | 0.83 (4) | 1.97 (4) | 2.705 (5) | 148 (7) |
O1—H1W···O3iii | 0.82 (4) | 1.90 (4) | 2.644 (5) | 149 (7) |
Symmetry codes: (ii) x+1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn2(C3H2O4)2(C4H4N2)(H2O)2] |
Mr | 430.10 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.0127 (10), 14.490 (2), 7.3711 (10) |
β (°) | 92.182 (1) |
V (Å3) | 748.45 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.74 |
Crystal size (mm) | 0.36 × 0.28 × 0.24 |
Data collection | |
Diffractometer | Bruker APEX II CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.573, 0.680 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2397, 1314, 1103 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.117, 1.00 |
No. of reflections | 1314 |
No. of parameters | 116 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.72, −0.40 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H2W···O2i | 0.83 (4) | 1.97 (4) | 2.705 (5) | 148 (7) |
O1—H1W···O3ii | 0.82 (4) | 1.90 (4) | 2.644 (5) | 149 (7) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2. |
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In recent years, dicarboxylic acids have been widely used as polydentate ligands, which undergo various metal chelation reactions to form transition or rare earth metal complexes with interesting properties in materials science and in biological systems (Church et al., 1971; Okabe & Oya, 2000; Serre et al., 2005; Pocker & Fong, 1980; Scapin et al., 1997). For example, Kim et al. (2001) focused on the syntheses of transition metal complexes containing benzene dicarboxylate and rigid aromatic pyridine ligands in order to study their electronic conductivity and magnetic properties. The importance of transition metal dicarboxylate complexes in materials science and biological systems prompted us to pursue synthetic strategies for these compounds, using malonate as a polydentate ligand and pyrazine as a rigid aromatic ligand. In this paper, we report the synthesis and X-ray crystal structure analysis of the title compound, [Mn2(C3H2O4)2(C4H4N2)(H2O)2]n.
The MnII atom has sixfold coordination, chelated by two O atoms from one malonate ligand to form a six-membered boat-type ring, and by two O atoms from two neighbouring malonates, one aqua molecule and one N atom from the bridging pyrazine ligand (Fig. 1). The Mn—O(carboxylate) and Mn—N bond lengths are in the range 2.060 (4) to 2.220 (4) and 2.269 (4) Å, respectively.
The packing diagram is shown in Fig. 2. If the pyrazine bridges are neglected, a two-dimensional network is formed by the [Mn(malonate)(H2O)] moieties parallel to the (010) plane. There are hydrogen bonds (Table 2) between the aqua and malonate ligands in this network.