Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106056022/av3056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106056022/av3056Isup2.hkl |
CCDC reference: 638307
The title complex was prepared by the addition of stoichiometric amounts of MnCl2·6H2O (0.234 g, 1 mmol) and 2,2'-bipy (0.156 g, 1 mmol) to an ethanol–water (1:1 v/v) solution of acetylenedicarboxylic acid (0.144 g, 1 mmol). The pH of the mixture was adjusted to 7 with 1.0 M NaOH solution. After stirring for 30 min, the mixture was filtered. The filtrate was allowed to stand for several days to give yellow crystals of (I). Analysis, calculated for C14H12N2O6Mn: C 46.81, H 3.37, N 7.80%; found: C 46.75, H 3.34, N 7.76%.
Water H atoms were located in a difference Fourier map and refined with O—H and H···H distance restraints of 0.85 (1) and 1.39 (1) Å, respectively, and with Uiso(H) = 1.5Ueq(O). All other H atoms were placed in calculated positions, with C—H = 0.93 (aromatic), and were refined in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).
As one of the great challenges encountered in crystal engineering of functional materials, the structural diversity of coordination polymers formed by similar metal–organic building blocks is of intense interest, both as a result of its scientific significance and its intrinsic aesthetic appeal (Carlucci et al., 2003). The deliberate design and control of self-assembly by the selection of ligands and transition metals has become extremely important to chemists (Bu et al., 2001; Reger et al., 2001). A number of metal–organic polymers with one-, two- and three-dimensional infinite frameworks have been generated, in which aliphatic carboxylic acids, such as maleate (Zheng & Xie, 2005), malonate (Zhang & Lu, 2004) or related species, have often been chosen to fabricate the complexes. Recently, our group has been interested in the solid-state coordination chemistry of acetylenedicarboxylic acid. As an aliphatic carboxylic acid, it can be also considered as a good candidate with specific properties for the construction of coordination polymers. However, the reaction of acetylenedicarboxylic acid with transition metal ions remains relatively unexplored (Sieroń & Bukowska-Strzyżewska, 1998; Stein & Ruschewitz, 2005). In these complexes, the acetylenedicarboxylic acid ligand (ace) displays diverse coordination modes, such as bis-monodentate (Billetter et al., 2003, Wang et al., 2006), chelating bis-bidentate (Ruschewitz & Pantenburg, 2002) and bridging bis-bidentate (Pantenburg & Ruschewitz, 2002; Hohn et al., 2002). In order to explore the behaviour of this ligand further, the title novel manganese complex, [Mn(ace2-)(2,2'-bipy)(H2O)]n.nH2O, (I) (2,2'-bipy is 2,2'-bipyridine), has been synthesized and we present its structure here.
Complex (I) crystallizes in a non-centrosymmetric space group Fdd2. The asymmetric unit consists of one MnII ion, one 2,2'-bipy ligand, one ace2- ligand, one coordinated water molecule and one free water molecule (Fig. 1). Each MnII ion displays a slightly distorted octahedral geometry, defined by three carboxylate O atoms of three different ace2- ligands [Mn1—O1 = 2.2581 (12) Å, Mn—O2i = 2.1454 (11) Å and Mn—O3ii 2.1648 (11) Å; symmetry codes: (i) -x - 1, -y - 1/2, z + 1/2; (ii) x - 1/2, y, z + 1/2], the two N atoms of the 2,2'-bipy ligand and one water molecule. The C—O bond distances are similar [C11—O1 = 1.2360 (18) Å, C11—O2 = 1.2615 (18) Å, C14—O3 = 1.260 (2) Å and C14—O4 = 1.229 (2) Å], suggesting delocalization of electrons throughout. The equatorial plane is defined by atoms O1W/O2i/N2/N1 [r.m.s. deviation = 0.02 (2) Å; deviation of atom MnII = 0.19 (1) Å]. Atoms O1 and O3ii occupy the apical sites, with an angle of 165.12 (5)°. There are two long Csp2—Csp1 bonds (C11—C12 and C13—C14), because of the C12≡C13 triple bond and the double bonds of the carboxylic acid groups.
The unusual feature of (I) is that the ace2- groups act as tridentate bridging ligands to connect the MnII ions into a two-dimensional layer structure. The two carboxyl units of the ace2- ligand adopt two different coordination modes, one monodentate and another bidentate. Firstly, the ace2- ligands connect the MnII ions into one-dimensional chains, which span two directions to give rise to a plywood-like stacking mode. The angle between adjacent chains in the two different directions is 42°. Secondly, the non-coplanar chains are bridged by the bidentate carboxylate into a two-dimensional structure along (010). Free water molecules occupy the hollow regions and form hydrogen bonds with carboxylate O atoms [O2W—H2W1···O4iii = 3.145 (2) Å and O2W—H2W2···O3i = 2.9054 (19) Å; symmetry code: (iii) -x - 1, -y - 1/2, z - 1/2] (Fig. 2). Adjacent layers are stacked in an offset manner through π–π stacking interactions between one of the rings of the 2,2'-bipy ligand (C6–C10/N2) and a symmetry-related ring at (1/4 + x, -3/4 - y, 1/4 + z), with a centroid-to-centroid distance of 3.692 Å, thus forming a three-dimensional supramolecular network (Fig. 3).
For related literature, see: Billetter et al. (2003); Bu et al. (2001); Carlucci et al. (2003); Hohn et al. (2002); Pantenburg & Ruschewitz (2002); Reger et al. (2001); Ruschewitz & Pantenburg (2002); Sieroń & Bukowska-Strzyżewska (1998); Stein & Ruschewitz (2005); Wang et al. (2006); Zhang & Lu (2004); Zheng & Xie (2005).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97.
[Mn(C4O4)(C10H8N2)(H2O)]·H2O | F(000) = 2928 |
Mr = 359.20 | Dx = 1.661 Mg m−3 |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: F 2 -2d | Cell parameters from 13207 reflections |
a = 18.769 (4) Å | θ = 3.1–27.5° |
b = 42.406 (9) Å | µ = 0.95 mm−1 |
c = 7.2170 (14) Å | T = 295 K |
V = 5744 (2) Å3 | Block, yellow |
Z = 16 | 0.30 × 0.20 × 0.15 mm |
Rigaku R-AXIS RAPID area-detector diffractometer | 3284 independent reflections |
Radiation source: fine-focus sealed tube | 3135 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 10.000 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −23→24 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −54→54 |
Tmin = 0.763, Tmax = 0.870 | l = −9→9 |
13905 measured reflections |
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)] = 0.019 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.0286P)2 + 1.958P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.003 |
3284 reflections | Δρmax = 0.18 e Å−3 |
220 parameters | Δρmin = −0.20 e Å−3 |
7 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.007 (10) |
[Mn(C4O4)(C10H8N2)(H2O)]·H2O | V = 5744 (2) Å3 |
Mr = 359.20 | Z = 16 |
Orthorhombic, Fdd2 | Mo Kα radiation |
a = 18.769 (4) Å | µ = 0.95 mm−1 |
b = 42.406 (9) Å | T = 295 K |
c = 7.2170 (14) Å | 0.30 × 0.20 × 0.15 mm |
Rigaku R-AXIS RAPID area-detector diffractometer | 3284 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 3135 reflections with I > 2σ(I) |
Tmin = 0.763, Tmax = 0.870 | Rint = 0.023 |
13905 measured reflections |
R[F2 > 2σ(F2)] = 0.019 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.049 | Δρmax = 0.18 e Å−3 |
S = 1.05 | Δρmin = −0.20 e Å−3 |
3284 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
220 parameters | Absolute structure parameter: 0.007 (10) |
7 restraints |
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 | −0.581205 (10) | −0.287792 (4) | 0.40061 (3) | 0.01931 (6) | |
O1W | −0.60690 (6) | −0.25687 (3) | 0.1688 (2) | 0.0370 (3) | |
H1W1 | −0.5677 (6) | −0.2501 (4) | 0.125 (3) | 0.055* | |
H1W2 | −0.6383 (7) | −0.2426 (4) | 0.156 (4) | 0.055* | |
O2W | −0.71646 (7) | −0.21393 (3) | 0.1273 (2) | 0.0448 (3) | |
H2W1 | −0.7437 (11) | −0.2150 (6) | 0.034 (2) | 0.067* | |
H2W2 | −0.7409 (12) | −0.2137 (6) | 0.226 (2) | 0.067* | |
O1 | −0.47245 (6) | −0.28901 (3) | 0.26702 (19) | 0.0358 (3) | |
O2 | −0.46232 (5) | −0.24731 (3) | 0.08228 (17) | 0.0329 (3) | |
O3 | −0.19451 (5) | −0.28915 (3) | −0.04384 (17) | 0.0313 (3) | |
O4 | −0.19401 (7) | −0.29557 (4) | 0.2632 (2) | 0.0551 (4) | |
N1 | −0.59845 (6) | −0.33421 (3) | 0.25783 (17) | 0.0226 (2) | |
N2 | −0.53787 (6) | −0.32647 (3) | 0.58823 (17) | 0.0237 (2) | |
C1 | −0.63132 (9) | −0.33631 (4) | 0.0950 (2) | 0.0303 (3) | |
H1 | −0.6434 | −0.3178 | 0.0330 | 0.036* | |
C2 | −0.64816 (10) | −0.36500 (4) | 0.0144 (3) | 0.0405 (4) | |
H2 | −0.6722 | −0.3658 | −0.0982 | 0.049* | |
C3 | −0.62851 (10) | −0.39237 (4) | 0.1043 (3) | 0.0408 (4) | |
H3 | −0.6390 | −0.4119 | 0.0529 | 0.049* | |
C4 | −0.59316 (9) | −0.39039 (4) | 0.2711 (3) | 0.0335 (3) | |
H4 | −0.5786 | −0.4086 | 0.3324 | 0.040* | |
C5 | −0.57957 (7) | −0.36076 (3) | 0.3467 (2) | 0.0225 (3) | |
C6 | −0.54466 (7) | −0.35649 (3) | 0.5297 (2) | 0.0227 (3) | |
C7 | −0.51976 (8) | −0.38165 (3) | 0.6345 (3) | 0.0324 (3) | |
H7 | −0.5262 | −0.4023 | 0.5937 | 0.039* | |
C8 | −0.48545 (10) | −0.37576 (4) | 0.7993 (3) | 0.0398 (4) | |
H8 | −0.4680 | −0.3923 | 0.8705 | 0.048* | |
C9 | −0.47719 (10) | −0.34488 (4) | 0.8581 (2) | 0.0405 (4) | |
H9 | −0.4534 | −0.3403 | 0.9678 | 0.049* | |
C10 | −0.50517 (9) | −0.32118 (4) | 0.7494 (2) | 0.0319 (3) | |
H10 | −0.5010 | −0.3005 | 0.7905 | 0.038* | |
C11 | −0.43817 (7) | −0.27132 (3) | 0.1642 (2) | 0.0237 (3) | |
C12 | −0.36280 (8) | −0.27918 (3) | 0.1341 (3) | 0.0286 (3) | |
C13 | −0.30105 (8) | −0.28522 (3) | 0.1190 (2) | 0.0273 (3) | |
C14 | −0.22326 (8) | −0.29053 (3) | 0.1138 (2) | 0.0268 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01604 (9) | 0.01841 (9) | 0.02348 (10) | 0.00006 (8) | −0.00028 (8) | −0.00090 (9) |
O1W | 0.0260 (5) | 0.0402 (6) | 0.0447 (7) | 0.0054 (5) | 0.0052 (5) | 0.0166 (6) |
O2W | 0.0340 (6) | 0.0469 (7) | 0.0537 (9) | 0.0063 (5) | 0.0036 (6) | 0.0092 (7) |
O1 | 0.0240 (5) | 0.0326 (6) | 0.0507 (8) | 0.0052 (4) | 0.0136 (5) | 0.0180 (5) |
O2 | 0.0226 (5) | 0.0286 (5) | 0.0474 (7) | 0.0033 (4) | 0.0076 (5) | 0.0145 (5) |
O3 | 0.0184 (4) | 0.0395 (6) | 0.0359 (7) | −0.0002 (4) | 0.0054 (4) | −0.0059 (5) |
O4 | 0.0354 (7) | 0.0867 (11) | 0.0432 (8) | 0.0116 (7) | −0.0026 (6) | 0.0218 (8) |
N1 | 0.0229 (5) | 0.0229 (6) | 0.0219 (6) | 0.0022 (5) | 0.0006 (5) | −0.0022 (5) |
N2 | 0.0248 (6) | 0.0226 (5) | 0.0236 (6) | 0.0014 (5) | −0.0006 (5) | 0.0003 (5) |
C1 | 0.0324 (8) | 0.0331 (8) | 0.0256 (7) | 0.0054 (7) | −0.0043 (6) | −0.0028 (6) |
C2 | 0.0459 (9) | 0.0446 (10) | 0.0310 (9) | −0.0007 (8) | −0.0110 (7) | −0.0119 (8) |
C3 | 0.0472 (9) | 0.0320 (8) | 0.0431 (10) | −0.0043 (8) | −0.0051 (8) | −0.0172 (7) |
C4 | 0.0366 (8) | 0.0228 (7) | 0.0412 (9) | 0.0015 (6) | −0.0019 (7) | −0.0036 (7) |
C5 | 0.0215 (6) | 0.0210 (6) | 0.0248 (7) | 0.0007 (5) | 0.0021 (6) | −0.0023 (5) |
C6 | 0.0209 (6) | 0.0233 (7) | 0.0240 (7) | −0.0003 (5) | 0.0014 (5) | 0.0005 (5) |
C7 | 0.0401 (8) | 0.0240 (6) | 0.0332 (8) | 0.0036 (6) | −0.0019 (7) | 0.0025 (7) |
C8 | 0.0508 (10) | 0.0351 (8) | 0.0335 (9) | 0.0089 (8) | −0.0080 (7) | 0.0095 (7) |
C9 | 0.0527 (10) | 0.0403 (9) | 0.0285 (9) | 0.0036 (8) | −0.0139 (7) | 0.0023 (7) |
C10 | 0.0419 (8) | 0.0268 (7) | 0.0271 (8) | 0.0015 (7) | −0.0086 (7) | −0.0020 (6) |
C11 | 0.0203 (6) | 0.0221 (6) | 0.0286 (7) | 0.0004 (5) | 0.0054 (6) | 0.0011 (6) |
C12 | 0.0258 (7) | 0.0240 (6) | 0.0360 (8) | 0.0017 (6) | 0.0077 (7) | 0.0087 (7) |
C13 | 0.0233 (7) | 0.0270 (7) | 0.0315 (9) | 0.0012 (6) | 0.0065 (6) | 0.0062 (6) |
C14 | 0.0200 (6) | 0.0235 (6) | 0.0369 (9) | 0.0020 (5) | 0.0021 (6) | 0.0038 (6) |
Mn1—O2i | 2.1454 (11) | C1—C2 | 1.385 (2) |
Mn1—O3ii | 2.1648 (11) | C1—H1 | 0.9300 |
Mn1—O1W | 2.1796 (12) | C2—C3 | 1.380 (3) |
Mn1—N1 | 2.2452 (12) | C2—H2 | 0.9300 |
Mn1—O1 | 2.2581 (12) | C3—C4 | 1.377 (2) |
Mn1—N2 | 2.2772 (12) | C3—H3 | 0.9300 |
O1W—H1W1 | 0.851 (9) | C4—C5 | 1.394 (2) |
O1W—H1W2 | 0.851 (9) | C4—H4 | 0.9300 |
O2W—H2W1 | 0.847 (9) | C5—C6 | 1.485 (2) |
O2W—H2W2 | 0.846 (9) | C6—C7 | 1.389 (2) |
O1—C11 | 1.2360 (18) | C7—C8 | 1.375 (2) |
O2—C11 | 1.2615 (18) | C7—H7 | 0.9300 |
O2—Mn1iii | 2.1454 (11) | C8—C9 | 1.385 (2) |
O3—C14 | 1.260 (2) | C8—H8 | 0.9300 |
O3—Mn1iv | 2.1648 (11) | C9—C10 | 1.379 (2) |
O4—C14 | 1.229 (2) | C9—H9 | 0.9300 |
N1—C1 | 1.3304 (19) | C10—H10 | 0.9300 |
N1—C5 | 1.3433 (19) | C11—C12 | 1.4694 (19) |
N2—C10 | 1.334 (2) | C12—C13 | 1.192 (2) |
N2—C6 | 1.3475 (18) | C13—C14 | 1.478 (2) |
O2i—Mn1—O3ii | 106.22 (4) | C1—C2—H2 | 120.7 |
O2i—Mn1—O1W | 97.81 (5) | C4—C3—C2 | 119.26 (15) |
O3ii—Mn1—O1W | 86.60 (4) | C4—C3—H3 | 120.4 |
O2i—Mn1—N1 | 160.68 (4) | C2—C3—H3 | 120.4 |
O3ii—Mn1—N1 | 85.41 (4) | C3—C4—C5 | 119.04 (15) |
O1W—Mn1—N1 | 98.23 (5) | C3—C4—H4 | 120.5 |
O2i—Mn1—O1 | 86.14 (5) | C5—C4—H4 | 120.5 |
O3ii—Mn1—O1 | 165.12 (5) | N1—C5—C4 | 121.36 (14) |
O1W—Mn1—O1 | 83.46 (4) | N1—C5—C6 | 116.04 (12) |
N1—Mn1—O1 | 85.08 (4) | C4—C5—C6 | 122.60 (13) |
O2i—Mn1—N2 | 90.02 (5) | N2—C6—C7 | 121.53 (14) |
O3ii—Mn1—N2 | 102.80 (4) | N2—C6—C5 | 115.82 (12) |
O1W—Mn1—N2 | 165.64 (5) | C7—C6—C5 | 122.65 (13) |
N1—Mn1—N2 | 72.12 (5) | C8—C7—C6 | 119.31 (15) |
O1—Mn1—N2 | 85.09 (4) | C8—C7—H7 | 120.3 |
Mn1—O1W—H1W1 | 107.2 (14) | C6—C7—H7 | 120.3 |
Mn1—O1W—H1W2 | 131.8 (16) | C7—C8—C9 | 119.24 (15) |
H1W1—O1W—H1W2 | 108.6 (13) | C7—C8—H8 | 120.4 |
H2W1—O2W—H2W2 | 110.1 (14) | C9—C8—H8 | 120.4 |
C11—O1—Mn1 | 135.48 (9) | C10—C9—C8 | 118.20 (15) |
C11—O2—Mn1iii | 135.20 (9) | C10—C9—H9 | 120.9 |
C14—O3—Mn1iv | 126.09 (10) | C8—C9—H9 | 120.9 |
C1—N1—C5 | 119.21 (13) | N2—C10—C9 | 123.26 (15) |
C1—N1—Mn1 | 122.08 (11) | N2—C10—H10 | 118.4 |
C5—N1—Mn1 | 118.53 (9) | C9—C10—H10 | 118.4 |
C10—N2—C6 | 118.42 (13) | O1—C11—O2 | 125.75 (12) |
C10—N2—Mn1 | 124.16 (10) | O1—C11—C12 | 116.88 (13) |
C6—N2—Mn1 | 117.41 (9) | O2—C11—C12 | 117.37 (13) |
N1—C1—C2 | 122.40 (16) | C13—C12—C11 | 176.70 (19) |
N1—C1—H1 | 118.8 | C12—C13—C14 | 174.69 (17) |
C2—C1—H1 | 118.8 | O4—C14—O3 | 127.49 (14) |
C3—C2—C1 | 118.69 (16) | O4—C14—C13 | 116.47 (14) |
C3—C2—H2 | 120.7 | O3—C14—C13 | 116.04 (14) |
O2i—Mn1—O1—C11 | −73.02 (17) | C2—C3—C4—C5 | 1.4 (3) |
O3ii—Mn1—O1—C11 | 73.7 (2) | C1—N1—C5—C4 | 0.6 (2) |
O1W—Mn1—O1—C11 | 25.31 (17) | Mn1—N1—C5—C4 | 175.70 (11) |
N1—Mn1—O1—C11 | 124.20 (17) | C1—N1—C5—C6 | −178.61 (12) |
N2—Mn1—O1—C11 | −163.38 (17) | Mn1—N1—C5—C6 | −3.47 (16) |
O2i—Mn1—N1—C1 | −159.10 (14) | C3—C4—C5—N1 | −1.9 (2) |
O3ii—Mn1—N1—C1 | 72.69 (11) | C3—C4—C5—C6 | 177.22 (14) |
O1W—Mn1—N1—C1 | −13.20 (12) | C10—N2—C6—C7 | 1.3 (2) |
O1—Mn1—N1—C1 | −95.85 (11) | Mn1—N2—C6—C7 | 179.91 (11) |
N2—Mn1—N1—C1 | 177.73 (12) | C10—N2—C6—C5 | −178.21 (13) |
O2i—Mn1—N1—C5 | 25.9 (2) | Mn1—N2—C6—C5 | 0.44 (16) |
O3ii—Mn1—N1—C5 | −102.30 (10) | N1—C5—C6—N2 | 1.96 (18) |
O1W—Mn1—N1—C5 | 171.81 (10) | C4—C5—C6—N2 | −177.20 (14) |
O1—Mn1—N1—C5 | 89.16 (10) | N1—C5—C6—C7 | −177.51 (14) |
N2—Mn1—N1—C5 | 2.74 (10) | C4—C5—C6—C7 | 3.3 (2) |
O2i—Mn1—N2—C10 | 4.45 (13) | N2—C6—C7—C8 | −2.0 (2) |
O3ii—Mn1—N2—C10 | −102.20 (12) | C5—C6—C7—C8 | 177.43 (15) |
O1W—Mn1—N2—C10 | 127.80 (19) | C6—C7—C8—C9 | 0.7 (3) |
N1—Mn1—N2—C10 | 176.97 (13) | C7—C8—C9—C10 | 1.2 (3) |
O1—Mn1—N2—C10 | 90.57 (12) | C6—N2—C10—C9 | 0.8 (2) |
O2i—Mn1—N2—C6 | −174.12 (10) | Mn1—N2—C10—C9 | −177.76 (14) |
O3ii—Mn1—N2—C6 | 79.23 (11) | C8—C9—C10—N2 | −2.0 (3) |
O1W—Mn1—N2—C6 | −50.8 (2) | Mn1—O1—C11—O2 | −10.3 (3) |
N1—Mn1—N2—C6 | −1.60 (10) | Mn1—O1—C11—C12 | 170.11 (12) |
O1—Mn1—N2—C6 | −88.00 (11) | Mn1iii—O2—C11—O1 | 179.47 (12) |
C5—N1—C1—C2 | 1.2 (2) | Mn1iii—O2—C11—C12 | −0.9 (2) |
Mn1—N1—C1—C2 | −173.73 (13) | Mn1iv—O3—C14—O4 | −10.5 (2) |
N1—C1—C2—C3 | −1.6 (3) | Mn1iv—O3—C14—C13 | 168.96 (9) |
C1—C2—C3—C4 | 0.2 (3) |
Symmetry codes: (i) −x−1, −y−1/2, z+1/2; (ii) x−1/2, y, z+1/2; (iii) −x−1, −y−1/2, z−1/2; (iv) x+1/2, y, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2 | 0.85 (2) | 2.01 (2) | 2.8139 (16) | 159 (2) |
O1W—H1W2···O2W | 0.85 (2) | 1.92 (2) | 2.7629 (17) | 174 (2) |
O2W—H2W1···O4iii | 0.85 (2) | 2.32 (2) | 3.145 (2) | 165 (2) |
O2W—H2W2···O3i | 0.85 (2) | 2.06 (2) | 2.9054 (19) | 176 (2) |
Symmetry codes: (i) −x−1, −y−1/2, z+1/2; (iii) −x−1, −y−1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C4O4)(C10H8N2)(H2O)]·H2O |
Mr | 359.20 |
Crystal system, space group | Orthorhombic, Fdd2 |
Temperature (K) | 295 |
a, b, c (Å) | 18.769 (4), 42.406 (9), 7.2170 (14) |
V (Å3) | 5744 (2) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.95 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID area-detector |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.763, 0.870 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13905, 3284, 3135 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.049, 1.05 |
No. of reflections | 3284 |
No. of parameters | 220 |
No. of restraints | 7 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.20 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | 0.007 (10) |
Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2001), SHELXL97.
Mn1—O2i | 2.1454 (11) | Mn1—N2 | 2.2772 (12) |
Mn1—O3ii | 2.1648 (11) | O1—C11 | 1.2360 (18) |
Mn1—O1W | 2.1796 (12) | O2—C11 | 1.2615 (18) |
Mn1—N1 | 2.2452 (12) | O3—C14 | 1.260 (2) |
Mn1—O1 | 2.2581 (12) | O4—C14 | 1.229 (2) |
O2i—Mn1—O3ii | 106.22 (4) | O1W—Mn1—O1 | 83.46 (4) |
O2i—Mn1—O1W | 97.81 (5) | N1—Mn1—O1 | 85.08 (4) |
O3ii—Mn1—O1W | 86.60 (4) | O2i—Mn1—N2 | 90.02 (5) |
O2i—Mn1—N1 | 160.68 (4) | O3ii—Mn1—N2 | 102.80 (4) |
O3ii—Mn1—N1 | 85.41 (4) | O1W—Mn1—N2 | 165.64 (5) |
O1W—Mn1—N1 | 98.23 (5) | N1—Mn1—N2 | 72.12 (5) |
O2i—Mn1—O1 | 86.14 (5) | O1—Mn1—N2 | 85.09 (4) |
O3ii—Mn1—O1 | 165.12 (5) |
Symmetry codes: (i) −x−1, −y−1/2, z+1/2; (ii) x−1/2, y, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2 | 0.85 (2) | 2.01 (2) | 2.8139 (16) | 159 (2) |
O1W—H1W2···O2W | 0.85 (2) | 1.92 (2) | 2.7629 (17) | 174 (2) |
O2W—H2W1···O4iii | 0.85 (2) | 2.32 (2) | 3.145 (2) | 165 (2) |
O2W—H2W2···O3i | 0.85 (2) | 2.06 (2) | 2.9054 (19) | 176 (2) |
Symmetry codes: (i) −x−1, −y−1/2, z+1/2; (iii) −x−1, −y−1/2, z−1/2. |
As one of the great challenges encountered in crystal engineering of functional materials, the structural diversity of coordination polymers formed by similar metal–organic building blocks is of intense interest, both as a result of its scientific significance and its intrinsic aesthetic appeal (Carlucci et al., 2003). The deliberate design and control of self-assembly by the selection of ligands and transition metals has become extremely important to chemists (Bu et al., 2001; Reger et al., 2001). A number of metal–organic polymers with one-, two- and three-dimensional infinite frameworks have been generated, in which aliphatic carboxylic acids, such as maleate (Zheng & Xie, 2005), malonate (Zhang & Lu, 2004) or related species, have often been chosen to fabricate the complexes. Recently, our group has been interested in the solid-state coordination chemistry of acetylenedicarboxylic acid. As an aliphatic carboxylic acid, it can be also considered as a good candidate with specific properties for the construction of coordination polymers. However, the reaction of acetylenedicarboxylic acid with transition metal ions remains relatively unexplored (Sieroń & Bukowska-Strzyżewska, 1998; Stein & Ruschewitz, 2005). In these complexes, the acetylenedicarboxylic acid ligand (ace) displays diverse coordination modes, such as bis-monodentate (Billetter et al., 2003, Wang et al., 2006), chelating bis-bidentate (Ruschewitz & Pantenburg, 2002) and bridging bis-bidentate (Pantenburg & Ruschewitz, 2002; Hohn et al., 2002). In order to explore the behaviour of this ligand further, the title novel manganese complex, [Mn(ace2-)(2,2'-bipy)(H2O)]n.nH2O, (I) (2,2'-bipy is 2,2'-bipyridine), has been synthesized and we present its structure here.
Complex (I) crystallizes in a non-centrosymmetric space group Fdd2. The asymmetric unit consists of one MnII ion, one 2,2'-bipy ligand, one ace2- ligand, one coordinated water molecule and one free water molecule (Fig. 1). Each MnII ion displays a slightly distorted octahedral geometry, defined by three carboxylate O atoms of three different ace2- ligands [Mn1—O1 = 2.2581 (12) Å, Mn—O2i = 2.1454 (11) Å and Mn—O3ii 2.1648 (11) Å; symmetry codes: (i) -x - 1, -y - 1/2, z + 1/2; (ii) x - 1/2, y, z + 1/2], the two N atoms of the 2,2'-bipy ligand and one water molecule. The C—O bond distances are similar [C11—O1 = 1.2360 (18) Å, C11—O2 = 1.2615 (18) Å, C14—O3 = 1.260 (2) Å and C14—O4 = 1.229 (2) Å], suggesting delocalization of electrons throughout. The equatorial plane is defined by atoms O1W/O2i/N2/N1 [r.m.s. deviation = 0.02 (2) Å; deviation of atom MnII = 0.19 (1) Å]. Atoms O1 and O3ii occupy the apical sites, with an angle of 165.12 (5)°. There are two long Csp2—Csp1 bonds (C11—C12 and C13—C14), because of the C12≡C13 triple bond and the double bonds of the carboxylic acid groups.
The unusual feature of (I) is that the ace2- groups act as tridentate bridging ligands to connect the MnII ions into a two-dimensional layer structure. The two carboxyl units of the ace2- ligand adopt two different coordination modes, one monodentate and another bidentate. Firstly, the ace2- ligands connect the MnII ions into one-dimensional chains, which span two directions to give rise to a plywood-like stacking mode. The angle between adjacent chains in the two different directions is 42°. Secondly, the non-coplanar chains are bridged by the bidentate carboxylate into a two-dimensional structure along (010). Free water molecules occupy the hollow regions and form hydrogen bonds with carboxylate O atoms [O2W—H2W1···O4iii = 3.145 (2) Å and O2W—H2W2···O3i = 2.9054 (19) Å; symmetry code: (iii) -x - 1, -y - 1/2, z - 1/2] (Fig. 2). Adjacent layers are stacked in an offset manner through π–π stacking interactions between one of the rings of the 2,2'-bipy ligand (C6–C10/N2) and a symmetry-related ring at (1/4 + x, -3/4 - y, 1/4 + z), with a centroid-to-centroid distance of 3.692 Å, thus forming a three-dimensional supramolecular network (Fig. 3).