Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109022331/sk3329sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109022331/sk3329Isup2.hkl |
CCDC reference: 746035
Manganese chloride hexahydrate (0.119 g, 0.5 mmol), H2chdc (0.135 g, 0.5 mmol) and 1,4-bix (0.093 g, 0.5 mmol) were placed in water (13 ml), and triethylamine was added until the pH value of the solution was 5.5. The solution was heated in a 23 ml Teflon-lined stainless steel autoclave at 445 K for 3 d. The autoclave was allowed to cool to room temperature over several hours. Block crystals of (I) were isolated in about 47% yield.
Carbon-bound H atoms were positioned geometrically, with C—H = 0.93 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C). The water H atoms were located in a difference Fourier map, and were refined freely.
Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); 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-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Mn(C8H10O4)(C14H14N4)(H2O)2] | Z = 1 |
Mr = 499.42 | F(000) = 261 |
Triclinic, P1 | Dx = 1.489 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.6645 (2) Å | Cell parameters from 2255 reflections |
b = 9.4282 (6) Å | θ = 3.0–26.4° |
c = 10.7437 (5) Å | µ = 0.64 mm−1 |
α = 91.907 (4)° | T = 293 K |
β = 95.553 (3)° | Block, colourless |
γ = 102.426 (4)° | 0.23 × 0.19 × 0.16 mm |
V = 556.84 (5) Å3 |
Bruker APEX diffractometer | 2255 independent reflections |
Radiation source: sealed tube | 1887 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ϕ and ω scans | θmax = 26.4°, θmin = 4.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→6 |
Tmin = 0.861, Tmax = 0.906 | k = −11→10 |
5312 measured reflections | l = −12→13 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.015P] where P = (Fo2 + 2Fc2)/3 |
2255 reflections | (Δ/σ)max < 0.001 |
159 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
[Mn(C8H10O4)(C14H14N4)(H2O)2] | γ = 102.426 (4)° |
Mr = 499.42 | V = 556.84 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.6645 (2) Å | Mo Kα radiation |
b = 9.4282 (6) Å | µ = 0.64 mm−1 |
c = 10.7437 (5) Å | T = 293 K |
α = 91.907 (4)° | 0.23 × 0.19 × 0.16 mm |
β = 95.553 (3)° |
Bruker APEX diffractometer | 2255 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1887 reflections with I > 2σ(I) |
Tmin = 0.861, Tmax = 0.906 | Rint = 0.025 |
5312 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.26 e Å−3 |
2255 reflections | Δρmin = −0.22 e Å−3 |
159 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 | ||
C1 | −0.1747 (3) | 0.3008 (2) | 0.0759 (2) | 0.0436 (5) | |
H1 | −0.3309 | 0.2675 | 0.0358 | 0.052* | |
C2 | −0.0904 (4) | 0.4328 (2) | 0.1351 (2) | 0.0473 (6) | |
H2 | −0.1756 | 0.5061 | 0.1430 | 0.057* | |
C3 | 0.1913 (3) | 0.3101 (2) | 0.14803 (18) | 0.0340 (4) | |
H3 | 0.3402 | 0.2855 | 0.1683 | 0.041* | |
C4 | 0.3124 (4) | 0.5616 (2) | 0.25080 (18) | 0.0387 (5) | |
H4A | 0.2294 | 0.6406 | 0.2597 | 0.046* | |
H4B | 0.4480 | 0.5950 | 0.2026 | 0.046* | |
C5 | 0.4095 (3) | 0.52626 (18) | 0.37907 (16) | 0.0287 (4) | |
C6 | 0.2643 (3) | 0.4373 (2) | 0.45444 (17) | 0.0338 (4) | |
H6 | 0.1047 | 0.3943 | 0.4240 | 0.041* | |
C7 | 0.6480 (3) | 0.5886 (2) | 0.42597 (17) | 0.0331 (4) | |
H7 | 0.7491 | 0.6482 | 0.3766 | 0.040* | |
C8 | 0.1839 (3) | −0.07995 (19) | 0.26423 (15) | 0.0243 (4) | |
C9 | 0.3820 (3) | −0.06034 (19) | 0.37445 (15) | 0.0254 (4) | |
H9 | 0.5024 | −0.1144 | 0.3515 | 0.031* | |
C10 | 0.2878 (3) | −0.1211 (2) | 0.49425 (15) | 0.0295 (4) | |
H10A | 0.2174 | −0.2243 | 0.4795 | 0.035* | |
H10B | 0.1605 | −0.0737 | 0.5164 | 0.035* | |
C11 | 0.5119 (3) | 0.0987 (2) | 0.39691 (16) | 0.0332 (4) | |
H11A | 0.3948 | 0.1562 | 0.4145 | 0.040* | |
H11B | 0.5820 | 0.1329 | 0.3216 | 0.040* | |
N1 | 0.0038 (2) | 0.22288 (17) | 0.08334 (13) | 0.0312 (4) | |
N2 | 0.1440 (3) | 0.43786 (16) | 0.18122 (14) | 0.0314 (4) | |
O1 | 0.24544 (19) | −0.02973 (14) | 0.16165 (10) | 0.0290 (3) | |
O2 | −0.0256 (2) | −0.14543 (18) | 0.27946 (13) | 0.0508 (4) | |
O1W | 0.3255 (2) | 0.09931 (16) | −0.09218 (12) | 0.0326 (3) | |
Mn1 | 0.0000 | 0.0000 | 0.0000 | 0.02103 (13) | |
HW12 | 0.256 (4) | 0.124 (3) | −0.157 (2) | 0.058 (7)* | |
HW11 | 0.437 (4) | 0.063 (3) | −0.113 (2) | 0.054 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0320 (9) | 0.0443 (12) | 0.0521 (13) | 0.0114 (9) | −0.0082 (9) | −0.0149 (10) |
C2 | 0.0418 (10) | 0.0457 (13) | 0.0570 (14) | 0.0235 (10) | −0.0067 (10) | −0.0149 (11) |
C3 | 0.0313 (9) | 0.0317 (10) | 0.0376 (10) | 0.0102 (8) | −0.0071 (8) | −0.0073 (8) |
C4 | 0.0507 (11) | 0.0247 (10) | 0.0353 (11) | 0.0020 (8) | −0.0071 (9) | −0.0036 (8) |
C5 | 0.0344 (9) | 0.0202 (9) | 0.0299 (9) | 0.0044 (7) | 0.0008 (8) | −0.0063 (7) |
C6 | 0.0268 (8) | 0.0324 (10) | 0.0374 (11) | −0.0013 (7) | −0.0004 (8) | −0.0060 (9) |
C7 | 0.0337 (9) | 0.0308 (10) | 0.0310 (10) | −0.0017 (8) | 0.0056 (8) | −0.0022 (8) |
C8 | 0.0245 (8) | 0.0259 (9) | 0.0224 (9) | 0.0077 (7) | −0.0020 (7) | 0.0008 (7) |
C9 | 0.0274 (8) | 0.0289 (9) | 0.0185 (8) | 0.0052 (7) | −0.0031 (7) | 0.0017 (7) |
C10 | 0.0328 (9) | 0.0294 (10) | 0.0215 (9) | −0.0011 (7) | −0.0036 (7) | 0.0041 (7) |
C11 | 0.0413 (10) | 0.0324 (11) | 0.0218 (9) | 0.0019 (8) | −0.0040 (8) | 0.0053 (8) |
N1 | 0.0307 (7) | 0.0323 (9) | 0.0289 (8) | 0.0077 (6) | −0.0040 (6) | −0.0075 (7) |
N2 | 0.0368 (8) | 0.0263 (8) | 0.0287 (8) | 0.0071 (6) | −0.0056 (6) | −0.0067 (7) |
O1 | 0.0257 (6) | 0.0440 (8) | 0.0168 (6) | 0.0082 (5) | −0.0022 (5) | 0.0033 (5) |
O2 | 0.0279 (7) | 0.0782 (11) | 0.0379 (8) | −0.0060 (7) | −0.0068 (6) | 0.0275 (8) |
O1W | 0.0230 (6) | 0.0491 (9) | 0.0252 (7) | 0.0073 (6) | 0.0009 (6) | 0.0033 (6) |
Mn1 | 0.02051 (19) | 0.0250 (2) | 0.01583 (19) | 0.00341 (14) | −0.00244 (13) | −0.00136 (14) |
C1—C2 | 1.347 (3) | C8—O1 | 1.264 (2) |
C1—N1 | 1.370 (2) | C8—C9 | 1.528 (2) |
C1—H1 | 0.9300 | C9—C11 | 1.522 (2) |
C2—N2 | 1.362 (2) | C9—C10 | 1.523 (2) |
C2—H2 | 0.9300 | C9—H9 | 0.9800 |
C3—N1 | 1.316 (2) | C10—C11ii | 1.524 (2) |
C3—N2 | 1.333 (2) | C10—H10A | 0.9700 |
C3—H3 | 0.9300 | C10—H10B | 0.9700 |
C4—N2 | 1.468 (2) | C11—C10ii | 1.524 (2) |
C4—C5 | 1.508 (2) | C11—H11A | 0.9700 |
C4—H4A | 0.9700 | C11—H11B | 0.9700 |
C4—H4B | 0.9700 | O1W—HW12 | 0.83 (3) |
C5—C6 | 1.383 (3) | O1W—HW11 | 0.83 (2) |
C5—C7 | 1.390 (2) | Mn1—N1 | 2.2515 (15) |
C6—C7i | 1.381 (3) | Mn1—O1 | 2.1819 (10) |
C6—H6 | 0.9300 | Mn1—O1W | 2.2203 (12) |
C7—C6i | 1.381 (3) | Mn1—O1iii | 2.1819 (10) |
C7—H7 | 0.9300 | Mn1—O1Wiii | 2.2203 (12) |
C8—O2 | 1.243 (2) | Mn1—N1iii | 2.2515 (15) |
C2—C1—N1 | 109.96 (16) | C11ii—C10—H10A | 109.2 |
C2—C1—H1 | 125.0 | C9—C10—H10B | 109.2 |
N1—C1—H1 | 125.0 | C11ii—C10—H10B | 109.2 |
C1—C2—N2 | 106.53 (17) | H10A—C10—H10B | 107.9 |
C1—C2—H2 | 126.7 | C9—C11—C10ii | 111.87 (15) |
N2—C2—H2 | 126.7 | C9—C11—H11A | 109.2 |
N1—C3—N2 | 112.47 (15) | C10ii—C11—H11A | 109.2 |
N1—C3—H3 | 123.8 | C9—C11—H11B | 109.2 |
N2—C3—H3 | 123.8 | C10ii—C11—H11B | 109.2 |
N2—C4—C5 | 113.55 (15) | H11A—C11—H11B | 107.9 |
N2—C4—H4A | 108.9 | C3—N1—C1 | 104.54 (16) |
C5—C4—H4A | 108.9 | C3—N1—Mn1 | 125.58 (12) |
N2—C4—H4B | 108.9 | C1—N1—Mn1 | 129.83 (12) |
C5—C4—H4B | 108.9 | C3—N2—C2 | 106.50 (15) |
H4A—C4—H4B | 107.7 | C3—N2—C4 | 127.03 (15) |
C6—C5—C7 | 118.46 (17) | C2—N2—C4 | 126.44 (16) |
C6—C5—C4 | 121.74 (16) | C8—O1—Mn1 | 126.24 (10) |
C7—C5—C4 | 119.75 (17) | Mn1—O1W—HW12 | 98.7 (16) |
C7i—C6—C5 | 121.19 (16) | Mn1—O1W—HW11 | 129.9 (17) |
C7i—C6—H6 | 119.4 | HW12—O1W—HW11 | 107 (2) |
C5—C6—H6 | 119.4 | O1—Mn1—O1iii | 180.00 (7) |
C6i—C7—C5 | 120.35 (17) | O1—Mn1—O1Wiii | 92.04 (5) |
C6i—C7—H7 | 119.8 | O1iii—Mn1—O1Wiii | 87.96 (5) |
C5—C7—H7 | 119.8 | O1—Mn1—O1W | 87.96 (5) |
O2—C8—O1 | 123.89 (14) | O1iii—Mn1—O1W | 92.04 (5) |
O2—C8—C9 | 118.78 (15) | O1Wiii—Mn1—O1W | 180.00 (9) |
O1—C8—C9 | 117.32 (14) | O1—Mn1—N1iii | 91.53 (5) |
C11—C9—C10 | 110.64 (14) | O1iii—Mn1—N1iii | 88.47 (5) |
C11—C9—C8 | 110.81 (14) | O1Wiii—Mn1—N1iii | 88.10 (5) |
C10—C9—C8 | 113.15 (13) | O1W—Mn1—N1iii | 91.90 (5) |
C11—C9—H9 | 107.3 | O1—Mn1—N1 | 88.47 (5) |
C10—C9—H9 | 107.3 | O1iii—Mn1—N1 | 91.53 (5) |
C8—C9—H9 | 107.3 | O1Wiii—Mn1—N1 | 91.90 (5) |
C9—C10—C11ii | 112.14 (14) | O1W—Mn1—N1 | 88.10 (5) |
C9—C10—H10A | 109.2 | N1iii—Mn1—N1 | 180.00 (10) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW11···O1iv | 0.83 (2) | 2.00 (2) | 2.8103 (18) | 165 (2) |
O1W—HW12···O2iii | 0.83 (3) | 1.81 (3) | 2.6150 (18) | 163 (2) |
Symmetry codes: (iii) −x, −y, −z; (iv) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C8H10O4)(C14H14N4)(H2O)2] |
Mr | 499.42 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 5.6645 (2), 9.4282 (6), 10.7437 (5) |
α, β, γ (°) | 91.907 (4), 95.553 (3), 102.426 (4) |
V (Å3) | 556.84 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.23 × 0.19 × 0.16 |
Data collection | |
Diffractometer | Bruker APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.861, 0.906 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5312, 2255, 1887 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.076, 1.05 |
No. of reflections | 2255 |
No. of parameters | 159 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.22 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).
Mn1—N1 | 2.2515 (15) | Mn1—O1i | 2.1819 (10) |
Mn1—O1 | 2.1819 (10) | Mn1—O1Wi | 2.2203 (12) |
Mn1—O1W | 2.2203 (12) | Mn1—N1i | 2.2515 (15) |
O1—Mn1—O1Wi | 92.04 (5) | O1Wi—Mn1—N1i | 88.10 (5) |
O1i—Mn1—O1Wi | 87.96 (5) | O1W—Mn1—N1i | 91.90 (5) |
O1—Mn1—O1W | 87.96 (5) | O1—Mn1—N1 | 88.47 (5) |
O1i—Mn1—O1W | 92.04 (5) | O1i—Mn1—N1 | 91.53 (5) |
O1—Mn1—N1i | 91.53 (5) | O1Wi—Mn1—N1 | 91.90 (5) |
O1i—Mn1—N1i | 88.47 (5) | O1W—Mn1—N1 | 88.10 (5) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—HW11···O1ii | 0.83 (2) | 2.00 (2) | 2.8103 (18) | 165 (2) |
O1W—HW12···O2i | 0.83 (3) | 1.81 (3) | 2.6150 (18) | 163 (2) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z. |
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The design and synthesis of metal–organic coordination polymers are of great interest, not only because of their wide range of potential applications in nonlinear optics, catalysis, gas absorption, luminescence, magnetism and medicine, but also because of their intriguing variety of architectures and topologies (Eddaoudi et al., 2001; Noveron et al., 2002; Batten & Robson, 1998). Generally, the topology of a coordination polymer can often be controlled and modified by selecting the coordination geometry preferred by the metal ion and the chemical structure of the organic ligand chosen (Carlucci et al., 2003). The use of aromatic carboxylic acids in the syntheses of coordination polymers has aroused enormous interest due to their versatile coordination modes and variety of structural conformations (Wang et al., 2005). Aromatic multicarboxylate ligands, such as 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid, are widely used to construct coordination polymers with interesting properties (Tao et al., 2002). However, flexible dicarboxylate ligands are rarely used in the construction of coordination polymers. The cyclohexane-1,4-dicarboxylate dianion (chdc) is an example of a flexible dianion because of the presence of cis and trans configurations. On the other hand, 4,4'-bipyridine is a rigid rod-like spacer, well known in the construction of metal–organic polymers, and it has adopted numerous interesting supramolecular architectures (Batten, 2001). However, flexible N-donor ligands such as 1,4-bis(imidazol-1-ylmethyl)benzene (1,4-bix) have not been so well explored to date (Wang et al., 2006). In this work, 1,4-bix assembles with manganese cyclohexane-1,4-dicarboxylate to furnish the title complex, [Mn(1,4-bix)(chdc)(H2O)2], (I), which exists as an unusual six-connected α-polonium network.
Selected bond lengths and angles for (I) are given in Table 1. As shown in Fig. 1, the repeat unit of (I) contains one MnII atom, one 1,4-bix ligand, one chdc anion and two coordination water molecules. Each MnII atom lies on a centre of symmetry, and is six-coordinated in an octahedral environment by two carboxylate O atoms from two different chdc anions, two water O atoms and two N atoms from two distinct 1,4-bix ligands. Atoms O1, O1iii, N1 and N1iii comprise the basal plane, and atoms O1W and O1Wiii occupy the axial positions of the octahedron [symmetry code: (iii) Please complete]. The average Mn—O(carboxylate) and Mn—N distances in (I) (Table 1) are comparable with those observed for [Mn(bza)2(ppz)2] [bza is benzoic acid and ppz is 3-(2-pyridyl)pyrazole; Zou et al., 2005]. As depicted in Fig. 2, each MnII centre is bridged by the chdc dianions and 1,4-bix ligands to give a two-dimensional four-connected (4,4) network. Along the [101] direction, adjacent MnII centres are linked via the two monodentate carboxylate groups of the chdc ligands to form one-dimensional chains. The 1,4-bix ligands further extend these chains along the [111] direction, resulting in the final two-dimensional (4,4) network, with dimensions of 13.96 (2) × 11.65 (2) Å for the repeat unit. Analysis of the crystal packing of (I) reveals that these two-dimensional layers adopt a parallel stacking mode in the (101) plane.
The driving force for the formation of this unusual topology becomes apparent when the structure of (I) is examined in detail. Along the [100] direction, there are hydrogen-bonding interactions between the water molecules and carboxylate O atoms (Table 2) of neighbouring (4,4) networks. The hydrogen bonds link neighbouring (4,4) networks, yielding a three-dimensional supramolecular architecture (Fig. 3). If each double hydrogen-bonded bridge is considered as one linker, each MnII atom can be regarded as a six-connected node, and the overall network topology is that of α-polonium (Batten & Robson, 1998). Recently, several six-connected nets, such as 44.611, LB-1 (44.610.8), pcu (412.63), roa (44.610.8), and rob (48.66.8), have been observed in coordination polymers (Zhang et al., 2007). It is noteworthy that the α-polonium net presented here is clearly different from the six-connected three-dimensional nets mentioned above. To the best of our knowledge, the structure of (I) is the first α-polonium net constructed from hydrogen-bonding interactions in a coordination polymer.