Crystals of the title compound, 2,5-dimethylpiperazinediium β-octamolybdate, were grown under mild hydrothermal conditions. The anion and cations lie on inversion centers. A network of N—H
O bonds helps to stabilize the crystal packing.
Supporting information
CCDC reference: 270425
Key indicators
- Single-crystal X-ray study
- T = 153 K
- Mean (C-C) = 0.014 Å
- R factor = 0.043
- wR factor = 0.095
- Data-to-parameter ratio = 12.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 14
PLAT353_ALERT_3_C Long N-H Bond (0.87A) N1 - H1 ... 1.01 Ang.
PLAT353_ALERT_3_C Long N-H Bond (0.87A) N2 - H10 ... 1.02 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact O9 .. C5 .. 3.01 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2
C6 H16 N2
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3
C6 H16 N2
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
7 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED; data reduction: CrysAlis RED (Oxford Diffraction, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ATOMS (Dowty, 2002); software used to prepare material for publication: CRYSTALS.
2,5-dimethylpiperazinediium
β-octamolybdate
top
Crystal data top
(C6H16N2)2[Mo8O26] | F(000) = 1352 |
Mr = 1415.92 | Dx = 2.867 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3088 reflections |
a = 11.0450 (11) Å | θ = 3.9–33.3° |
b = 12.3699 (11) Å | µ = 3.06 mm−1 |
c = 13.0539 (15) Å | T = 153 K |
β = 113.148 (10)° | Plate, colourless |
V = 1639.9 (3) Å3 | 0.09 × 0.08 × 0.02 mm |
Z = 2 | |
Data collection top
CrysAlis CCD diffractometer | 2797 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 33.4°, θmin = 3.9° |
Absorption correction: analytical (multifaceted crystal model; Clark & Reid, 1995) | h = −15→16 |
Tmin = 0.636, Tmax = 0.862 | k = −16→18 |
14643 measured reflections | l = −19→18 |
5519 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.095 | Robust weighting scheme (Prince, 1982) fitted by a five-term Chebychev
polynomial (Watkin, 1994) with coefficients 12.6, 20.2, 12.3, 5.21 and 1.63. |
S = 0.85 | (Δ/σ)max < 0.001 |
2797 reflections | Δρmax = 2.41 e Å−3 |
226 parameters | Δρmin = −1.35 e Å−3 |
0 restraints | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mo1 | −0.03461 (7) | −0.07093 (6) | 1.19739 (6) | 0.0108 | |
Mo2 | 0.14345 (6) | −0.08308 (5) | 1.05363 (6) | 0.0095 | |
Mo3 | 0.18253 (6) | 0.17511 (5) | 1.06758 (6) | 0.0105 | |
Mo4 | 0.00342 (7) | 0.19058 (5) | 1.21254 (6) | 0.0114 | |
O1 | 0.1085 (6) | −0.0865 (5) | 1.3120 (5) | 0.0153 | |
O2 | −0.1479 (6) | −0.1510 (5) | 1.2183 (5) | 0.0177 | |
O3 | −0.0930 (6) | 0.0681 (5) | 1.2254 (5) | 0.0133 | |
O4 | 0.0150 (5) | −0.1609 (4) | 1.0925 (5) | 0.0112 | |
O5 | 0.0530 (5) | 0.0476 (5) | 1.1038 (5) | 0.0115 | |
O6 | −0.1937 (6) | −0.0417 (5) | 1.0171 (5) | 0.0125 | |
O7 | 0.2826 (6) | −0.0935 (5) | 1.1702 (5) | 0.0142 | |
O8 | 0.1596 (5) | −0.1804 (5) | 0.9615 (5) | 0.0116 | |
O9 | 0.3192 (6) | 0.1506 (5) | 1.1862 (5) | 0.0151 | |
O10 | 0.2324 (6) | 0.2640 (5) | 0.9924 (5) | 0.0155 | |
O11 | 0.0759 (6) | 0.2643 (5) | 1.1193 (5) | 0.0155 | |
O12 | 0.1474 (6) | 0.1665 (5) | 1.3232 (5) | 0.0150 | |
O13 | −0.0717 (6) | 0.2938 (5) | 1.2537 (5) | 0.0163 | |
N1 | −0.4153 (7) | −0.0782 (6) | 1.0756 (6) | 0.0159 | |
N2 | 0.0924 (9) | −0.4156 (7) | 1.0492 (8) | 0.0322 | |
C1 | −0.5441 (8) | −0.1125 (7) | 0.9854 (7) | 0.0166 | |
C2 | −0.4203 (8) | 0.0366 (7) | 1.1117 (7) | 0.0169 | |
C3 | −0.5382 (9) | −0.2307 (8) | 0.9527 (8) | 0.0193 | |
C4 | 0.1280 (10) | −0.5050 (9) | 0.9916 (9) | 0.0294 | |
C5 | −0.0012 (10) | −0.4520 (9) | 1.0994 (9) | 0.0301 | |
C6 | 0.2297 (9) | −0.4772 (7) | 0.9464 (8) | 0.0204 | |
H1 | −0.3940 | −0.1275 | 1.1419 | 0.0167* | |
H2 | −0.3436 | −0.0841 | 1.0472 | 0.0167* | |
H3 | −0.6162 | −0.1089 | 1.0141 | 0.0189* | |
H4 | −0.5194 | −0.2785 | 1.0187 | 0.0223* | |
H5 | −0.4669 | −0.2392 | 0.9239 | 0.0223* | |
H6 | −0.6246 | −0.2518 | 0.8925 | 0.0223* | |
H7 | −0.4896 | 0.0418 | 1.1445 | 0.0202* | |
H8 | −0.3333 | 0.0570 | 1.1708 | 0.0202* | |
H9 | 0.0502 | −0.3554 | 0.9960 | 0.0212* | |
H10 | 0.1747 | −0.3859 | 1.1111 | 0.0212* | |
H11 | 0.1739 | −0.5617 | 1.0484 | 0.0364* | |
H12 | 0.1963 | −0.4169 | 0.8911 | 0.0225* | |
H13 | 0.3127 | −0.4541 | 1.0086 | 0.0225* | |
H14 | 0.2473 | −0.5421 | 0.9087 | 0.0225* | |
H15 | −0.0221 | −0.3904 | 1.1404 | 0.0353* | |
H16 | 0.0417 | −0.5114 | 1.1557 | 0.0353* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mo1 | 0.0096 (3) | 0.0121 (3) | 0.0089 (3) | 0.0005 (2) | 0.0020 (2) | 0.0007 (2) |
Mo2 | 0.0076 (3) | 0.0100 (3) | 0.0090 (3) | 0.0009 (2) | 0.0011 (2) | 0.0006 (2) |
Mo3 | 0.0084 (3) | 0.0104 (3) | 0.0105 (3) | −0.0005 (2) | 0.0013 (2) | 0.0001 (2) |
Mo4 | 0.0106 (3) | 0.0121 (3) | 0.0097 (3) | 0.0005 (2) | 0.0021 (2) | −0.0007 (2) |
O1 | 0.013 (3) | 0.016 (3) | 0.012 (3) | 0.003 (2) | −0.001 (2) | 0.000 (2) |
O2 | 0.011 (3) | 0.025 (3) | 0.016 (3) | −0.002 (2) | 0.002 (2) | −0.001 (2) |
O3 | 0.013 (3) | 0.016 (3) | 0.013 (3) | 0.001 (2) | 0.008 (2) | 0.002 (2) |
O4 | 0.010 (3) | 0.010 (2) | 0.010 (2) | 0.000 (2) | 0.000 (2) | 0.001 (2) |
O5 | 0.007 (3) | 0.013 (3) | 0.012 (3) | 0.0017 (19) | 0.001 (2) | −0.002 (2) |
O6 | 0.012 (3) | 0.013 (3) | 0.013 (3) | 0.001 (2) | 0.005 (2) | 0.002 (2) |
O7 | 0.011 (3) | 0.015 (3) | 0.015 (3) | −0.001 (2) | 0.003 (2) | 0.003 (2) |
O8 | 0.009 (2) | 0.015 (3) | 0.010 (2) | 0.000 (2) | 0.003 (2) | −0.004 (2) |
O9 | 0.014 (3) | 0.014 (3) | 0.013 (3) | 0.001 (2) | 0.002 (2) | −0.002 (2) |
O10 | 0.012 (3) | 0.011 (3) | 0.021 (3) | −0.004 (2) | 0.004 (2) | 0.001 (2) |
O11 | 0.019 (3) | 0.014 (3) | 0.012 (3) | −0.001 (2) | 0.004 (2) | 0.000 (2) |
O12 | 0.014 (3) | 0.017 (3) | 0.009 (3) | 0.003 (2) | 0.000 (2) | 0.003 (2) |
O13 | 0.017 (3) | 0.020 (3) | 0.012 (3) | 0.003 (2) | 0.005 (2) | −0.002 (2) |
N1 | 0.011 (3) | 0.021 (3) | 0.012 (3) | −0.001 (3) | 0.002 (3) | 0.000 (3) |
N2 | 0.026 (4) | 0.029 (5) | 0.028 (5) | 0.002 (4) | −0.004 (4) | −0.002 (4) |
C1 | 0.015 (4) | 0.014 (4) | 0.016 (4) | 0.000 (3) | 0.002 (3) | −0.001 (3) |
C2 | 0.015 (4) | 0.020 (4) | 0.015 (4) | 0.002 (3) | 0.005 (3) | −0.002 (3) |
C3 | 0.016 (4) | 0.023 (4) | 0.015 (4) | 0.002 (3) | 0.003 (3) | −0.003 (3) |
C4 | 0.021 (5) | 0.038 (6) | 0.022 (5) | −0.004 (4) | 0.002 (4) | 0.000 (4) |
C5 | 0.021 (5) | 0.040 (6) | 0.025 (5) | −0.011 (4) | 0.005 (4) | −0.008 (4) |
C6 | 0.015 (4) | 0.015 (4) | 0.025 (5) | −0.003 (3) | 0.001 (3) | 0.002 (3) |
Geometric parameters (Å, º) top
Mo1—O1 | 1.708 (6) | N1—C1 | 1.508 (10) |
Mo1—O2 | 1.700 (6) | N1—C2 | 1.504 (11) |
Mo1—O3 | 1.922 (6) | N1—H1 | 1.009 |
Mo1—O4 | 2.001 (6) | N1—H2 | 1.000 |
Mo1—O5 | 2.346 (6) | N2—C4 | 1.474 (15) |
Mo1—O6 | 2.347 (6) | N2—C5 | 1.494 (15) |
Mo2—O4 | 1.940 (6) | N2—H9 | 1.000 |
Mo2—O5 | 2.134 (6) | N2—H10 | 1.018 |
Mo2—O5i | 2.371 (5) | C1—C2ii | 1.500 (12) |
Mo2—O6i | 1.986 (6) | C1—C3 | 1.531 (12) |
Mo2—O7 | 1.690 (6) | C1—H3 | 1.005 |
Mo2—O8 | 1.760 (6) | C2—H7 | 1.015 |
Mo3—O4i | 2.360 (5) | C2—H8 | 1.000 |
Mo3—O5 | 2.301 (6) | C3—H4 | 0.997 |
Mo3—O6i | 2.016 (6) | C3—H5 | 1.003 |
Mo3—O9 | 1.712 (6) | C3—H6 | 1.004 |
Mo3—O10 | 1.702 (6) | C4—C5iii | 1.532 (14) |
Mo3—O11 | 1.919 (6) | C4—C6 | 1.500 (14) |
Mo4—O3 | 1.897 (6) | C4—H11 | 1.001 |
Mo4—O5 | 2.460 (6) | C5—H15 | 1.010 |
Mo4—O8i | 2.282 (5) | C5—H16 | 1.015 |
Mo4—O11 | 1.929 (6) | C6—H12 | 1.001 |
Mo4—O12 | 1.702 (6) | C6—H13 | 0.999 |
Mo4—O13 | 1.720 (6) | C6—H14 | 1.000 |
| | | |
Mo2—Mo1—Mo4 | 89.31 (3) | Mo1—Mo4—O8i | 81.51 (14) |
Mo2—Mo1—O1 | 86.4 (2) | Mo3—Mo4—O8i | 80.74 (14) |
Mo4—Mo1—O1 | 90.3 (2) | O3—Mo4—O8i | 78.1 (2) |
Mo2—Mo1—O2 | 136.5 (2) | O5—Mo4—O8i | 69.73 (19) |
Mo4—Mo1—O2 | 130.9 (2) | Mo1—Mo4—O11 | 120.44 (18) |
O1—Mo1—O2 | 106.2 (3) | Mo3—Mo4—O11 | 32.67 (18) |
Mo2—Mo1—O3 | 118.80 (17) | O3—Mo4—O11 | 145.1 (3) |
Mo4—Mo1—O3 | 31.22 (17) | O5—Mo4—O11 | 74.6 (2) |
O1—Mo1—O3 | 101.5 (3) | O8i—Mo4—O11 | 76.0 (2) |
O2—Mo1—O3 | 99.7 (3) | Mo1—Mo4—O12 | 86.1 (2) |
Mo2—Mo1—O4 | 34.79 (16) | Mo3—Mo4—O12 | 84.5 (2) |
Mo4—Mo1—O4 | 122.03 (16) | O3—Mo4—O12 | 98.9 (3) |
O1—Mo1—O4 | 97.4 (3) | O5—Mo4—O12 | 91.0 (2) |
O2—Mo1—O4 | 101.7 (3) | O8i—Mo4—O12 | 160.7 (3) |
O3—Mo1—O4 | 146.2 (2) | Mo1—Mo4—O13 | 133.6 (2) |
Mo2—Mo1—O5 | 41.63 (14) | Mo3—Mo4—O13 | 135.0 (2) |
Mo4—Mo1—O5 | 48.82 (14) | O3—Mo4—O13 | 102.0 (3) |
O1—Mo1—O5 | 95.6 (3) | O5—Mo4—O13 | 163.3 (2) |
O2—Mo1—O5 | 158.1 (2) | O8i—Mo4—O13 | 93.6 (2) |
O3—Mo1—O5 | 77.2 (2) | O11—Mo4—O12 | 97.9 (3) |
Mo2—Mo1—O6 | 79.06 (14) | O11—Mo4—O13 | 102.5 (3) |
Mo4—Mo1—O6 | 86.32 (14) | O12—Mo4—O13 | 105.6 (3) |
O1—Mo1—O6 | 165.1 (3) | Mo1—O3—Mo4 | 117.1 (3) |
O2—Mo1—O6 | 86.7 (2) | Mo1—O4—Mo2 | 109.1 (3) |
O3—Mo1—O6 | 83.0 (2) | Mo1—O4—Mo3i | 103.9 (2) |
O4—Mo1—O5 | 73.2 (2) | Mo2—O4—Mo3i | 108.8 (3) |
O4—Mo1—O6 | 72.4 (2) | Mo1—O5—Mo2 | 91.5 (2) |
O5—Mo1—O6 | 71.41 (19) | Mo1—O5—Mo2i | 98.2 (2) |
Mo1—Mo2—Mo3 | 91.13 (3) | Mo2—O5—Mo2i | 104.7 (2) |
Mo1—Mo2—O4 | 36.06 (17) | Mo1—O5—Mo3 | 162.3 (3) |
Mo3—Mo2—O4 | 124.98 (17) | Mo2—O5—Mo3 | 93.0 (2) |
Mo1—Mo2—O5 | 46.91 (16) | Mo2i—O5—Mo3 | 97.2 (2) |
Mo3—Mo2—O5 | 45.55 (16) | Mo1—O5—Mo4 | 85.31 (19) |
O4—Mo2—O5 | 79.4 (2) | Mo2—O5—Mo4 | 163.5 (3) |
Mo1—Mo2—O5i | 86.33 (14) | Mo2i—O5—Mo4 | 91.81 (19) |
Mo3—Mo2—O5i | 85.52 (14) | Mo3—O5—Mo4 | 85.58 (18) |
O4—Mo2—O5i | 78.7 (2) | Mo1—O6—Mo2i | 110.5 (3) |
O5—Mo2—O5i | 75.3 (2) | Mo1—O6—Mo3i | 103.9 (2) |
Mo1—Mo2—O6i | 125.61 (17) | Mo2i—O6—Mo3i | 107.0 (3) |
Mo3—Mo2—O6i | 36.80 (17) | Mo2—O8—Mo4i | 117.8 (3) |
O4—Mo2—O6i | 150.9 (2) | Mo3—O11—Mo4 | 114.5 (3) |
O5—Mo2—O6i | 78.7 (2) | C1—N1—C2 | 111.7 (6) |
O5i—Mo2—O6i | 77.3 (2) | C1—N1—H1 | 109.3 |
Mo1—Mo2—O7 | 91.5 (2) | C2—N1—H1 | 109.1 |
Mo3—Mo2—O7 | 88.3 (2) | C1—N1—H2 | 109.4 |
O4—Mo2—O7 | 103.1 (3) | C2—N1—H2 | 108.5 |
O5—Mo2—O7 | 98.7 (3) | H1—N1—H2 | 108.8 |
O5i—Mo2—O7 | 173.4 (2) | C4—N2—C5 | 111.5 (9) |
Mo1—Mo2—O8 | 132.95 (19) | C4—N2—H9 | 110.5 |
Mo3—Mo2—O8 | 132.09 (19) | C5—N2—H9 | 108.3 |
O4—Mo2—O8 | 96.9 (2) | C4—N2—H10 | 110.0 |
O5—Mo2—O8 | 156.0 (2) | C5—N2—H10 | 108.4 |
O5i—Mo2—O8 | 80.7 (2) | H9—N2—H10 | 108.0 |
O6i—Mo2—O7 | 99.0 (3) | N1—C1—C2ii | 109.7 (7) |
O6i—Mo2—O8 | 95.3 (2) | N1—C1—C3 | 110.9 (7) |
O7—Mo2—O8 | 105.2 (3) | C2ii—C1—C3 | 112.8 (7) |
Mo2—Mo3—Mo4 | 89.57 (3) | N1—C1—H3 | 109.8 |
Mo2—Mo3—O4i | 79.59 (14) | C2ii—C1—H3 | 107.7 |
Mo4—Mo3—O4i | 87.55 (15) | C3—C1—H3 | 105.8 |
Mo2—Mo3—O5 | 41.47 (14) | N1—C2—C1ii | 110.9 (7) |
Mo4—Mo3—O5 | 49.29 (14) | N1—C2—H7 | 108.6 |
O4i—Mo3—O5 | 72.4 (2) | C1ii—C2—H7 | 109.1 |
Mo2—Mo3—O6i | 36.17 (16) | N1—C2—H8 | 109.7 |
Mo4—Mo3—O6i | 123.51 (17) | C1ii—C2—H8 | 110.3 |
O4i—Mo3—O6i | 71.9 (2) | H7—C2—H8 | 108.2 |
O5—Mo3—O6i | 74.3 (2) | C1—C3—H4 | 110.1 |
Mo2—Mo3—O9 | 85.8 (2) | C1—C3—H5 | 109.3 |
Mo4—Mo3—O9 | 90.3 (2) | H4—C3—H5 | 109.5 |
O4i—Mo3—O9 | 165.2 (2) | C1—C3—H6 | 109.7 |
O5—Mo3—O9 | 95.2 (3) | H4—C3—H6 | 109.4 |
O6i—Mo3—O9 | 97.4 (3) | H5—C3—H6 | 108.9 |
Mo2—Mo3—O10 | 132.4 (2) | N2—C4—C5iii | 108.1 (9) |
Mo4—Mo3—O10 | 135.2 (2) | N2—C4—C6 | 114.8 (9) |
O4i—Mo3—O10 | 86.2 (2) | C5iii—C4—C6 | 111.8 (9) |
O5—Mo3—O10 | 158.4 (2) | N2—C4—H11 | 107.9 |
O6i—Mo3—O10 | 96.3 (3) | C5iii—C4—H11 | 112.0 |
Mo2—Mo3—O11 | 120.21 (18) | C6—C4—H11 | 102.2 |
Mo4—Mo3—O11 | 32.85 (18) | N2—C5—C4iii | 110.1 (9) |
O4i—Mo3—O11 | 82.7 (2) | N2—C5—H15 | 110.3 |
O5—Mo3—O11 | 78.7 (2) | C4iii—C5—H15 | 110.1 |
O6i—Mo3—O11 | 147.3 (2) | N2—C5—H16 | 109.2 |
O9—Mo3—O10 | 105.4 (3) | C4iii—C5—H16 | 109.6 |
O9—Mo3—O11 | 103.2 (3) | H15—C5—H16 | 107.5 |
O10—Mo3—O11 | 102.3 (3) | C4—C6—H12 | 109.6 |
Mo1—Mo4—Mo3 | 89.98 (3) | C4—C6—H13 | 109.6 |
Mo1—Mo4—O3 | 31.68 (17) | H12—C6—H13 | 109.5 |
Mo3—Mo4—O3 | 119.88 (18) | C4—C6—H14 | 109.2 |
Mo1—Mo4—O5 | 45.87 (14) | H12—C6—H14 | 109.4 |
Mo3—Mo4—O5 | 45.13 (14) | H13—C6—H14 | 109.6 |
O3—Mo4—O5 | 74.7 (2) | | |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x−1, −y, −z+2; (iii) −x, −y−1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O13iv | 1.01 | 1.83 | 2.783 (9) | 156 |
N1—H2···O6 | 1.00 | 1.92 | 2.871 (9) | 158 |
N2—H9···O11i | 1.00 | 1.96 | 2.929 (11) | 164 |
N2—H10···O12v | 1.02 | 1.92 | 2.882 (10) | 156 |
Symmetry codes: (i) −x, −y, −z+2; (iv) −x−1/2, y−1/2, −z+5/2; (v) −x+1/2, y−1/2, −z+5/2. |