Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104014453/jz1634sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104014453/jz1634Isup2.hkl |
CCDC reference: 248128
An aqueous solution (10 ml) of NaN3 (0.163 g, 2.5 mmol) was mixed with an aqueous solution (10 ml) of MnSO4·H2O (0.085 g, 0.5 mmol) and stirred for 20 min. Then an ethanol solution (10 ml) of 1,2-bis(imidazol-1-yl)ethane (0.081 g, 0.5 mmol) was added slowly to the above solution. The mixture was stirred at room temperature for 30 min and the resultant solution was filtered. After allowing the filtrate to stand in air at room temperature for two weeks, well formed yellow single crystals of (I) were obtained. The product is stable under an ambient atmosphere and is insoluble in most common inorganic and organic solvents. Analysis, found: C 41.43, H 4.37, N 42.36%; calculated for C16H20MnN14: C 41.47, H 4.35, N 42.33%.
H atoms were placed in idealized positions and refined as riding, with C—H distances of 0.93 (imidazole) and 0.97 Å (CH2), and with Uiso(H) = 1.2Ueq(C). Please check added text.
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[Mn(N3)2(C8H10N4)2] | F(000) = 478 |
Mr = 463.40 | Dx = 1.464 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4684 reflections |
a = 6.9636 (16) Å | θ = 3.3–27.5° |
b = 14.819 (3) Å | µ = 0.66 mm−1 |
c = 10.256 (2) Å | T = 193 K |
β = 96.702 (5)° | Polyhedron, yellow |
V = 1051.1 (4) Å3 | 0.51 × 0.32 × 0.25 mm |
Z = 2 |
Rigaku Mercury CCD area-detector diffractometer | 2393 independent reflections |
Radiation source: fine-focus sealed tube | 2287 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω scans | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan (North et al., 1968) | h = −9→9 |
Tmin = 0.769, Tmax = 0.851 | k = −19→19 |
11499 measured reflections | l = −13→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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0335P)2 + 1.025P] where P = (Fo2 + 2Fc2)/3 |
2393 reflections | (Δ/σ)max < 0.001 |
142 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
[Mn(N3)2(C8H10N4)2] | V = 1051.1 (4) Å3 |
Mr = 463.40 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.9636 (16) Å | µ = 0.66 mm−1 |
b = 14.819 (3) Å | T = 193 K |
c = 10.256 (2) Å | 0.51 × 0.32 × 0.25 mm |
β = 96.702 (5)° |
Rigaku Mercury CCD area-detector diffractometer | 2393 independent reflections |
Absorption correction: multi-scan (North et al., 1968) | 2287 reflections with I > 2σ(I) |
Tmin = 0.769, Tmax = 0.851 | Rint = 0.027 |
11499 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.34 e Å−3 |
2393 reflections | Δρmin = −0.23 e Å−3 |
142 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 | 0.0000 | 0.0000 | 0.01531 (11) | |
N1 | 0.1244 (2) | 0.14032 (10) | −0.01270 (16) | 0.0234 (3) | |
N2 | 0.3487 (2) | 0.24076 (10) | −0.04455 (15) | 0.0231 (3) | |
N3 | 0.8648 (2) | 0.45944 (10) | −0.32108 (14) | 0.0196 (3) | |
N4 | 0.6546 (2) | 0.40931 (10) | −0.19334 (15) | 0.0218 (3) | |
N5 | −0.2775 (2) | 0.04100 (13) | −0.11625 (16) | 0.0285 (4) | |
N6 | −0.3219 (2) | 0.07325 (11) | −0.21954 (16) | 0.0261 (4) | |
N7 | −0.3730 (3) | 0.10376 (17) | −0.3224 (2) | 0.0522 (6) | |
C1 | 0.1044 (3) | 0.21480 (13) | 0.0651 (2) | 0.0281 (4) | |
H1A | 0.0104 | 0.2214 | 0.1218 | 0.034* | |
C2 | 0.2414 (3) | 0.27703 (13) | 0.0471 (2) | 0.0296 (4) | |
H2A | 0.2593 | 0.3328 | 0.0882 | 0.036* | |
C3 | 0.2731 (3) | 0.15922 (12) | −0.07735 (19) | 0.0244 (4) | |
H3A | 0.3197 | 0.1208 | −0.1381 | 0.029* | |
C4 | 0.9450 (3) | 0.46356 (16) | −0.19227 (19) | 0.0314 (5) | |
H4A | 1.0688 | 0.4845 | −0.1639 | 0.038* | |
C5 | 0.8175 (3) | 0.43264 (17) | −0.1126 (2) | 0.0355 (5) | |
H5A | 0.8367 | 0.4282 | −0.0215 | 0.043* | |
C6 | 0.6900 (3) | 0.42610 (12) | −0.31707 (17) | 0.0205 (4) | |
H6A | 0.6019 | 0.4155 | −0.3909 | 0.025* | |
C7 | 0.5205 (3) | 0.27938 (13) | −0.0924 (2) | 0.0266 (4) | |
H7A | 0.5642 | 0.2398 | −0.1582 | 0.032* | |
H7B | 0.6233 | 0.2841 | −0.0203 | 0.032* | |
C8 | 0.4780 (3) | 0.37185 (13) | −0.15148 (19) | 0.0246 (4) | |
H8A | 0.3793 | 0.3672 | −0.2261 | 0.030* | |
H8B | 0.4303 | 0.4113 | −0.0870 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01532 (19) | 0.01622 (18) | 0.01504 (18) | −0.00171 (14) | 0.00455 (13) | −0.00029 (13) |
N1 | 0.0244 (8) | 0.0199 (7) | 0.0270 (8) | −0.0046 (6) | 0.0079 (6) | 0.0001 (6) |
N2 | 0.0251 (8) | 0.0196 (7) | 0.0257 (8) | −0.0062 (6) | 0.0082 (6) | 0.0005 (6) |
N3 | 0.0196 (7) | 0.0220 (7) | 0.0180 (7) | −0.0013 (6) | 0.0056 (6) | 0.0001 (6) |
N4 | 0.0216 (8) | 0.0241 (8) | 0.0205 (7) | −0.0074 (6) | 0.0057 (6) | 0.0010 (6) |
N5 | 0.0198 (8) | 0.0419 (10) | 0.0233 (8) | 0.0028 (7) | 0.0005 (6) | 0.0049 (7) |
N6 | 0.0256 (8) | 0.0308 (9) | 0.0221 (8) | 0.0111 (7) | 0.0039 (6) | −0.0029 (7) |
N7 | 0.0660 (15) | 0.0649 (15) | 0.0260 (10) | 0.0361 (12) | 0.0061 (10) | 0.0092 (10) |
C1 | 0.0325 (10) | 0.0239 (9) | 0.0307 (10) | −0.0049 (8) | 0.0157 (8) | −0.0020 (8) |
C2 | 0.0383 (11) | 0.0227 (9) | 0.0303 (10) | −0.0079 (8) | 0.0147 (9) | −0.0050 (8) |
C3 | 0.0279 (9) | 0.0190 (8) | 0.0278 (9) | −0.0041 (7) | 0.0102 (8) | −0.0014 (7) |
C4 | 0.0275 (10) | 0.0459 (12) | 0.0202 (9) | −0.0159 (9) | 0.0012 (8) | −0.0010 (9) |
C5 | 0.0360 (11) | 0.0543 (14) | 0.0164 (9) | −0.0224 (10) | 0.0029 (8) | −0.0009 (9) |
C6 | 0.0212 (8) | 0.0238 (9) | 0.0167 (8) | −0.0020 (7) | 0.0025 (7) | 0.0020 (7) |
C7 | 0.0242 (9) | 0.0227 (9) | 0.0348 (10) | −0.0063 (7) | 0.0114 (8) | 0.0004 (8) |
C8 | 0.0213 (9) | 0.0270 (9) | 0.0268 (9) | −0.0059 (7) | 0.0084 (7) | 0.0038 (7) |
Mn1—N5 | 2.2334 (16) | N4—C8 | 1.458 (2) |
Mn1—N5i | 2.2334 (16) | N5—N6 | 1.170 (2) |
Mn1—N3ii | 2.2400 (15) | N6—N7 | 1.164 (2) |
Mn1—N3iii | 2.2400 (15) | C1—C2 | 1.355 (3) |
Mn1—N1 | 2.2622 (16) | C1—H1A | 0.9300 |
Mn1—N1i | 2.2622 (16) | C2—H2A | 0.9300 |
N1—C3 | 1.323 (2) | C3—H3A | 0.9300 |
N1—C1 | 1.379 (2) | C4—C5 | 1.355 (3) |
N2—C3 | 1.345 (2) | C4—H4A | 0.9300 |
N2—C2 | 1.376 (2) | C5—H5A | 0.9300 |
N2—C7 | 1.461 (2) | C6—H6A | 0.9300 |
N3—C6 | 1.319 (2) | C7—C8 | 1.513 (3) |
N3—C4 | 1.374 (2) | C7—H7A | 0.9700 |
N3—Mn1iv | 2.2400 (15) | C7—H7B | 0.9700 |
N4—C6 | 1.344 (2) | C8—H8A | 0.9700 |
N4—C5 | 1.369 (3) | C8—H8B | 0.9700 |
N5—Mn1—N5i | 180.00 (12) | C2—C1—H1A | 124.9 |
N5—Mn1—N3ii | 86.80 (6) | N1—C1—H1A | 124.9 |
N5i—Mn1—N3ii | 93.20 (6) | C1—C2—N2 | 105.94 (17) |
N5—Mn1—N3iii | 93.20 (6) | C1—C2—H2A | 127.0 |
N5i—Mn1—N3iii | 86.80 (6) | N2—C2—H2A | 127.0 |
N3ii—Mn1—N3iii | 180.00 (4) | N1—C3—N2 | 111.79 (16) |
N5—Mn1—N1 | 91.86 (6) | N1—C3—H3A | 124.1 |
N5i—Mn1—N1 | 88.14 (6) | N2—C3—H3A | 124.1 |
N3ii—Mn1—N1 | 90.05 (6) | C5—C4—N3 | 110.08 (17) |
N3iii—Mn1—N1 | 89.95 (6) | C5—C4—H4A | 125.0 |
N5—Mn1—N1i | 88.14 (6) | N3—C4—H4A | 125.0 |
N5i—Mn1—N1i | 91.86 (6) | C4—C5—N4 | 106.01 (17) |
N3ii—Mn1—N1i | 89.95 (6) | C4—C5—H5A | 127.0 |
N3iii—Mn1—N1i | 90.05 (6) | N4—C5—H5A | 127.0 |
N1—Mn1—N1i | 180.00 (3) | N3—C6—N4 | 111.75 (16) |
C3—N1—C1 | 104.99 (15) | N3—C6—H6A | 124.1 |
C3—N1—Mn1 | 123.41 (13) | N4—C6—H6A | 124.1 |
C1—N1—Mn1 | 129.59 (12) | N2—C7—C8 | 111.09 (16) |
C3—N2—C2 | 107.08 (15) | N2—C7—H7A | 109.4 |
C3—N2—C7 | 125.42 (16) | C8—C7—H7A | 109.4 |
C2—N2—C7 | 127.39 (16) | N2—C7—H7B | 109.4 |
C6—N3—C4 | 105.05 (15) | C8—C7—H7B | 109.4 |
C6—N3—Mn1iv | 127.14 (12) | H7A—C7—H7B | 108.0 |
C4—N3—Mn1iv | 127.81 (12) | N4—C8—C7 | 109.30 (15) |
C6—N4—C5 | 107.12 (15) | N4—C8—H8A | 109.8 |
C6—N4—C8 | 127.03 (16) | C7—C8—H8A | 109.8 |
C5—N4—C8 | 125.84 (16) | N4—C8—H8B | 109.8 |
N6—N5—Mn1 | 135.64 (14) | C7—C8—H8B | 109.8 |
N7—N6—N5 | 177.4 (2) | H8A—C8—H8B | 108.3 |
C2—C1—N1 | 110.20 (17) | ||
N5—Mn1—N1—C3 | −113.76 (16) | Mn1—N1—C3—N2 | −164.90 (12) |
N5i—Mn1—N1—C3 | 66.24 (16) | C2—N2—C3—N1 | −0.2 (2) |
N3ii—Mn1—N1—C3 | 159.44 (16) | C7—N2—C3—N1 | 176.25 (17) |
N3iii—Mn1—N1—C3 | −20.56 (16) | C6—N3—C4—C5 | 0.0 (3) |
N5—Mn1—N1—C1 | 84.86 (18) | Mn1iv—N3—C4—C5 | −179.86 (15) |
N5i—Mn1—N1—C1 | −95.14 (18) | N3—C4—C5—N4 | −0.3 (3) |
N3ii—Mn1—N1—C1 | −1.94 (18) | C6—N4—C5—C4 | 0.5 (2) |
N3iii—Mn1—N1—C1 | 178.06 (18) | C8—N4—C5—C4 | 179.53 (19) |
N3ii—Mn1—N5—N6 | 146.2 (2) | C4—N3—C6—N4 | 0.3 (2) |
N3iii—Mn1—N5—N6 | −33.8 (2) | Mn1iv—N3—C6—N4 | −179.82 (12) |
N1—Mn1—N5—N6 | 56.3 (2) | C5—N4—C6—N3 | −0.5 (2) |
N1i—Mn1—N5—N6 | −123.7 (2) | C8—N4—C6—N3 | −179.53 (17) |
C3—N1—C1—C2 | −0.4 (2) | C3—N2—C7—C8 | 126.5 (2) |
Mn1—N1—C1—C2 | 163.58 (14) | C2—N2—C7—C8 | −57.8 (3) |
N1—C1—C2—N2 | 0.3 (2) | C6—N4—C8—C7 | 113.3 (2) |
C3—N2—C2—C1 | −0.1 (2) | C5—N4—C8—C7 | −65.6 (3) |
C7—N2—C2—C1 | −176.42 (19) | N2—C7—C8—N4 | 177.85 (15) |
C1—N1—C3—N2 | 0.3 (2) |
Symmetry codes: (i) −x, −y, −z; (ii) x−1, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z−1/2; (iv) −x+1, y+1/2, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(N3)2(C8H10N4)2] |
Mr | 463.40 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 193 |
a, b, c (Å) | 6.9636 (16), 14.819 (3), 10.256 (2) |
β (°) | 96.702 (5) |
V (Å3) | 1051.1 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.66 |
Crystal size (mm) | 0.51 × 0.32 × 0.25 |
Data collection | |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan (North et al., 1968) |
Tmin, Tmax | 0.769, 0.851 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11499, 2393, 2287 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.087, 1.07 |
No. of reflections | 2393 |
No. of parameters | 142 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.23 |
Computer programs: CrystalClear (Rigaku, 2000), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
Mn1—N5 | 2.2334 (16) | N5—N6 | 1.170 (2) |
Mn1—N3i | 2.2400 (15) | N6—N7 | 1.164 (2) |
Mn1—N1 | 2.2622 (16) | ||
N5—Mn1—N5ii | 180.00 (12) | N3i—Mn1—N1 | 90.05 (6) |
N5—Mn1—N3i | 86.80 (6) | N1—Mn1—N1ii | 180.00 (3) |
N3i—Mn1—N3iii | 180.00 (4) | N6—N5—Mn1 | 135.64 (14) |
N5—Mn1—N1 | 91.86 (6) | N7—N6—N5 | 177.4 (2) |
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) −x, −y, −z; (iii) −x+1, y−1/2, −z−1/2. |
The design of coordination polymers has been developing rapidly because of their fascinating structures and potential applications as functional materials (Batten & Robson, 1998; Blake et al., 1999). A number of infinite one-, two- and three-dimensional frameworks have been synthesized with rigid rod-like organic building blocks, such as 4,4'-bipyridine (Fujita et al., 1994) and 4,4'-azobispyridine (Li et al., 2001). Relatively few studies of flexible ligands have been reported. Recently, we synthesized several coordination polymers with the flexible ligand 1,2-bis(1,2,4-triazol-1-yl)ethane (bte; Li et al., 1999, 2003; Zhu et al., 2004). In order to extend our research, we have now chosen a similar ligand, 1,2-bis(imidazol-1-yl)ethane (bim; Wu et al., 1997). Here, we report the preparation and crystal structure of the title novel two-dimensional coordination polymer incorporating the bim ligand, [Mn(bim)2(N3)2]n, (I). \sch
As shown in Fig. 1, the MnII atom of (I) occupies an inversion centre. The coordination geometry of the MnII atom is distorted octahedral; it is coordinated equatorially by four N atoms from the imidazole rings of four symmetry-related bim ligands, and axially by two N atoms from two symmetry-related azide ligands. The azide anion acts as a monodentate ligand (Ribas et al., 1999). The bim ligands exhibit the anti conformation in (I). The two imidazole ring planes, C1—C3/N1/N2 and C4—C6/N3/N4, are planar, with r.m.s. deviations of 0.0015 (12) and 0.0019 (13) Å, respectively. The dihedral angle between these two imidazole ring planes is 177.85 (15)°. The N2—C7—C8—N4 torsion angle is 57.79 (9)°.
As illustrated in Fig. 2, each bim ligand in (I) coordinates two MnII atoms through its two imidazole N atoms, thus acting as a bridging bidentate ligand. The MnII atoms are bridged by four bim ligands to form a two-dimensional neutral (4,4) network. The networks contain square grids (36-membered ring), with an MnII atom at each corner and a bim ligand at each edge connecting two MnII atoms. Due to the symmetry of the crystal structure, the edge lengths are equal, and the value of 11.7484 (16) Å is similar to what was observed in the related bte ligand compound [Cu(TTA)2]2(bte)] [TTA is 1,1,1-trifloro-3-(2-thenoyl)acetone; Li et al., 1999].
The square-grid sheets are stacked in an off-set fashion parallel to the c direction. The off-set superpositions of each pair of adjacent networks by half of the edges divide the voids into smaller rectangles. The azide anions of one sheet project into the holes of the next sheet. In the superposition structure, the sheets are arranged in the sequence ···A—B—A—B···.