

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810020714/su2182sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810020714/su2182Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.022
- wR factor = 0.098
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.96 PLAT919_ALERT_3_B Reflection(s) # Likely Affected by the Beamstop 5
Alert level C PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C6 - C7 ... 1.55 Ang. PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 208 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 1 PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings Differ ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A .. O7 .. 2.61 Ang. PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 2
Alert level G PLAT432_ALERT_2_G Short Inter X...Y Contact O10 .. C6 .. 2.86 Ang. PLAT432_ALERT_2_G Short Inter X...Y Contact O10 .. C7 .. 2.87 Ang. PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) . 1.12 Ratio
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of L (0.05 mmol, 0.012 g), Na2MoO4(0.05 mmol, 0.012 g) and water(10 ml) was adjusted to pH = 3.0 by HCl. The synthesis was carried out hydrothermally using a Teflon-lined autoclave. The reaction mixture was heated at 393 K for 3 days, followed by slow cooling to rt. The resulting colorless prismatic crystals were filtered off and washed with water (yield: ca. 90% based on Mo). Elemental analyse - found: C, 17.45; H, 1.58; N, 6.56; Mo, 46.11; calcd: C, 17.22; H, 1.44; N, 6.70; Mo, 45.93.
The H-atoms were positioned geometrically and refined as riding atoms: C—H = 0.93Å, N—H = 0.86Å and Uiso(H) = 1.2Ueq(N,C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
(C12H12N4O2)2[Mo8O26] | F(000) = 1592 |
Mr = 1672.03 | Dx = 2.670 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5569 reflections |
a = 10.633 (2) Å | θ = 2.1–27.5° |
b = 11.552 (2) Å | µ = 2.45 mm−1 |
c = 17.240 (4) Å | T = 293 K |
β = 101.553 (3)° | Prism, colorless |
V = 2074.7 (8) Å3 | 0.23 × 0.22 × 0.05 mm |
Z = 2 |
Siemens CCD area-detector diffractometer | 4534 independent reflections |
Radiation source: fine-focus sealed tube | 4215 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.829, Tmax = 1.000 | k = −13→14 |
14669 measured reflections | l = −22→17 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.40 | w = 1/[σ2(Fo2) + (0.054P)2 + 0.4946P] where P = (Fo2 + 2Fc2)/3 |
4534 reflections | (Δ/σ)max = 0.001 |
316 parameters | Δρmax = 1.40 e Å−3 |
0 restraints | Δρmin = −2.27 e Å−3 |
(C12H12N4O2)2[Mo8O26] | V = 2074.7 (8) Å3 |
Mr = 1672.03 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.633 (2) Å | µ = 2.45 mm−1 |
b = 11.552 (2) Å | T = 293 K |
c = 17.240 (4) Å | 0.23 × 0.22 × 0.05 mm |
β = 101.553 (3)° |
Siemens CCD area-detector diffractometer | 4534 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4215 reflections with I > 2σ(I) |
Tmin = 0.829, Tmax = 1.000 | Rint = 0.021 |
14669 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.40 | Δρmax = 1.40 e Å−3 |
4534 reflections | Δρmin = −2.27 e Å−3 |
316 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
Mo1 | 0.08119 (2) | 0.53770 (2) | 0.098624 (15) | 0.01481 (10) | |
Mo2 | 0.03951 (3) | 0.71904 (2) | −0.069243 (16) | 0.01713 (10) | |
Mo3 | 0.25513 (2) | 0.49409 (2) | −0.029720 (16) | 0.01602 (10) | |
Mo4 | −0.13294 (3) | 0.77083 (2) | 0.064661 (17) | 0.01917 (10) | |
O12 | 0.0104 (2) | 0.8099 (2) | 0.01704 (14) | 0.0218 (5) | |
O6 | 0.2011 (2) | 0.4893 (2) | 0.17096 (15) | 0.0252 (5) | |
O15 | 0.1779 (2) | 0.61483 (18) | 0.02814 (13) | 0.0168 (4) | |
O5 | −0.0636 (2) | 0.44017 (19) | 0.11312 (13) | 0.0165 (4) | |
O4 | −0.2513 (2) | 0.8238 (2) | −0.00841 (16) | 0.0297 (6) | |
O7 | 0.3709 (2) | 0.4459 (2) | 0.04628 (15) | 0.0275 (5) | |
N2 | 0.5229 (3) | 0.1925 (2) | 1.09498 (17) | 0.0221 (6) | |
H2A | 0.5102 | 0.2587 | 1.0720 | 0.026* | |
O13 | 0.0261 (2) | 0.6628 (2) | 0.13799 (13) | 0.0205 (5) | |
C2 | 0.3935 (3) | 0.2606 (3) | 1.1832 (2) | 0.0259 (7) | |
H2 | 0.3675 | 0.3224 | 1.1491 | 0.031* | |
O11 | 0.3343 (2) | 0.5745 (2) | −0.08718 (14) | 0.0242 (5) | |
O9 | −0.0852 (3) | 0.7563 (2) | −0.14308 (15) | 0.0274 (5) | |
O10 | 0.1691 (3) | 0.7832 (2) | −0.09476 (16) | 0.0273 (5) | |
C5 | 0.4718 (4) | 0.0833 (3) | 1.2863 (2) | 0.0301 (8) | |
H5 | 0.4985 | 0.0245 | 1.3227 | 0.036* | |
C4 | 0.5210 (4) | 0.0892 (3) | 1.2190 (2) | 0.0265 (7) | |
H4 | 0.5801 | 0.0346 | 1.2091 | 0.032* | |
N1 | 0.3858 (3) | 0.1609 (3) | 1.30054 (17) | 0.0280 (7) | |
H1 | 0.3545 | 0.1541 | 1.3426 | 0.034* | |
O3 | −0.1253 (3) | 0.8654 (2) | 0.14042 (16) | 0.0321 (6) | |
C3 | 0.4805 (3) | 0.1793 (3) | 1.16520 (18) | 0.0196 (6) | |
C1 | 0.3471 (4) | 0.2490 (3) | 1.2508 (2) | 0.0286 (8) | |
H1A | 0.2882 | 0.3025 | 1.2626 | 0.034* | |
O14 | 0.0844 (2) | 0.40727 (19) | 0.01120 (12) | 0.0173 (4) | |
O8 | 0.2273 (2) | 0.3590 (2) | −0.09586 (13) | 0.0205 (5) | |
N3 | 0.8440 (3) | 0.0969 (3) | 0.75088 (17) | 0.0285 (7) | |
H3 | 0.8761 | 0.0988 | 0.7089 | 0.034* | |
O2 | 0.5624 (3) | 0.2419 (2) | 0.94778 (15) | 0.0289 (6) | |
O1 | 0.6119 (3) | 0.0145 (2) | 1.08260 (16) | 0.0334 (6) | |
N4 | 0.6865 (3) | 0.0776 (3) | 0.94989 (17) | 0.0236 (6) | |
H4A | 0.7065 | 0.0154 | 0.9770 | 0.028* | |
C11 | 0.7132 (3) | 0.1824 (3) | 0.8303 (2) | 0.0261 (7) | |
H11 | 0.6606 | 0.2428 | 0.8399 | 0.031* | |
C10 | 0.7680 (4) | 0.1841 (3) | 0.7648 (2) | 0.0298 (8) | |
H10 | 0.7525 | 0.2461 | 0.7297 | 0.036* | |
C8 | 0.8193 (4) | 0.0012 (3) | 0.8668 (2) | 0.0303 (8) | |
H8 | 0.8384 | −0.0609 | 0.9015 | 0.036* | |
C9 | 0.8712 (4) | 0.0072 (3) | 0.8005 (2) | 0.0333 (9) | |
H9 | 0.9256 | −0.0512 | 0.7898 | 0.040* | |
C12 | 0.7373 (3) | 0.0892 (3) | 0.88212 (18) | 0.0204 (6) | |
C6 | 0.5830 (3) | 0.1107 (3) | 1.05882 (19) | 0.0206 (6) | |
C7 | 0.6084 (3) | 0.1539 (3) | 0.97837 (19) | 0.0226 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.01333 (15) | 0.02061 (16) | 0.01084 (15) | −0.00116 (9) | 0.00325 (10) | −0.00091 (10) |
Mo2 | 0.01807 (16) | 0.01867 (16) | 0.01602 (16) | 0.00122 (10) | 0.00673 (11) | 0.00088 (10) |
Mo3 | 0.01266 (15) | 0.02166 (17) | 0.01468 (16) | 0.00069 (9) | 0.00496 (11) | 0.00006 (10) |
Mo4 | 0.01891 (17) | 0.02088 (16) | 0.01936 (16) | 0.00103 (10) | 0.00773 (12) | −0.00038 (10) |
O12 | 0.0232 (12) | 0.0214 (11) | 0.0228 (11) | −0.0027 (9) | 0.0093 (10) | −0.0038 (9) |
O6 | 0.0216 (12) | 0.0342 (13) | 0.0184 (12) | 0.0020 (10) | 0.0003 (10) | 0.0029 (10) |
O15 | 0.0156 (10) | 0.0194 (10) | 0.0160 (10) | −0.0018 (8) | 0.0047 (8) | −0.0007 (9) |
O5 | 0.0162 (10) | 0.0199 (10) | 0.0146 (10) | 0.0006 (8) | 0.0057 (8) | 0.0005 (9) |
O4 | 0.0250 (13) | 0.0339 (14) | 0.0311 (14) | 0.0052 (11) | 0.0073 (11) | 0.0089 (11) |
O7 | 0.0216 (12) | 0.0381 (14) | 0.0221 (12) | 0.0048 (11) | 0.0026 (10) | 0.0052 (11) |
N2 | 0.0260 (15) | 0.0251 (14) | 0.0176 (13) | 0.0021 (12) | 0.0105 (11) | 0.0042 (11) |
O13 | 0.0204 (11) | 0.0226 (11) | 0.0192 (11) | −0.0004 (9) | 0.0059 (9) | −0.0040 (9) |
C2 | 0.0268 (18) | 0.0300 (17) | 0.0226 (17) | 0.0055 (14) | 0.0089 (14) | 0.0044 (14) |
O11 | 0.0217 (12) | 0.0292 (12) | 0.0237 (12) | −0.0022 (10) | 0.0091 (10) | 0.0032 (10) |
O9 | 0.0291 (13) | 0.0281 (12) | 0.0232 (12) | 0.0072 (11) | 0.0010 (11) | 0.0008 (11) |
O10 | 0.0272 (13) | 0.0269 (13) | 0.0305 (13) | −0.0026 (10) | 0.0127 (11) | 0.0019 (10) |
C5 | 0.038 (2) | 0.0303 (18) | 0.0222 (17) | 0.0010 (16) | 0.0069 (15) | 0.0068 (15) |
C4 | 0.0269 (18) | 0.0316 (18) | 0.0222 (17) | 0.0038 (14) | 0.0074 (14) | 0.0026 (15) |
N1 | 0.0295 (16) | 0.0401 (17) | 0.0171 (13) | −0.0029 (13) | 0.0114 (12) | −0.0004 (13) |
O3 | 0.0354 (14) | 0.0310 (13) | 0.0332 (14) | 0.0015 (11) | 0.0146 (12) | −0.0097 (12) |
C3 | 0.0180 (15) | 0.0268 (16) | 0.0148 (14) | −0.0016 (12) | 0.0053 (12) | 0.0005 (13) |
C1 | 0.0263 (18) | 0.0380 (19) | 0.0235 (17) | 0.0048 (15) | 0.0097 (15) | −0.0007 (16) |
O14 | 0.0169 (10) | 0.0209 (10) | 0.0153 (10) | 0.0003 (8) | 0.0063 (8) | 0.0001 (9) |
O8 | 0.0223 (11) | 0.0228 (11) | 0.0193 (11) | 0.0002 (9) | 0.0110 (9) | −0.0029 (9) |
N3 | 0.0311 (16) | 0.0405 (17) | 0.0173 (13) | −0.0040 (14) | 0.0130 (12) | −0.0015 (13) |
O2 | 0.0333 (14) | 0.0309 (13) | 0.0244 (13) | 0.0054 (11) | 0.0104 (11) | 0.0031 (11) |
O1 | 0.0461 (17) | 0.0300 (14) | 0.0293 (14) | 0.0072 (12) | 0.0204 (13) | 0.0039 (11) |
N4 | 0.0278 (15) | 0.0276 (14) | 0.0188 (13) | 0.0042 (12) | 0.0127 (12) | 0.0029 (12) |
C11 | 0.0261 (17) | 0.0322 (18) | 0.0218 (16) | 0.0051 (14) | 0.0090 (14) | 0.0019 (14) |
C10 | 0.0299 (19) | 0.040 (2) | 0.0209 (17) | 0.0027 (16) | 0.0074 (15) | 0.0061 (15) |
C8 | 0.040 (2) | 0.0269 (18) | 0.0284 (19) | 0.0052 (15) | 0.0175 (17) | 0.0041 (15) |
C9 | 0.042 (2) | 0.0317 (19) | 0.032 (2) | −0.0007 (16) | 0.0210 (18) | −0.0033 (16) |
C12 | 0.0232 (16) | 0.0244 (16) | 0.0155 (14) | −0.0036 (13) | 0.0081 (12) | −0.0026 (12) |
C6 | 0.0195 (15) | 0.0278 (16) | 0.0171 (14) | −0.0042 (13) | 0.0094 (12) | −0.0017 (13) |
C7 | 0.0235 (16) | 0.0286 (16) | 0.0172 (15) | −0.0049 (14) | 0.0076 (13) | −0.0018 (14) |
Mo1—O6 | 1.690 (2) | C2—C3 | 1.395 (5) |
Mo1—O13 | 1.747 (2) | C2—H2 | 0.9300 |
Mo1—O15 | 1.956 (2) | C5—N1 | 1.338 (5) |
Mo1—O5 | 1.964 (2) | C5—C4 | 1.366 (5) |
Mo1—O14 | 2.136 (2) | C5—H5 | 0.9300 |
Mo1—O14i | 2.399 (2) | C4—C3 | 1.403 (5) |
Mo1—Mo3 | 3.1951 (6) | C4—H4 | 0.9300 |
Mo2—O10 | 1.699 (3) | N1—C1 | 1.342 (5) |
Mo2—O9 | 1.699 (3) | N1—H1 | 0.8600 |
Mo2—O12 | 1.896 (2) | C1—H1A | 0.9300 |
Mo2—O5i | 2.024 (2) | O14—Mo2i | 2.322 (2) |
Mo2—O14i | 2.322 (2) | O14—Mo1i | 2.399 (2) |
Mo2—O15 | 2.333 (2) | O8—Mo4i | 1.939 (2) |
Mo3—O11 | 1.699 (2) | N3—C9 | 1.338 (5) |
Mo3—O7 | 1.702 (2) | N3—C10 | 1.342 (5) |
Mo3—O8 | 1.921 (2) | N3—H3 | 0.8600 |
Mo3—O15 | 1.986 (2) | O2—C7 | 1.203 (4) |
Mo3—O14 | 2.305 (2) | O1—C6 | 1.203 (4) |
Mo3—O5i | 2.370 (2) | N4—C7 | 1.368 (4) |
Mo4—O3 | 1.692 (3) | N4—C12 | 1.388 (4) |
Mo4—O4 | 1.706 (3) | N4—H4A | 0.8600 |
Mo4—O12 | 1.924 (2) | C11—C10 | 1.371 (5) |
Mo4—O8i | 1.939 (2) | C11—C12 | 1.390 (5) |
Mo4—O13 | 2.271 (2) | C11—H11 | 0.9300 |
O5—Mo2i | 2.024 (2) | C10—H10 | 0.9300 |
O5—Mo3i | 2.370 (2) | C8—C9 | 1.368 (5) |
N2—C6 | 1.360 (4) | C8—C12 | 1.398 (5) |
N2—C3 | 1.383 (4) | C8—H8 | 0.9300 |
N2—H2A | 0.8600 | C9—H9 | 0.9300 |
C2—C1 | 1.361 (5) | C6—C7 | 1.548 (5) |
O6—Mo1—O13 | 104.42 (12) | O12—Mo4—O13 | 78.54 (10) |
O6—Mo1—O15 | 101.34 (11) | O8i—Mo4—O13 | 77.86 (9) |
O13—Mo1—O15 | 97.08 (10) | Mo2—O12—Mo4 | 118.21 (12) |
O6—Mo1—O5 | 102.18 (11) | Mo1—O15—Mo3 | 108.29 (10) |
O13—Mo1—O5 | 95.32 (10) | Mo1—O15—Mo2 | 110.37 (10) |
O15—Mo1—O5 | 149.67 (9) | Mo3—O15—Mo2 | 105.41 (9) |
O6—Mo1—O14 | 99.85 (11) | Mo1—O5—Mo2i | 108.21 (10) |
O13—Mo1—O14 | 155.72 (10) | Mo1—O5—Mo3i | 109.83 (10) |
O15—Mo1—O14 | 78.37 (9) | Mo2i—O5—Mo3i | 102.84 (9) |
O5—Mo1—O14 | 78.98 (9) | C6—N2—C3 | 126.2 (3) |
O6—Mo1—O14i | 174.94 (10) | C6—N2—H2A | 116.9 |
O13—Mo1—O14i | 80.62 (9) | C3—N2—H2A | 116.9 |
O15—Mo1—O14i | 77.46 (8) | Mo1—O13—Mo4 | 120.57 (11) |
O5—Mo1—O14i | 77.42 (8) | C1—C2—C3 | 119.6 (3) |
O14—Mo1—O14i | 75.11 (9) | C1—C2—H2 | 120.2 |
O6—Mo1—Mo3 | 90.19 (9) | C3—C2—H2 | 120.2 |
O13—Mo1—Mo3 | 133.25 (8) | N1—C5—C4 | 121.0 (3) |
O15—Mo1—Mo3 | 36.17 (6) | N1—C5—H5 | 119.5 |
O5—Mo1—Mo3 | 125.10 (6) | C4—C5—H5 | 119.5 |
O14—Mo1—Mo3 | 46.13 (6) | C5—C4—C3 | 118.6 (3) |
O14i—Mo1—Mo3 | 86.01 (5) | C5—C4—H4 | 120.7 |
O10—Mo2—O9 | 104.31 (13) | C3—C4—H4 | 120.7 |
O10—Mo2—O12 | 103.29 (11) | C5—N1—C1 | 121.6 (3) |
O9—Mo2—O12 | 102.84 (11) | C5—N1—H1 | 119.2 |
O10—Mo2—O5i | 97.46 (11) | C1—N1—H1 | 119.2 |
O9—Mo2—O5i | 95.06 (11) | N2—C3—C2 | 117.9 (3) |
O12—Mo2—O5i | 148.09 (10) | N2—C3—C4 | 123.3 (3) |
O10—Mo2—O14i | 160.99 (11) | C2—C3—C4 | 118.8 (3) |
O9—Mo2—O14i | 93.28 (11) | N1—C1—C2 | 120.3 (3) |
O12—Mo2—O14i | 79.28 (9) | N1—C1—H1A | 119.8 |
O5i—Mo2—O14i | 73.47 (8) | C2—C1—H1A | 119.8 |
O10—Mo2—O15 | 89.10 (11) | Mo1—O14—Mo3 | 91.94 (8) |
O9—Mo2—O15 | 162.69 (11) | Mo1—O14—Mo2i | 92.79 (8) |
O12—Mo2—O15 | 84.24 (9) | Mo3—O14—Mo2i | 162.71 (11) |
O5i—Mo2—O15 | 72.02 (8) | Mo1—O14—Mo1i | 104.89 (9) |
O14i—Mo2—O15 | 72.31 (8) | Mo3—O14—Mo1i | 98.15 (8) |
O11—Mo3—O7 | 105.16 (12) | Mo2i—O14—Mo1i | 96.69 (8) |
O11—Mo3—O8 | 97.69 (11) | Mo3—O8—Mo4i | 119.38 (11) |
O7—Mo3—O8 | 101.11 (12) | C9—N3—C10 | 121.9 (3) |
O11—Mo3—O15 | 102.23 (11) | C9—N3—H3 | 119.1 |
O7—Mo3—O15 | 98.71 (11) | C10—N3—H3 | 119.1 |
O8—Mo3—O15 | 147.03 (9) | C7—N4—C12 | 127.3 (3) |
O11—Mo3—O14 | 158.28 (10) | C7—N4—H4A | 116.3 |
O7—Mo3—O14 | 96.57 (11) | C12—N4—H4A | 116.3 |
O8—Mo3—O14 | 77.93 (9) | C10—C11—C12 | 119.1 (3) |
O15—Mo3—O14 | 73.83 (8) | C10—C11—H11 | 120.4 |
O11—Mo3—O5i | 86.39 (10) | C12—C11—H11 | 120.4 |
O7—Mo3—O5i | 166.64 (10) | N3—C10—C11 | 120.4 (3) |
O8—Mo3—O5i | 83.62 (9) | N3—C10—H10 | 119.8 |
O15—Mo3—O5i | 71.82 (8) | C11—C10—H10 | 119.8 |
O14—Mo3—O5i | 72.03 (8) | C9—C8—C12 | 119.5 (3) |
O11—Mo3—Mo1 | 137.78 (9) | C9—C8—H8 | 120.3 |
O7—Mo3—Mo1 | 87.02 (9) | C12—C8—H8 | 120.3 |
O8—Mo3—Mo1 | 119.84 (7) | N3—C9—C8 | 120.1 (4) |
O15—Mo3—Mo1 | 35.55 (6) | N3—C9—H9 | 119.9 |
O14—Mo3—Mo1 | 41.93 (5) | C8—C9—H9 | 119.9 |
O5i—Mo3—Mo1 | 79.83 (5) | N4—C12—C11 | 124.3 (3) |
O3—Mo4—O4 | 104.63 (14) | N4—C12—C8 | 116.8 (3) |
O3—Mo4—O12 | 104.98 (12) | C11—C12—C8 | 118.9 (3) |
O4—Mo4—O12 | 97.54 (12) | O1—C6—N2 | 126.7 (3) |
O3—Mo4—O8i | 103.44 (11) | O1—C6—C7 | 121.6 (3) |
O4—Mo4—O8i | 97.81 (12) | N2—C6—C7 | 111.6 (3) |
O12—Mo4—O8i | 142.92 (9) | O2—C7—N4 | 127.6 (3) |
O3—Mo4—O13 | 90.56 (11) | O2—C7—C6 | 122.5 (3) |
O4—Mo4—O13 | 164.80 (11) | N4—C7—C6 | 110.0 (3) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O7ii | 0.86 | 2.61 | 3.368 (4) | 148 |
N1—H1···O8iii | 0.86 | 1.89 | 2.699 (4) | 158 |
N3—H3···O5iv | 0.86 | 1.94 | 2.779 (4) | 165 |
N4—H4A···O1 | 0.86 | 2.25 | 2.669 (4) | 110 |
N4—H4A···O4v | 0.86 | 2.26 | 3.059 (4) | 154 |
Symmetry codes: (ii) x, y, z+1; (iii) x, −y+1/2, z+3/2; (iv) x+1, −y+1/2, z+1/2; (v) x+1, y−1, z+1. |
Experimental details
Crystal data | |
Chemical formula | (C12H12N4O2)2[Mo8O26] |
Mr | 1672.03 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.633 (2), 11.552 (2), 17.240 (4) |
β (°) | 101.553 (3) |
V (Å3) | 2074.7 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.45 |
Crystal size (mm) | 0.23 × 0.22 × 0.05 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.829, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14669, 4534, 4215 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.098, 1.40 |
No. of reflections | 4534 |
No. of parameters | 316 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.40, −2.27 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O7i | 0.86 | 2.608 | 3.368 (4) | 148 |
N1—H1···O8ii | 0.86 | 1.885 | 2.699 (4) | 158 |
N3—H3···O5iii | 0.86 | 1.940 | 2.779 (4) | 165 |
N4—H4A···O1 | 0.86 | 2.248 | 2.669 (4) | 110 |
N4—H4A···O4iv | 0.86 | 2.263 | 3.059 (4) | 154 |
Symmetry codes: (i) x, y, z+1; (ii) x, −y+1/2, z+3/2; (iii) x+1, −y+1/2, z+1/2; (iv) x+1, y−1, z+1. |
Polyoxometalates (POMs) are early transition metal oxygen anion clusters. They are an outstanding class of anionic compounds due to their wealthy topology, superior physical and chemical properties (Pope & Muller, 1991; Katsoulis, 1988). The nanoscopic sizes (Cronin, et al., 2002; Fukaya & Yamase, 2003,) and thier diversified shapes of discrete POMs have attracted great interest. The design, synthesis and structural characterization of inorganic-organic hybrid compounds base on POMs, for which many properties and applications can be predicted, have established a new field of research in the chemistry of biology and materials sciences (Luan, et al., 2002; Cui, et al., 2003; Wang, et al., 2003). Different N-heterocycle ligands can lead to different inorganic-organic hybrid compounds based on POMs. N1,N2-di(pyridin-4-yl)oxalamide (L), is a bis-pyridine ligand, which has been reported only rarely in the construction of hybrid compounds based on POMs. In the present work, the title complex was synthesized hydrothermally by reacting L with the isopolyoxometalate, Mo8O26.
The molecular structure of the title complex is illustrated in Fig. 1. In the asymmetric unit there is a doublely protonated L molecule, and half an isopolyoxometalate unit. The bond distances and angles in the cation are similar to those observed previously for N1,N2-di(pyridin-4-yl)oxalamide (Tzeng, et al., 2007). For the anion, [Mo8O26]4-, the geometrical parameters are similar to those reported by (Gong, et al., 2007).
In the crystal the protonated pyrdidinium groups and the amino group form N-H···O hydrogen bonds with the oxygen atoms of the centrosymmetric [Mo8O26]4- anions, leading to the formation of a three dimensional supramolecular network (Table 1 and Fig. 2).