Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107056259/av3119sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107056259/av3119Isup2.hkl |
CCDC reference: 677205
For related literature, see: Cao, Sun, Liang, Hong, Tatsumi & Shi (2002); Ding et al. (2006); Janiak (2003); Jones et al. (2004); Laye & McInnes (2004); Li et al. (2007); Ouellette et al. (2006); Zhou et al. (2005).
The synthesis of complex (I) was achieved by two processes. In the first method, a solution of Htrz (60.1 mg, 0.87 mmol), Mn(CH3COO)2·4H2O (245.3 mg, 1 mmol), triethylamine (0.1 ml), CH3CN (8 ml), EtOH (8 ml) and water (1 ml) was stirred briefly before being moved into a 25 ml autoclave and heated at 423 K for 4 d, followed by slow cooling to room temperature. The product was washed with EtOH and water, and colorless block crystals suitable for X-ray diffraction were collected and dried in air (80 mg, 66% in yield). In the second method, a solution of Htrz (70.1 mg, 1.01 mmol), Mn(CH3COCHCOCH3)2 (253 mg, 1 mmol), NaOH (40 mg, 1 mmol), CH3CN (3 ml), EtOH (9 ml) and water (3 ml) was stirred briefly before being moved into a 25 ml autoclave and heated at 443 K for 3 d, followed by slow cooling to room temperature. The product was washed with EtOH and water, and colorless block crystals suitable for X-ray diffraction were collected and dried in air (65 mg, 43% in yield).
The H atom of the hydroxy group were located in an electron density map and were refined with distance restraints [O—H = 0.84 (6) Å]. The other H atoms were refined as riding on their parent C atoms [Uiso(H) = 1.2Ueq(C)].
Data collection: SMART (Bruker, 1998); cell refinement: SMART or SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
[Mn7(C2H2N3)8(C2H3O2)4(OH)2] | Z = 2 |
Mr = 1199.30 | F(000) = 1194 |
Monoclinic, P21/n | Dx = 1.832 Mg m−3 |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 14.677 (2) Å | θ = 1.6–25.0° |
b = 9.2626 (15) Å | µ = 2.05 mm−1 |
c = 16.990 (3) Å | T = 298 K |
β = 109.717 (2)° | Block, colorless |
V = 2174.3 (6) Å3 | 0.22 × 0.20 × 0.17 mm |
Bruker SMART CCD area-detector diffractometer | 3788 independent reflections |
Radiation source: fine-focus sealed tube | 2800 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
phi and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −17→13 |
Tmin = 0.662, Tmax = 0.723 | k = −11→11 |
10662 measured reflections | l = −18→20 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0507P)2 + 1.8699P] where P = (Fo2 + 2Fc2)/3 |
3788 reflections | (Δ/σ)max = 0.001 |
298 parameters | Δρmax = 1.12 e Å−3 |
2 restraints | Δρmin = −0.44 e Å−3 |
[Mn7(C2H2N3)8(C2H3O2)4(OH)2] | V = 2174.3 (6) Å3 |
Mr = 1199.30 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.677 (2) Å | µ = 2.05 mm−1 |
b = 9.2626 (15) Å | T = 298 K |
c = 16.990 (3) Å | 0.22 × 0.20 × 0.17 mm |
β = 109.717 (2)° |
Bruker SMART CCD area-detector diffractometer | 3788 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 2800 reflections with I > 2σ(I) |
Tmin = 0.662, Tmax = 0.723 | Rint = 0.061 |
10662 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 2 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 1.12 e Å−3 |
3788 reflections | Δρmin = −0.44 e Å−3 |
298 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 | 0.75874 (4) | 0.58288 (7) | 0.05458 (4) | 0.02058 (18) | |
Mn2 | 1.01098 (5) | 0.58805 (7) | 0.19767 (4) | 0.02079 (18) | |
Mn3 | 0.5000 | 0.5000 | 0.0000 | 0.0217 (2) | |
Mn4 | 0.88824 (5) | 0.25403 (6) | 0.13261 (4) | 0.02212 (18) | |
N1 | 0.8443 (3) | 0.7891 (4) | 0.0833 (2) | 0.0272 (8) | |
N2 | 0.9352 (3) | 0.7896 (4) | 0.1424 (2) | 0.0263 (8) | |
N3 | 0.8961 (3) | 1.0172 (4) | 0.1041 (2) | 0.0317 (9) | |
N4 | 0.6778 (3) | 0.6400 (4) | 0.1398 (2) | 0.0324 (9) | |
N5 | 0.5842 (3) | 0.6016 (4) | 0.1177 (2) | 0.0305 (9) | |
N6 | 0.6240 (3) | 0.7009 (4) | 0.2427 (2) | 0.0346 (9) | |
N7 | 0.6471 (3) | 0.6946 (4) | −0.0583 (2) | 0.0273 (8) | |
N8 | 0.5525 (3) | 0.6570 (4) | −0.0762 (2) | 0.0292 (9) | |
N9 | 0.5613 (3) | 0.7933 (4) | −0.1807 (2) | 0.0313 (9) | |
N10 | 0.8408 (3) | 0.4749 (4) | −0.0165 (2) | 0.0256 (8) | |
N11 | 0.8865 (3) | 0.3456 (4) | 0.0123 (2) | 0.0272 (8) | |
N12 | 0.9242 (3) | 0.4126 (4) | −0.0989 (2) | 0.0257 (8) | |
O1 | 0.8749 (2) | 0.4857 (3) | 0.16275 (17) | 0.0216 (6) | |
O2 | 0.6402 (2) | 0.3942 (3) | 0.01183 (19) | 0.0291 (7) | |
O3 | 0.7334 (2) | 0.2210 (4) | 0.0860 (2) | 0.0438 (9) | |
O4 | 1.1104 (3) | 0.4285 (4) | 0.2638 (2) | 0.0429 (9) | |
O5 | 1.0453 (2) | 0.2377 (3) | 0.1882 (2) | 0.0376 (8) | |
C1 | 0.9622 (3) | 0.9269 (5) | 0.1526 (3) | 0.0305 (10) | |
H1 | 1.0214 | 0.9572 | 0.1898 | 0.037* | |
C2 | 0.8256 (4) | 0.9262 (5) | 0.0631 (3) | 0.0362 (11) | |
H2 | 0.7680 | 0.9569 | 0.0234 | 0.043* | |
C3 | 0.5556 (3) | 0.6412 (5) | 0.1802 (3) | 0.0326 (11) | |
H3 | 0.4927 | 0.6279 | 0.1801 | 0.039* | |
C4 | 0.6986 (4) | 0.6970 (6) | 0.2144 (3) | 0.0454 (14) | |
H4 | 0.7599 | 0.7317 | 0.2449 | 0.054* | |
C5 | 0.5050 (4) | 0.7173 (5) | −0.1486 (3) | 0.0354 (11) | |
H5 | 0.4386 | 0.7079 | −0.1749 | 0.042* | |
C6 | 0.6483 (3) | 0.7756 (5) | −0.1216 (3) | 0.0311 (11) | |
H6 | 0.7046 | 0.8170 | −0.1251 | 0.037* | |
C7 | 0.9344 (3) | 0.3150 (5) | −0.0378 (3) | 0.0306 (10) | |
H7 | 0.9725 | 0.2328 | −0.0318 | 0.037* | |
C8 | 0.8650 (3) | 0.5084 (5) | −0.0813 (3) | 0.0262 (10) | |
H8 | 0.8431 | 0.5915 | −0.1127 | 0.031* | |
C9 | 0.6590 (3) | 0.2616 (4) | 0.0307 (3) | 0.0252 (9) | |
C10 | 0.5874 (4) | 0.1493 (6) | −0.0158 (4) | 0.0509 (15) | |
H10A | 0.6024 | 0.1186 | −0.0640 | 0.061* | |
H10B | 0.5233 | 0.1894 | −0.0333 | 0.061* | |
H10C | 0.5906 | 0.0680 | 0.0201 | 0.061* | |
C11 | 1.1119 (3) | 0.2985 (5) | 0.2448 (3) | 0.0293 (10) | |
C12 | 1.1990 (5) | 0.2119 (7) | 0.2903 (4) | 0.0657 (18) | |
H12A | 1.1994 | 0.1248 | 0.2598 | 0.079* | |
H12B | 1.1978 | 0.1881 | 0.3449 | 0.079* | |
H12C | 1.2562 | 0.2670 | 0.2956 | 0.079* | |
H15 | 0.852 (5) | 0.482 (8) | 0.202 (3) | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0180 (3) | 0.0224 (3) | 0.0190 (3) | 0.0014 (3) | 0.0033 (3) | −0.0005 (3) |
Mn2 | 0.0201 (3) | 0.0208 (3) | 0.0186 (3) | 0.0007 (3) | 0.0027 (3) | −0.0017 (3) |
Mn3 | 0.0190 (5) | 0.0260 (5) | 0.0166 (4) | −0.0020 (4) | 0.0015 (4) | 0.0000 (4) |
Mn4 | 0.0252 (4) | 0.0183 (3) | 0.0199 (3) | 0.0004 (3) | 0.0038 (3) | 0.0030 (3) |
N1 | 0.022 (2) | 0.0206 (19) | 0.0319 (19) | 0.0015 (15) | −0.0005 (16) | 0.0008 (16) |
N2 | 0.024 (2) | 0.0213 (19) | 0.0273 (19) | 0.0018 (15) | 0.0001 (16) | −0.0024 (16) |
N3 | 0.032 (2) | 0.0176 (19) | 0.037 (2) | 0.0012 (17) | 0.0004 (18) | 0.0003 (17) |
N4 | 0.022 (2) | 0.047 (2) | 0.0282 (19) | −0.0059 (18) | 0.0085 (17) | −0.0126 (18) |
N5 | 0.023 (2) | 0.043 (2) | 0.0233 (18) | −0.0021 (18) | 0.0049 (16) | −0.0082 (17) |
N6 | 0.031 (2) | 0.045 (2) | 0.0252 (19) | −0.0030 (19) | 0.0069 (18) | −0.0105 (18) |
N7 | 0.024 (2) | 0.031 (2) | 0.0216 (18) | −0.0012 (16) | 0.0008 (15) | 0.0073 (16) |
N8 | 0.021 (2) | 0.036 (2) | 0.0246 (18) | 0.0021 (17) | 0.0002 (16) | 0.0104 (17) |
N9 | 0.034 (2) | 0.034 (2) | 0.0212 (18) | −0.0029 (18) | 0.0031 (17) | 0.0083 (17) |
N10 | 0.028 (2) | 0.0251 (19) | 0.0207 (17) | 0.0017 (16) | 0.0045 (16) | 0.0019 (15) |
N11 | 0.036 (2) | 0.0241 (19) | 0.0228 (18) | 0.0048 (17) | 0.0118 (17) | 0.0036 (16) |
N12 | 0.028 (2) | 0.0256 (19) | 0.0245 (18) | 0.0013 (16) | 0.0098 (16) | −0.0005 (16) |
O1 | 0.0207 (15) | 0.0223 (15) | 0.0200 (14) | 0.0008 (12) | 0.0044 (12) | 0.0025 (12) |
O2 | 0.0233 (17) | 0.0239 (16) | 0.0361 (17) | 0.0035 (13) | 0.0046 (14) | 0.0021 (13) |
O3 | 0.0241 (19) | 0.041 (2) | 0.054 (2) | −0.0011 (15) | −0.0035 (17) | 0.0138 (17) |
O4 | 0.043 (2) | 0.0336 (19) | 0.0390 (18) | 0.0103 (16) | −0.0036 (16) | 0.0024 (16) |
O5 | 0.0299 (19) | 0.0368 (19) | 0.0424 (19) | −0.0003 (15) | 0.0074 (16) | 0.0012 (16) |
C1 | 0.024 (2) | 0.025 (2) | 0.036 (2) | −0.0014 (19) | 0.001 (2) | −0.003 (2) |
C2 | 0.030 (3) | 0.025 (2) | 0.040 (3) | 0.001 (2) | −0.006 (2) | −0.001 (2) |
C3 | 0.024 (3) | 0.045 (3) | 0.026 (2) | −0.005 (2) | 0.005 (2) | −0.006 (2) |
C4 | 0.025 (3) | 0.072 (4) | 0.036 (3) | −0.012 (3) | 0.007 (2) | −0.027 (3) |
C5 | 0.027 (3) | 0.044 (3) | 0.028 (2) | −0.004 (2) | −0.001 (2) | 0.009 (2) |
C6 | 0.022 (2) | 0.038 (3) | 0.028 (2) | −0.005 (2) | 0.002 (2) | 0.003 (2) |
C7 | 0.036 (3) | 0.028 (2) | 0.028 (2) | 0.007 (2) | 0.011 (2) | 0.003 (2) |
C8 | 0.028 (2) | 0.024 (2) | 0.027 (2) | 0.0039 (19) | 0.010 (2) | 0.0048 (19) |
C9 | 0.020 (2) | 0.022 (2) | 0.035 (2) | 0.0007 (18) | 0.010 (2) | −0.0019 (19) |
C10 | 0.038 (3) | 0.030 (3) | 0.069 (4) | −0.005 (2) | −0.004 (3) | −0.004 (3) |
C11 | 0.025 (2) | 0.034 (3) | 0.029 (2) | −0.001 (2) | 0.009 (2) | 0.001 (2) |
C12 | 0.053 (4) | 0.048 (3) | 0.072 (4) | 0.018 (3) | −0.010 (3) | 0.001 (3) |
Mn1—N10 | 2.211 (4) | N6—Mn4vii | 2.240 (4) |
Mn1—N4 | 2.224 (4) | N7—C6 | 1.317 (5) |
Mn1—O1 | 2.232 (3) | N7—N8 | 1.363 (5) |
Mn1—N1 | 2.247 (4) | N8—C5 | 1.316 (6) |
Mn1—N7 | 2.305 (3) | N9—C5 | 1.335 (6) |
Mn1—O2 | 2.399 (3) | N9—C6 | 1.342 (6) |
Mn2—O1 | 2.107 (3) | N9—Mn2viii | 2.234 (3) |
Mn2—O4 | 2.114 (3) | N10—C8 | 1.303 (5) |
Mn2—N12i | 2.191 (3) | N10—N11 | 1.379 (5) |
Mn2—N2 | 2.213 (3) | N11—C7 | 1.305 (5) |
Mn2—N9ii | 2.234 (3) | N12—C8 | 1.345 (5) |
Mn3—N5 | 2.178 (4) | N12—C7 | 1.345 (5) |
Mn3—N5iii | 2.178 (4) | N12—Mn2i | 2.191 (3) |
Mn3—O2iii | 2.226 (3) | O1—H15 | 0.84 (6) |
Mn3—O2 | 2.226 (3) | O2—C9 | 1.276 (5) |
Mn3—N8iii | 2.248 (3) | O3—C9 | 1.234 (5) |
Mn3—N8 | 2.248 (3) | O4—C11 | 1.250 (5) |
Mn4—O3 | 2.162 (3) | O5—C11 | 1.250 (6) |
Mn4—O5 | 2.181 (3) | C1—H1 | 0.9300 |
Mn4—N11 | 2.206 (3) | C2—H2 | 0.9300 |
Mn4—O1 | 2.230 (3) | C3—H3 | 0.9300 |
Mn4—N6iv | 2.240 (4) | C4—H4 | 0.9300 |
Mn4—N3v | 2.258 (4) | C5—H5 | 0.9300 |
N1—C2 | 1.320 (6) | C6—H6 | 0.9300 |
N1—N2 | 1.374 (5) | C7—H7 | 0.9300 |
N2—C1 | 1.325 (5) | C8—H8 | 0.9300 |
N3—C1 | 1.334 (6) | C9—C10 | 1.500 (6) |
N3—C2 | 1.335 (6) | C10—H10A | 0.9600 |
N3—Mn4vi | 2.258 (4) | C10—H10B | 0.9600 |
N4—C4 | 1.310 (6) | C10—H10C | 0.9600 |
N4—N5 | 1.344 (5) | C11—C12 | 1.486 (7) |
N5—C3 | 1.320 (5) | C12—H12A | 0.9600 |
N6—C3 | 1.313 (6) | C12—H12B | 0.9600 |
N6—C4 | 1.337 (6) | C12—H12C | 0.9600 |
N10—Mn1—N4 | 166.36 (14) | C6—N7—N8 | 104.9 (3) |
N10—Mn1—O1 | 82.04 (12) | C6—N7—Mn1 | 137.2 (3) |
N4—Mn1—O1 | 89.26 (13) | N8—N7—Mn1 | 117.1 (2) |
N10—Mn1—N1 | 97.77 (13) | C5—N8—N7 | 106.1 (3) |
N4—Mn1—N1 | 92.21 (14) | C5—N8—Mn3 | 129.5 (3) |
O1—Mn1—N1 | 87.04 (12) | N7—N8—Mn3 | 123.9 (3) |
N10—Mn1—N7 | 96.56 (13) | C5—N9—C6 | 101.1 (3) |
N4—Mn1—N7 | 92.81 (14) | C5—N9—Mn2viii | 125.5 (3) |
O1—Mn1—N7 | 175.83 (12) | C6—N9—Mn2viii | 133.4 (3) |
N1—Mn1—N7 | 89.27 (13) | C8—N10—N11 | 105.5 (3) |
N10—Mn1—O2 | 88.77 (12) | C8—N10—Mn1 | 135.0 (3) |
N4—Mn1—O2 | 83.00 (12) | N11—N10—Mn1 | 119.3 (2) |
O1—Mn1—O2 | 103.30 (10) | C7—N11—N10 | 105.2 (3) |
N1—Mn1—O2 | 168.49 (12) | C7—N11—Mn4 | 132.9 (3) |
N7—Mn1—O2 | 80.55 (12) | N10—N11—Mn4 | 121.0 (2) |
O1—Mn2—O4 | 104.72 (13) | C8—N12—C7 | 100.6 (4) |
O1—Mn2—N12i | 113.49 (12) | C8—N12—Mn2i | 130.7 (3) |
O4—Mn2—N12i | 90.30 (14) | C7—N12—Mn2i | 128.7 (3) |
O1—Mn2—N2 | 88.12 (12) | Mn2—O1—Mn4 | 110.43 (12) |
O4—Mn2—N2 | 166.63 (14) | Mn2—O1—Mn1 | 116.03 (12) |
N12i—Mn2—N2 | 87.90 (13) | Mn4—O1—Mn1 | 107.50 (12) |
O1—Mn2—N9ii | 117.89 (13) | Mn2—O1—H15 | 113 (5) |
O4—Mn2—N9ii | 84.18 (14) | Mn4—O1—H15 | 104 (5) |
N12i—Mn2—N9ii | 128.03 (14) | Mn1—O1—H15 | 106 (5) |
N2—Mn2—N9ii | 86.51 (13) | C9—O2—Mn3 | 124.1 (3) |
N5—Mn3—N5iii | 180.0 | C9—O2—Mn1 | 123.5 (3) |
N5—Mn3—O2iii | 96.53 (13) | Mn3—O2—Mn1 | 105.11 (11) |
N5iii—Mn3—O2iii | 83.47 (13) | C9—O3—Mn4 | 141.9 (3) |
N5—Mn3—O2 | 83.47 (13) | C11—O4—Mn2 | 127.3 (3) |
N5iii—Mn3—O2 | 96.53 (13) | C11—O5—Mn4 | 137.7 (3) |
O2iii—Mn3—O2 | 180.0 | N2—C1—N3 | 113.5 (4) |
N5—Mn3—N8iii | 87.11 (14) | N2—C1—H1 | 123.2 |
N5iii—Mn3—N8iii | 92.89 (14) | N3—C1—H1 | 123.2 |
O2iii—Mn3—N8iii | 81.43 (12) | N1—C2—N3 | 114.5 (4) |
O2—Mn3—N8iii | 98.57 (12) | N1—C2—H2 | 122.7 |
N5—Mn3—N8 | 92.89 (14) | N3—C2—H2 | 122.7 |
N5iii—Mn3—N8 | 87.11 (14) | N6—C3—N5 | 113.8 (4) |
O2iii—Mn3—N8 | 98.57 (12) | N6—C3—H3 | 123.1 |
O2—Mn3—N8 | 81.43 (12) | N5—C3—H3 | 123.1 |
N8iii—Mn3—N8 | 180.0 | N4—C4—N6 | 114.0 (4) |
O3—Mn4—O5 | 167.34 (13) | N4—C4—H4 | 123.0 |
O3—Mn4—N11 | 91.90 (14) | N6—C4—H4 | 123.0 |
O5—Mn4—N11 | 96.21 (13) | N8—C5—N9 | 113.7 (4) |
O3—Mn4—O1 | 93.28 (12) | N8—C5—H5 | 123.2 |
O5—Mn4—O1 | 97.41 (11) | N9—C5—H5 | 123.2 |
N11—Mn4—O1 | 82.43 (11) | N7—C6—N9 | 114.2 (4) |
O3—Mn4—N6iv | 84.55 (14) | N7—C6—H6 | 122.9 |
O5—Mn4—N6iv | 89.18 (13) | N9—C6—H6 | 122.9 |
N11—Mn4—N6iv | 168.93 (14) | N11—C7—N12 | 114.4 (4) |
O1—Mn4—N6iv | 87.30 (13) | N11—C7—H7 | 122.8 |
O3—Mn4—N3v | 84.71 (14) | N12—C7—H7 | 122.8 |
O5—Mn4—N3v | 84.41 (13) | N10—C8—N12 | 114.3 (4) |
N11—Mn4—N3v | 99.23 (13) | N10—C8—H8 | 122.8 |
O1—Mn4—N3v | 177.41 (12) | N12—C8—H8 | 122.8 |
N6iv—Mn4—N3v | 90.89 (14) | O3—C9—O2 | 123.0 (4) |
C2—N1—N2 | 104.6 (3) | O3—C9—C10 | 118.2 (4) |
C2—N1—Mn1 | 135.2 (3) | O2—C9—C10 | 118.8 (4) |
N2—N1—Mn1 | 119.7 (2) | C9—C10—H10A | 109.5 |
C1—N2—N1 | 105.8 (3) | C9—C10—H10B | 109.5 |
C1—N2—Mn2 | 132.0 (3) | H10A—C10—H10B | 109.5 |
N1—N2—Mn2 | 122.2 (2) | C9—C10—H10C | 109.5 |
C1—N3—C2 | 101.5 (4) | H10A—C10—H10C | 109.5 |
C1—N3—Mn4vi | 123.8 (3) | H10B—C10—H10C | 109.5 |
C2—N3—Mn4vi | 129.7 (3) | O4—C11—O5 | 123.7 (4) |
C4—N4—N5 | 105.1 (4) | O4—C11—C12 | 118.2 (5) |
C4—N4—Mn1 | 136.4 (3) | O5—C11—C12 | 118.0 (4) |
N5—N4—Mn1 | 118.4 (3) | C11—C12—H12A | 109.5 |
C3—N5—N4 | 106.0 (3) | C11—C12—H12B | 109.5 |
C3—N5—Mn3 | 128.5 (3) | H12A—C12—H12B | 109.5 |
N4—N5—Mn3 | 125.5 (3) | C11—C12—H12C | 109.5 |
C3—N6—C4 | 101.2 (4) | H12A—C12—H12C | 109.5 |
C3—N6—Mn4vii | 125.0 (3) | H12B—C12—H12C | 109.5 |
C4—N6—Mn4vii | 133.1 (3) | ||
N10—Mn1—N1—C2 | 115.5 (4) | N12i—Mn2—O1—Mn1 | −61.26 (17) |
N4—Mn1—N1—C2 | −73.8 (5) | N2—Mn2—O1—Mn1 | 25.63 (15) |
O1—Mn1—N1—C2 | −162.9 (4) | N9ii—Mn2—O1—Mn1 | 110.68 (16) |
N7—Mn1—N1—C2 | 19.0 (5) | O3—Mn4—O1—Mn2 | −172.02 (14) |
O2—Mn1—N1—C2 | −8.7 (9) | O5—Mn4—O1—Mn2 | 14.78 (14) |
N10—Mn1—N1—N2 | −73.8 (3) | N11—Mn4—O1—Mn2 | −80.54 (14) |
N4—Mn1—N1—N2 | 96.9 (3) | N6iv—Mn4—O1—Mn2 | 103.59 (15) |
O1—Mn1—N1—N2 | 7.7 (3) | O3—Mn4—O1—Mn1 | −44.55 (14) |
N7—Mn1—N1—N2 | −170.3 (3) | O5—Mn4—O1—Mn1 | 142.25 (12) |
O2—Mn1—N1—N2 | 162.0 (5) | N11—Mn4—O1—Mn1 | 46.93 (14) |
C2—N1—N2—C1 | 0.4 (4) | N6iv—Mn4—O1—Mn1 | −128.93 (14) |
Mn1—N1—N2—C1 | −172.8 (3) | N10—Mn1—O1—Mn2 | 75.58 (15) |
C2—N1—N2—Mn2 | −177.2 (3) | N4—Mn1—O1—Mn2 | −114.96 (15) |
Mn1—N1—N2—Mn2 | 9.6 (4) | N1—Mn1—O1—Mn2 | −22.70 (15) |
O1—Mn2—N2—C1 | 161.1 (4) | O2—Mn1—O1—Mn2 | 162.41 (13) |
O4—Mn2—N2—C1 | −2.8 (8) | N10—Mn1—O1—Mn4 | −48.57 (13) |
N12i—Mn2—N2—C1 | −85.3 (4) | N4—Mn1—O1—Mn4 | 120.90 (14) |
N9ii—Mn2—N2—C1 | 43.1 (4) | N1—Mn1—O1—Mn4 | −146.85 (14) |
O1—Mn2—N2—N1 | −21.9 (3) | O2—Mn1—O1—Mn4 | 38.27 (13) |
O4—Mn2—N2—N1 | 174.1 (5) | N5—Mn3—O2—C9 | 107.1 (3) |
N12i—Mn2—N2—N1 | 91.7 (3) | N5iii—Mn3—O2—C9 | −72.9 (3) |
N9ii—Mn2—N2—N1 | −140.0 (3) | N8iii—Mn3—O2—C9 | 21.0 (3) |
N10—Mn1—N4—C4 | 95.1 (8) | N8—Mn3—O2—C9 | −159.0 (3) |
O1—Mn1—N4—C4 | 44.9 (5) | N5—Mn3—O2—Mn1 | −43.82 (13) |
N1—Mn1—N4—C4 | −42.1 (5) | N5iii—Mn3—O2—Mn1 | 136.18 (13) |
N7—Mn1—N4—C4 | −131.5 (5) | N8iii—Mn3—O2—Mn1 | −129.89 (13) |
O2—Mn1—N4—C4 | 148.4 (5) | N8—Mn3—O2—Mn1 | 50.11 (13) |
N10—Mn1—N4—N5 | −78.9 (7) | N10—Mn1—O2—C9 | 61.5 (3) |
O1—Mn1—N4—N5 | −129.1 (3) | N4—Mn1—O2—C9 | −107.6 (3) |
N1—Mn1—N4—N5 | 143.9 (3) | O1—Mn1—O2—C9 | −20.0 (3) |
N7—Mn1—N4—N5 | 54.5 (3) | N1—Mn1—O2—C9 | −173.5 (6) |
O2—Mn1—N4—N5 | −25.6 (3) | N7—Mn1—O2—C9 | 158.4 (3) |
C4—N4—N5—C3 | 1.1 (5) | N10—Mn1—O2—Mn3 | −147.35 (14) |
Mn1—N4—N5—C3 | 176.8 (3) | N4—Mn1—O2—Mn3 | 43.55 (14) |
C4—N4—N5—Mn3 | 179.7 (4) | O1—Mn1—O2—Mn3 | 131.13 (12) |
Mn1—N4—N5—Mn3 | −4.6 (5) | N1—Mn1—O2—Mn3 | −22.4 (7) |
O2iii—Mn3—N5—C3 | 32.4 (4) | N7—Mn1—O2—Mn3 | −50.49 (13) |
O2—Mn3—N5—C3 | −147.6 (4) | O5—Mn4—O3—C9 | −150.1 (5) |
N8iii—Mn3—N5—C3 | −48.6 (4) | N11—Mn4—O3—C9 | −20.2 (5) |
N8—Mn3—N5—C3 | 131.4 (4) | O1—Mn4—O3—C9 | 62.3 (5) |
O2iii—Mn3—N5—N4 | −145.9 (4) | N6iv—Mn4—O3—C9 | 149.2 (5) |
O2—Mn3—N5—N4 | 34.1 (4) | N3v—Mn4—O3—C9 | −119.3 (5) |
N8iii—Mn3—N5—N4 | 133.1 (4) | O1—Mn2—O4—C11 | 43.0 (4) |
N8—Mn3—N5—N4 | −46.9 (4) | N12i—Mn2—O4—C11 | −71.4 (4) |
N10—Mn1—N7—C6 | −50.2 (5) | N2—Mn2—O4—C11 | −153.5 (5) |
N4—Mn1—N7—C6 | 139.7 (5) | N9ii—Mn2—O4—C11 | 160.4 (4) |
N1—Mn1—N7—C6 | 47.5 (5) | O3—Mn4—O5—C11 | −121.2 (6) |
O2—Mn1—N7—C6 | −137.8 (5) | N11—Mn4—O5—C11 | 109.3 (4) |
N10—Mn1—N7—N8 | 117.8 (3) | O1—Mn4—O5—C11 | 26.2 (5) |
N4—Mn1—N7—N8 | −52.3 (3) | N6iv—Mn4—O5—C11 | −61.0 (5) |
N1—Mn1—N7—N8 | −144.4 (3) | N3v—Mn4—O5—C11 | −152.0 (5) |
O2—Mn1—N7—N8 | 30.2 (3) | N1—N2—C1—N3 | −0.4 (5) |
C6—N7—N8—C5 | 0.4 (5) | Mn2—N2—C1—N3 | 176.9 (3) |
Mn1—N7—N8—C5 | −171.2 (3) | C2—N3—C1—N2 | 0.2 (5) |
C6—N7—N8—Mn3 | 173.7 (3) | Mn4vi—N3—C1—N2 | 157.4 (3) |
Mn1—N7—N8—Mn3 | 2.1 (4) | N2—N1—C2—N3 | −0.4 (5) |
N5—Mn3—N8—C5 | −141.1 (4) | Mn1—N1—C2—N3 | 171.3 (3) |
N5iii—Mn3—N8—C5 | 38.9 (4) | C1—N3—C2—N1 | 0.1 (6) |
O2iii—Mn3—N8—C5 | −44.1 (4) | Mn4vi—N3—C2—N1 | −155.1 (3) |
O2—Mn3—N8—C5 | 135.9 (4) | C4—N6—C3—N5 | 0.4 (6) |
N5—Mn3—N8—N7 | 47.2 (3) | Mn4vii—N6—C3—N5 | −170.8 (3) |
N5iii—Mn3—N8—N7 | −132.8 (3) | N4—N5—C3—N6 | −1.0 (6) |
O2iii—Mn3—N8—N7 | 144.2 (3) | Mn3—N5—C3—N6 | −179.5 (3) |
O2—Mn3—N8—N7 | −35.8 (3) | N5—N4—C4—N6 | −1.0 (6) |
N4—Mn1—N10—C8 | 168.7 (5) | Mn1—N4—C4—N6 | −175.5 (4) |
O1—Mn1—N10—C8 | −140.5 (4) | C3—N6—C4—N4 | 0.4 (6) |
N1—Mn1—N10—C8 | −54.6 (4) | Mn4vii—N6—C4—N4 | 170.6 (3) |
N7—Mn1—N10—C8 | 35.6 (4) | N7—N8—C5—N9 | −0.1 (6) |
O2—Mn1—N10—C8 | 115.9 (4) | Mn3—N8—C5—N9 | −172.9 (3) |
N4—Mn1—N10—N11 | −17.2 (7) | C6—N9—C5—N8 | −0.3 (5) |
O1—Mn1—N10—N11 | 33.7 (3) | Mn2viii—N9—C5—N8 | 179.7 (3) |
N1—Mn1—N10—N11 | 119.5 (3) | N8—N7—C6—N9 | −0.6 (5) |
N7—Mn1—N10—N11 | −150.3 (3) | Mn1—N7—C6—N9 | 168.3 (3) |
O2—Mn1—N10—N11 | −70.0 (3) | C5—N9—C6—N7 | 0.6 (5) |
C8—N10—N11—C7 | 0.6 (4) | Mn2viii—N9—C6—N7 | −179.4 (3) |
Mn1—N10—N11—C7 | −175.1 (3) | N10—N11—C7—N12 | −0.7 (5) |
C8—N10—N11—Mn4 | 170.9 (3) | Mn4—N11—C7—N12 | −169.3 (3) |
Mn1—N10—N11—Mn4 | −4.8 (4) | C8—N12—C7—N11 | 0.4 (5) |
O3—Mn4—N11—C7 | −126.9 (4) | Mn2i—N12—C7—N11 | 179.8 (3) |
O5—Mn4—N11—C7 | 43.4 (4) | N11—N10—C8—N12 | −0.4 (5) |
O1—Mn4—N11—C7 | 140.0 (4) | Mn1—N10—C8—N12 | 174.3 (3) |
N6iv—Mn4—N11—C7 | 162.1 (7) | C7—N12—C8—N10 | 0.1 (5) |
N3v—Mn4—N11—C7 | −42.0 (4) | Mn2i—N12—C8—N10 | −179.3 (3) |
O3—Mn4—N11—N10 | 65.9 (3) | Mn4—O3—C9—O2 | −45.7 (7) |
O5—Mn4—N11—N10 | −123.8 (3) | Mn4—O3—C9—C10 | 134.6 (5) |
O1—Mn4—N11—N10 | −27.1 (3) | Mn3—O2—C9—O3 | −130.5 (4) |
N6iv—Mn4—N11—N10 | −5.1 (9) | Mn1—O2—C9—O3 | 15.2 (6) |
N3v—Mn4—N11—N10 | 150.9 (3) | Mn3—O2—C9—C10 | 49.2 (5) |
O4—Mn2—O1—Mn4 | −35.54 (15) | Mn1—O2—C9—C10 | −165.1 (3) |
N12i—Mn2—O1—Mn4 | 61.35 (16) | Mn2—O4—C11—O5 | −10.2 (7) |
N2—Mn2—O1—Mn4 | 148.24 (14) | Mn2—O4—C11—C12 | 167.9 (4) |
N9ii—Mn2—O1—Mn4 | −126.71 (14) | Mn4—O5—C11—O4 | −32.0 (7) |
O4—Mn2—O1—Mn1 | −158.16 (14) | Mn4—O5—C11—C12 | 149.8 (4) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z; (iv) −x+3/2, y−1/2, −z+1/2; (v) x, y−1, z; (vi) x, y+1, z; (vii) −x+3/2, y+1/2, −z+1/2; (viii) x−1/2, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn7(C2H2N3)8(C2H3O2)4(OH)2] |
Mr | 1199.30 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 14.677 (2), 9.2626 (15), 16.990 (3) |
β (°) | 109.717 (2) |
V (Å3) | 2174.3 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.05 |
Crystal size (mm) | 0.22 × 0.20 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.662, 0.723 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10662, 3788, 2800 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.113, 1.07 |
No. of reflections | 3788 |
No. of parameters | 298 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.12, −0.44 |
Computer programs: SMART (Bruker, 1998), SMART or SAINT (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Mn1—N10 | 2.211 (4) | Mn3—O2 | 2.226 (3) |
Mn1—N4 | 2.224 (4) | Mn3—N8iii | 2.248 (3) |
Mn1—O1 | 2.232 (3) | Mn3—N8 | 2.248 (3) |
Mn1—N1 | 2.247 (4) | Mn4—O3 | 2.162 (3) |
Mn1—N7 | 2.305 (3) | Mn4—O5 | 2.181 (3) |
Mn1—O2 | 2.399 (3) | Mn4—N11 | 2.206 (3) |
Mn2—O1 | 2.107 (3) | Mn4—O1 | 2.230 (3) |
Mn2—N12i | 2.191 (3) | Mn4—N6iv | 2.240 (4) |
Mn2—N2 | 2.213 (3) | Mn4—N3v | 2.258 (4) |
Mn2—N9ii | 2.234 (3) | N3—Mn4vi | 2.258 (4) |
Mn3—N5 | 2.178 (4) | N6—Mn4vii | 2.240 (4) |
Mn3—N5iii | 2.178 (4) | N9—Mn2viii | 2.234 (3) |
Mn3—O2iii | 2.226 (3) | N12—Mn2i | 2.191 (3) |
N10—Mn1—N4 | 166.36 (14) | N5iii—Mn3—O2 | 96.53 (13) |
N10—Mn1—O1 | 82.04 (12) | O2iii—Mn3—O2 | 180.0 |
N4—Mn1—O1 | 89.26 (13) | N5—Mn3—N8iii | 87.11 (14) |
N10—Mn1—N1 | 97.77 (13) | N5iii—Mn3—N8iii | 92.89 (14) |
N4—Mn1—N1 | 92.21 (14) | O2iii—Mn3—N8iii | 81.43 (12) |
O1—Mn1—N1 | 87.04 (12) | O2—Mn3—N8iii | 98.57 (12) |
N10—Mn1—N7 | 96.56 (13) | N5—Mn3—N8 | 92.89 (14) |
N4—Mn1—N7 | 92.81 (14) | N5iii—Mn3—N8 | 87.11 (14) |
O1—Mn1—N7 | 175.83 (12) | O2iii—Mn3—N8 | 98.57 (12) |
N1—Mn1—N7 | 89.27 (13) | O2—Mn3—N8 | 81.43 (12) |
N10—Mn1—O2 | 88.77 (12) | N8iii—Mn3—N8 | 180.0 |
N4—Mn1—O2 | 83.00 (12) | O3—Mn4—O5 | 167.34 (13) |
O1—Mn1—O2 | 103.30 (10) | O3—Mn4—N11 | 91.90 (14) |
N1—Mn1—O2 | 168.49 (12) | O5—Mn4—N11 | 96.21 (13) |
N7—Mn1—O2 | 80.55 (12) | O3—Mn4—O1 | 93.28 (12) |
O1—Mn2—O4 | 104.72 (13) | O5—Mn4—O1 | 97.41 (11) |
O1—Mn2—N12i | 113.49 (12) | N11—Mn4—O1 | 82.43 (11) |
O4—Mn2—N12i | 90.30 (14) | O3—Mn4—N6iv | 84.55 (14) |
O1—Mn2—N2 | 88.12 (12) | O5—Mn4—N6iv | 89.18 (13) |
O4—Mn2—N2 | 166.63 (14) | N11—Mn4—N6iv | 168.93 (14) |
N12i—Mn2—N2 | 87.90 (13) | O1—Mn4—N6iv | 87.30 (13) |
O1—Mn2—N9ii | 117.89 (13) | O3—Mn4—N3v | 84.71 (14) |
O4—Mn2—N9ii | 84.18 (14) | O5—Mn4—N3v | 84.41 (13) |
N12i—Mn2—N9ii | 128.03 (14) | N11—Mn4—N3v | 99.23 (13) |
N2—Mn2—N9ii | 86.51 (13) | O1—Mn4—N3v | 177.41 (12) |
N5—Mn3—N5iii | 180.0 | N6iv—Mn4—N3v | 90.89 (14) |
N5—Mn3—O2 | 83.47 (13) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z; (iv) −x+3/2, y−1/2, −z+1/2; (v) x, y−1, z; (vi) x, y+1, z; (vii) −x+3/2, y+1/2, −z+1/2; (viii) x−1/2, −y+3/2, z−1/2. |
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Synthesis of inorganic coordination polymeric complexes has developed rapidly in recent years owing to their fascinating variety of topologies as well as the potential applications in many fields such as catalysis, electrical conductivity, luminescene, magnetism and nonlinear optics (Cao et al., 2002; Janiak, 2003). Ligands used in construction polymers to bridge metals usually contain oxygen or nitrogen donors, in which multitopic carboxylate and pyridine ligands are most extensively exploited as linkers. However, more and more attention is being paid to ligands that could offer alternative tether lengths, different charge-balance requirements and orientations of donor groups, and 1,2,4-triazole is one such ligand (Ouellette et al., 2006). 1,2,4-Triazole and its derivatives are very interesting ligands that can bridge as well as chelate metals, with 1,2-bridging (Milios et al., 2006) or 1,2,4-bridging forms (Ouellette et al., 2006). It can also be used as a monodentate ligand (Li et al., 2007), and most complexes with this ligand exhibit antiferromagnetic coupling (Zhou et al., 2005; Ding et al., 2006).
On the other hand, Mn-based complexes have been widely reported over the past two decades, one of the most important reasons for this interest being their paramagnetic nature. Many exhibit large ground spin states (Jones et al., 2004), many of which are thought to be the origin of the magnetic bistability displayed by single-molecule magnets (Laye & McInnes, 2004).
With this in mind, we decided to introduce MnII into the triazole ligand, considering that such metal-organic frameworks would exhibit unusual magnetic exchanging behavior (Tangoulis et al., 1998). The title complex, (I), was obtained by solvothermal reaction of 1,2,4-triazole (Htrz) with Mn(CH3COO)2·4H2O at 423 K or with Mn(CH3COCHCOCH3)2 at 443 K.
Single crystal structure analysis reveals that complex (I) is composed of heptanuclear [Mn7(trz)8(CH3COO)4(OH)2] building units, which are further interlinked through bonds formed by Mn and N atoms into a three-dimensional polymer. The heptanuclear Mn building unit, consisting of two [Mn3.5(trz)4(CH3COO)2(OH)] subunits with atom Mn4 lying on an inversion center, is centrosymmetric (Fig. 1).
In the asymmetric unit of (I), atoms Mn1, Mn2 and Mn3 are held together by three distinct bridging systems to form an Mn3 cluster, viz. (i) two µ2-bridging acetate ligands, with Mn—O distances of 2.121 (O4—Mn2), 2.175 (O2—Mn3), 2.158 (Mn3—O3) and 2.424 Å (O2—Mn1) [please check; atom labelling used in text and Fig. 1 seems to be different from that used in the CIF, and values of bond lengths and angles quoted in the text do not appear to match those provided in the CIF; s.u. values should also be given for all distances and angles where available], which are within the range 1.857–2.443 Å reported by Ouellette et al. (2006) for a similar compound; (ii) two 1,2-bridging trz ligands, with an Mn3—N5 distance of 2.198 Å, Mn1—N4 of 2.221 Å, Mn1—N1 of 2.250 Å and an Mn2—N2 distance of 2.231 Å, which are slightly longer than those reported by Milios et al. (2006); (iii) the O atom of the tridentate hydroxy group, lying out of the plane defined by the Mn3 triangle by 0.6686 Å, with distances from each of the Mn atoms of 2.2241 (Mn1), 2.1009 (Mn2) and 2.2328 Å (please check values and provide s.u. values) (Mn3), and these are also longer than those in related compounds (Ouellette et al., 2006; Milios et al., 2006). Two Mn3 clusters are bridged by the Mn4 atom via two µ2-trz ligands and two µ2-O atoms from two acetate ions to construct a heptanuclear building block, with an Mn4—O2 distance of 2.240 Å, Mn1—N7 of 2.219 Å and Mn4—N8 of 2.180 Å. To the best of our knowledge, this kind of heptanuclear building block is unprecedented.
In the asymmetric unit of complex (I), four MnII ions have two different coordination modes. Mn1, Mn3 and Mn4 are six-coordinated in a slightly distorted octahedron with coordination angles in the ranges 82.0–98.5° or 166.4–180°. Atom Mn2 possesses a twisted trigonal-bipyramidal geometry, with the equatorial atoms O4, N6 and N2 and axial atoms N12 and O1. The O4—Mn2—N12, N12—Mn2—N2 and N6—Mn2—N2 angles are 83.9, 86.8 and 87.9°, respectively.
The heptanuclear units are aligned along the b direction parallel to each other in a shoulder-to-shoulder fashion, and both sides of the two adjacent units are connected by two trz ligands, resulting in the formation of one-dimension ladder-like chains along the b axis (Fig. 2). Each chain is further interlinked with four other chains by coordination of the remaining N atoms of the trz ligands to the MnII ions in neighboring chains. This leads to the construction of a three-dimensional framework (Fig. 3).