Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104020050/ta1439sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104020050/ta1439Isup2.hkl |
CCDC reference: 254903
All reagents were of AR grade and were used without further purification. A mixture of 2,2'-diphenic acid (0.242 g, 1 mmol), benzidine (0.184 g, 1 mmol) and MnCl2 (0.170 g, 1 mmol) with H2O (15 ml) was placed in a Teflon-lined stainless steel vessel, heated to 333 K and maintained at that temperature for 96 h, and then cooled slowly to room temperature. The resulting deep-orange crystals were collected by filtration and washed with water (yield 80%). Interestingly, although we changed the ratio of the mixture to 1:2:1 and 1:2:2, we got the same deep-orange crystals.
H atoms attached to C atoms were treated as riding, with C—H distances of 0.93 Å and N—H distances of 0.90 Å, and with Uiso(H) values of 1.2Ueq(C,N).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 2000); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.
[Mn(C14H8O4)(C12H12N2)] | F(000) = 988 |
Mr = 479.38 | Dx = 1.407 Mg m−3 |
Monoclinic, C2/c | Melting point: not measured K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 24.309 (10) Å | Cell parameters from 1010 reflections |
b = 10.161 (4) Å | θ = 2.2–21.8° |
c = 9.326 (4) Å | µ = 0.62 mm−1 |
β = 100.677 (7)° | T = 293 K |
V = 2263.7 (16) Å3 | Needle, dark orange |
Z = 4 | 0.42 × 0.28 × 0.23 mm |
Bruker SMART 1K CCD area-detector diffractometer | 2005 independent reflections |
Radiation source: fine-focus sealed tube | 1313 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −23→28 |
Tmin = 0.781, Tmax = 0.871 | k = −12→11 |
5868 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.87 | w = 1/[σ2(Fo2) + (0.0322P)2] where P = (Fo2 + 2Fc2)/3 |
2005 reflections | (Δ/σ)max = 0.012 |
150 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
[Mn(C14H8O4)(C12H12N2)] | V = 2263.7 (16) Å3 |
Mr = 479.38 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.309 (10) Å | µ = 0.62 mm−1 |
b = 10.161 (4) Å | T = 293 K |
c = 9.326 (4) Å | 0.42 × 0.28 × 0.23 mm |
β = 100.677 (7)° |
Bruker SMART 1K CCD area-detector diffractometer | 2005 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 1313 reflections with I > 2σ(I) |
Tmin = 0.781, Tmax = 0.871 | Rint = 0.053 |
5868 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 0.87 | Δρmax = 0.39 e Å−3 |
2005 reflections | Δρmin = −0.22 e Å−3 |
150 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 | ||
Mn1 | 0.0000 | 1.02748 (6) | 0.2500 | 0.0341 (2) | |
N1 | 0.08919 (9) | 1.0167 (2) | 0.1954 (2) | 0.0403 (6) | |
H1A | 0.0980 | 0.9307 | 0.1943 | 0.048* | |
H1B | 0.0862 | 1.0456 | 0.1030 | 0.048* | |
O1 | −0.02209 (7) | 0.87500 (16) | 0.08064 (18) | 0.0340 (5) | |
O2 | 0.02422 (8) | 0.82012 (17) | −0.0958 (2) | 0.0438 (5) | |
C1 | 0.01373 (11) | 0.8068 (3) | 0.0298 (3) | 0.0331 (7) | |
C2 | 0.04916 (12) | 0.7112 (2) | 0.1287 (3) | 0.0329 (7) | |
C3 | 0.03001 (12) | 0.6489 (2) | 0.2438 (3) | 0.0364 (7) | |
C4 | 0.06742 (15) | 0.5777 (3) | 0.3431 (3) | 0.0576 (9) | |
H4 | 0.0548 | 0.5349 | 0.4191 | 0.069* | |
C5 | 0.12285 (16) | 0.5684 (3) | 0.3326 (4) | 0.0711 (11) | |
H5 | 0.1476 | 0.5230 | 0.4034 | 0.085* | |
C6 | 0.14186 (14) | 0.6264 (3) | 0.2174 (4) | 0.0611 (10) | |
H6 | 0.1792 | 0.6186 | 0.2085 | 0.073* | |
C7 | 0.10477 (12) | 0.6961 (3) | 0.1157 (3) | 0.0437 (8) | |
H7 | 0.1173 | 0.7338 | 0.0367 | 0.052* | |
C8 | 0.13668 (11) | 1.0814 (3) | 0.2784 (3) | 0.0374 (7) | |
C9 | 0.16671 (12) | 1.0233 (3) | 0.4007 (3) | 0.0489 (8) | |
H9 | 0.1575 | 0.9387 | 0.4261 | 0.059* | |
C10 | 0.21072 (12) | 1.0890 (3) | 0.4872 (3) | 0.0516 (8) | |
H10 | 0.2300 | 1.0480 | 0.5708 | 0.062* | |
C11 | 0.22682 (11) | 1.2141 (3) | 0.4525 (3) | 0.0364 (7) | |
C12 | 0.19660 (12) | 1.2679 (3) | 0.3265 (3) | 0.0454 (8) | |
H12 | 0.2069 | 1.3505 | 0.2976 | 0.054* | |
C13 | 0.15205 (12) | 1.2056 (3) | 0.2415 (3) | 0.0466 (8) | |
H13 | 0.1322 | 1.2472 | 0.1590 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0340 (4) | 0.0410 (4) | 0.0264 (4) | 0.000 | 0.0033 (3) | 0.000 |
N1 | 0.0341 (14) | 0.0472 (14) | 0.0381 (14) | −0.0052 (12) | 0.0026 (11) | −0.0098 (12) |
O1 | 0.0345 (12) | 0.0374 (11) | 0.0301 (11) | 0.0019 (9) | 0.0058 (9) | −0.0021 (9) |
O2 | 0.0578 (14) | 0.0482 (12) | 0.0276 (11) | 0.0107 (11) | 0.0136 (10) | 0.0060 (9) |
C1 | 0.0337 (18) | 0.0323 (16) | 0.0317 (18) | −0.0064 (14) | 0.0016 (14) | −0.0034 (13) |
C2 | 0.0410 (18) | 0.0303 (15) | 0.0278 (16) | 0.0030 (14) | 0.0074 (13) | −0.0019 (13) |
C3 | 0.0496 (19) | 0.0300 (14) | 0.0317 (16) | 0.0050 (14) | 0.0126 (15) | −0.0023 (13) |
C4 | 0.073 (3) | 0.054 (2) | 0.052 (2) | 0.0235 (19) | 0.0274 (19) | 0.0217 (17) |
C5 | 0.078 (3) | 0.080 (3) | 0.059 (2) | 0.045 (2) | 0.022 (2) | 0.029 (2) |
C6 | 0.049 (2) | 0.070 (2) | 0.067 (3) | 0.0235 (19) | 0.0178 (19) | 0.016 (2) |
C7 | 0.050 (2) | 0.0416 (18) | 0.043 (2) | 0.0068 (16) | 0.0184 (16) | 0.0029 (15) |
C8 | 0.0277 (16) | 0.0465 (17) | 0.0384 (18) | −0.0006 (14) | 0.0066 (14) | −0.0101 (15) |
C9 | 0.0435 (19) | 0.0403 (17) | 0.057 (2) | −0.0090 (16) | −0.0049 (16) | 0.0030 (16) |
C10 | 0.042 (2) | 0.0534 (19) | 0.052 (2) | −0.0047 (17) | −0.0095 (16) | 0.0092 (17) |
C11 | 0.0286 (16) | 0.0392 (17) | 0.0411 (19) | −0.0043 (14) | 0.0060 (14) | −0.0044 (14) |
C12 | 0.0460 (19) | 0.0409 (18) | 0.046 (2) | −0.0104 (16) | −0.0010 (16) | 0.0035 (15) |
C13 | 0.048 (2) | 0.0451 (18) | 0.0418 (19) | −0.0025 (16) | −0.0045 (16) | 0.0035 (15) |
Mn1—O2i | 2.1214 (19) | C4—H4 | 0.9300 |
Mn1—O2ii | 2.1214 (19) | C5—C6 | 1.378 (4) |
Mn1—O1 | 2.2066 (18) | C5—H5 | 0.9300 |
Mn1—O1iii | 2.2066 (18) | C6—C7 | 1.377 (4) |
Mn1—N1iii | 2.320 (2) | C6—H6 | 0.9300 |
Mn1—N1 | 2.320 (2) | C7—H7 | 0.9300 |
N1—C8 | 1.426 (3) | C8—C9 | 1.369 (4) |
N1—H1A | 0.9000 | C8—C13 | 1.378 (4) |
N1—H1B | 0.9000 | C9—C10 | 1.386 (4) |
O1—C1 | 1.271 (3) | C9—H9 | 0.9300 |
O2—C1 | 1.251 (3) | C10—C11 | 1.385 (4) |
O2—Mn1ii | 2.1214 (19) | C10—H10 | 0.9300 |
C1—C2 | 1.498 (3) | C11—C12 | 1.378 (4) |
C2—C7 | 1.388 (4) | C11—C11iv | 1.490 (5) |
C2—C3 | 1.398 (3) | C12—C13 | 1.372 (4) |
C3—C4 | 1.377 (4) | C12—H12 | 0.9300 |
C3—C3iii | 1.485 (5) | C13—H13 | 0.9300 |
C4—C5 | 1.372 (4) | ||
O2i—Mn1—O2ii | 86.23 (11) | C2—C3—C3iii | 122.1 (3) |
O2i—Mn1—O1 | 176.45 (7) | C5—C4—C3 | 121.5 (3) |
O2ii—Mn1—O1 | 91.55 (7) | C5—C4—H4 | 119.2 |
O2i—Mn1—O1iii | 91.55 (7) | C3—C4—H4 | 119.2 |
O2ii—Mn1—O1iii | 176.45 (7) | C4—C5—C6 | 120.1 (3) |
O1—Mn1—O1iii | 90.81 (9) | C4—C5—H5 | 119.9 |
O2i—Mn1—N1iii | 92.22 (8) | C6—C5—H5 | 119.9 |
O2ii—Mn1—N1iii | 91.73 (7) | C7—C6—C5 | 119.0 (3) |
O1—Mn1—N1iii | 90.61 (7) | C7—C6—H6 | 120.5 |
O1iii—Mn1—N1iii | 85.58 (7) | C5—C6—H6 | 120.5 |
O2i—Mn1—N1 | 91.73 (7) | C6—C7—C2 | 121.4 (3) |
O2ii—Mn1—N1 | 92.22 (8) | C6—C7—H7 | 119.3 |
O1—Mn1—N1 | 85.58 (7) | C2—C7—H7 | 119.3 |
O1iii—Mn1—N1 | 90.61 (7) | C9—C8—C13 | 118.4 (3) |
N1iii—Mn1—N1 | 174.58 (11) | C9—C8—N1 | 120.5 (3) |
C8—N1—Mn1 | 123.66 (16) | C13—C8—N1 | 121.1 (3) |
C8—N1—H1A | 106.4 | C8—C9—C10 | 120.8 (3) |
Mn1—N1—H1A | 106.4 | C8—C9—H9 | 119.6 |
C8—N1—H1B | 106.4 | C10—C9—H9 | 119.6 |
Mn1—N1—H1B | 106.4 | C11—C10—C9 | 121.8 (3) |
H1A—N1—H1B | 106.5 | C11—C10—H10 | 119.1 |
C1—O1—Mn1 | 123.84 (16) | C9—C10—H10 | 119.1 |
C1—O2—Mn1ii | 129.37 (18) | C12—C11—C10 | 115.7 (3) |
O2—C1—O1 | 124.3 (3) | C12—C11—C11iv | 122.5 (3) |
O2—C1—C2 | 116.9 (2) | C10—C11—C11iv | 121.7 (3) |
O1—C1—C2 | 118.6 (2) | C13—C12—C11 | 123.3 (3) |
C7—C2—C3 | 119.0 (3) | C13—C12—H12 | 118.4 |
C7—C2—C1 | 118.5 (2) | C11—C12—H12 | 118.4 |
C3—C2—C1 | 122.1 (3) | C12—C13—C8 | 119.9 (3) |
C4—C3—C2 | 118.8 (3) | C12—C13—H13 | 120.0 |
C4—C3—C3iii | 118.9 (3) | C8—C13—H13 | 120.0 |
Symmetry codes: (i) x, −y+2, z+1/2; (ii) −x, −y+2, −z; (iii) −x, y, −z+1/2; (iv) −x+1/2, −y+5/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O1ii | 0.90 | 2.24 | 2.990 (3) | 140 |
Symmetry code: (ii) −x, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C14H8O4)(C12H12N2)] |
Mr | 479.38 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 24.309 (10), 10.161 (4), 9.326 (4) |
β (°) | 100.677 (7) |
V (Å3) | 2263.7 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.62 |
Crystal size (mm) | 0.42 × 0.28 × 0.23 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.781, 0.871 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5868, 2005, 1313 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.083, 0.87 |
No. of reflections | 2005 |
No. of parameters | 150 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.22 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 2000), SHELXL97 (Sheldrick, 2000), SHELXTL/PC (Sheldrick, 1999), SHELXTL/PC.
Mn1—O2i | 2.1214 (19) | N1—C8 | 1.426 (3) |
Mn1—O1 | 2.2066 (18) | O1—C1 | 1.271 (3) |
Mn1—N1 | 2.320 (2) | O2—C1 | 1.251 (3) |
O2i—Mn1—O2ii | 86.23 (11) | O2i—Mn1—N1 | 91.73 (7) |
O2i—Mn1—O1 | 176.45 (7) | O2ii—Mn1—N1 | 92.22 (8) |
O2ii—Mn1—O1 | 91.55 (7) | O1—Mn1—N1 | 85.58 (7) |
O1—Mn1—O1iii | 90.81 (9) | N1iii—Mn1—N1 | 174.58 (11) |
O1—Mn1—N1iii | 90.61 (7) |
Symmetry codes: (i) x, −y+2, z+1/2; (ii) −x, −y+2, −z; (iii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O1ii | 0.90 | 2.24 | 2.990 (3) | 140 |
Symmetry code: (ii) −x, −y+2, −z. |
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The design and syntheses of multidimensional coordination polymers are an attractive area of research because of their intriguing structural diversity and potential applications in functional materials (Moulton & Zaworotko, 2001). Coordination polymers are built by the rational selection of metal ions and the use of structurally interesting ligands with specific functionality to construct metal-organic frameworks. 2,2'-Diphenyldicarboxylic acid (H2bpdc) is useful as a building block for the construction of coordination polymers, and a few coordination polymers using 2,2'-biphenyldicarboxylate (bpdc) as a bridging ligand have been reported (Speier et al., 2001; Rueff et al., 2002; Wang et al., 2002; Wang et al., 2003a; Kumagai et al., 2002; Wang et al., 2003b; Wang et al., 2003c; Thirumurugan et al., 2003). We report here a novel three-dimensional manganese polymer, [Mn(C14H8O4)(C12H12N2)]n, (I), constructed from bpdc and benzidine.
The coordination environment of the MnII ion is shown in Fig.1, with the geometry listed in Table 1. Atom Mn1, which lies on a crystallographic twofold axis, is coordinated to three symmetrically related bpdc ligands via atoms O2i [symmetry code: (i) x, 1 − y, 1/2 + z] and O2ii [symmetry code: (ii) −x, 1 − y, −z] of two bpdc ligands related by the twofold axis, and atoms O1 and O1iii [symmetry code: (iii) −x, y, 1/2 − z] of one bpdc ligand, which itself lies on the twofold axis through atom Mn1. The axial coordination sites of the resulting octahedral environment of atom Mn1 are occupied by N atoms of the benzidine moiety, which itself lies astride a centre of symmetry.
This configuration results in columns (or chains) of linked MnII ions coordinated to an approximately square array of O atoms, as shown in Fig. 2 and end on in Fig. 3. The benzidine ligands link adjacent columns but bind to different columns alternately along the chain, thus producing a three-dimensional network structure in which every MnII column is linked to four adjacent columns. The MnII–benzidine links can be thought of as forming a network of distorted hexagonal holes in which the phenyl rings of the bpdc ligands are contained along the b direction (Fig. 3).
The bpdc group acts as a quadridentate µ3-bridging ligand to link three Mn atoms (Fig. 2). Each bpdc ligand is in a twisted mode, and the dihedral angle between the planes of the two phenyl rings in the bpdc ligand is 68.53 (7)°. The two phenyl rings are coplanar in the centrosymmetric benzidine ligands, but the two benzidine ligands that are linked to the same Mn atom are not in parallel planes. This mode of µ3 binding is found for one of the bpdc ligands in seven, apparently isostructural, complexes of Nd, Dy and Y (Thirumurugan et al., 2003), and La, Pr, Eu and Tb (Wang et al., 2003b), but in these structures a second crystallographically distinct bpdc ligand binds in a different way. The continuous µ3 mode of binding of bpdc ligands to produce the tertiary structure found in (I) (Fig. 2) is unique according to the Cambridge Structural Database (Version 5.25 of July 2004; Allen, 2002).
Only one of the H atoms attached to atoms N1 appears to take part in hydorgen bonding (Table 2).