In the title compound, (C2H8N)3[Mo12O40P], the Keggin ion [PO40Mo12]3- lies on a special position of site symmetry 3m and the [(CH3)2NH2]+ cation on a special position of site symmetry m.
Supporting information
CCDC reference: 258646
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (N-C) = 0.009 Å
- R factor = 0.027
- wR factor = 0.069
- Data-to-parameter ratio = 11.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.56
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.58 Ratio
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 44.00 A 3
PLAT731_ALERT_1_C Bond Calc 1.909(4), Rep 1.9100(10) ...... 4.00 su-Rat
MO1 -O2 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 1.911(3), Rep 1.9100(10) ...... 3.00 su-Rat
MO1 -O2 1.555 4.555
PLAT731_ALERT_1_C Bond Calc 1.926(5), Rep 1.927(2) ...... 2.50 su-Rat
MO3 -O8 1.555 2.555
PLAT733_ALERT_1_C Torsion Calc 179.7(3), Rep 179.70(10) ...... 3.00 su-Rat
O10 -P1 -O10 -MO2 21.555 1.555 1.555 23.555
PLAT733_ALERT_1_C Torsion Calc -179.7(3), Rep -179.70(10) ...... 3.00 su-Rat
O10 -P1 -O10 -MO2 2.555 1.555 1.555 1.555
Alert level G
ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be
replaced by the scaled T values. Since the ratio of scaled T's
is identical to the ratio of reported T values, the scaling
does not imply a change to the absorption corrections used in
the study.
Ratio of Tmax expected/reported 0.565
Tmax scaled 0.274 Tmin scaled 0.167
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
12 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: XSCANS (Bruker, 1994); cell refinement: LEAST SQUARES in XSCANS (Bruker, 1994); data reduction: REDUCE in XSCANS (Bruker, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
tris(dimethylammonium) dodecamolybdophosphate
top
Crystal data top
(C2H8N)3[Mo12O40P] | Dx = 3.277 Mg m−3 |
Mr = 1960.53 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3m | Cell parameters from 34 reflections |
Hall symbol: -R 3 2" | θ = 5.0–12.9° |
a = 16.541 (2) Å | µ = 3.81 mm−1 |
c = 25.154 (7) Å | T = 295 K |
V = 5960 (2) Å3 | Block, yellow |
Z = 6 | 0.52 × 0.34 × 0.34 mm |
F(000) = 5520 | |
Data collection top
Siemens P4 four-circle diffractometer | 1150 reflections with I > 2σ(I) |
Radiation source: medium-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 25.0°, θmin = 1.6° |
ω scans | h = −1→19 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = −19→1 |
Tmin = 0.295, Tmax = 0.484 | l = −6→29 |
3044 measured reflections | 3 standard reflections every 97 reflections |
1304 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.069 | w = 1/[σ2(Fo2) + (0.038P)2 + 0.2473P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
1304 reflections | Δρmax = 1.35 e Å−3 |
116 parameters | Δρmin = −0.91 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00054 (3) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mo1 | 0.14951 (4) | 0.07476 (2) | 0.15295 (2) | 0.0182 (2) | |
Mo2 | 0.21887 (3) | 0.00563 (3) | 0.26271 (2) | 0.0187 (2) | |
Mo3 | 0.06896 (2) | −0.06896 (2) | 0.38322 (2) | 0.0178 (2) | |
P1 | 0.0000 | 0.0000 | 0.26541 (9) | 0.0102 (5) | |
O1 | 0.1960 (3) | 0.0980 (2) | 0.0916 (2) | 0.027 (1) | |
O2 | 0.0520 (2) | 0.1041 (3) | 0.1459 (2) | 0.020 (1) | |
O3 | 0.2239 (2) | 0.0319 (2) | 0.1886 (1) | 0.020 (1) | |
O4 | 0.1175 (1) | −0.1175 (1) | 0.2503 (2) | 0.020 (1) | |
O5 | 0.2753 (3) | 0.1377 (1) | 0.2747 (2) | 0.022 (1) | |
O6 | 0.3118 (2) | −0.0095 (2) | 0.2699 (1) | 0.026 (1) | |
O7 | 0.1707 (2) | −0.0126 (2) | 0.3341 (1) | 0.022 (1) | |
O8 | −0.0539 (2) | −0.1077 (3) | 0.4107 (2) | 0.020 (1) | |
O9 | 0.1102 (2) | −0.1102 (2) | 0.4304 (2) | 0.028 (1) | |
O10 | 0.1008 (3) | 0.0504 (1) | 0.2452 (2) | 0.014 (1) | |
O11 | 0.0000 | 0.0000 | 0.3261 (3) | 0.011 (1) | |
N1 | 0.4930 (2) | −0.0140 (4) | 0.2694 (2) | 0.0230 (1) | |
C1 | 0.5405 (3) | 0.0809 (5) | 0.2921 (3) | 0.038 (2) | |
C2 | 0.4920 (3) | −0.0159 (5) | 0.2107 (3) | 0.040 (2) | |
H1 | 0.4337 | −0.0447 | 0.2812 | 0.044* | 0.50 |
H1a | 0.5384 | 0.0770 | 0.3302 | 0.057* | |
H1b | 0.5096 | 0.1138 | 0.2804 | 0.057* | |
H2a | 0.4606 | −0.0795 | 0.1986 | 0.060* | |
H2b | 0.5550 | 0.0155 | 0.1976 | 0.060* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mo1 | 0.0185 (3) | 0.0228 (2) | 0.0119 (3) | 0.0092 (2) | 0.0038 (2) | 0.0019 (1) |
Mo2 | 0.0156 (2) | 0.0221 (2) | 0.0219 (3) | 0.0121 (2) | 0.0005 (1) | 0.0024 (2) |
Mo3 | 0.0209 (2) | 0.0209 (2) | 0.0144 (3) | 0.0128 (2) | −0.0021 (1) | 0.0021 (1) |
P1 | 0.0105 (8) | 0.0105 (8) | 0.0095 (12) | 0.0053 (4) | 0.000 | 0.000 |
O1 | 0.028 (3) | 0.033 (2) | 0.017 (2) | 0.014 (1) | 0.005 (2) | 0.003 (1) |
O2 | 0.019 (2) | 0.024 (2) | 0.020 (2) | 0.012 (1) | 0.001 (1) | 0.002 (2) |
O3 | 0.018 (2) | 0.026 (2) | 0.018 (2) | 0.013 (1) | 0.003 (1) | 0.000 (1) |
O4 | 0.020 (2) | 0.020 (2) | 0.023 (2) | 0.011 (2) | −0.001 (1) | 0.001 (1) |
O5 | 0.015 (2) | 0.021 (2) | 0.028 (2) | 0.008 (1) | 0.001 (2) | 0.001 (1) |
O6 | 0.020 (2) | 0.031 (2) | 0.033 (2) | 0.016 (1) | 0.002 (1) | 0.006 (2) |
O7 | 0.021 (2) | 0.028 (2) | 0.017 (1) | 0.014 (1) | 0.000 (1) | 0.003 (1) |
O8 | 0.022 (2) | 0.024 (2) | 0.015 (2) | 0.012 (1) | 0.002 (1) | 0.004 (2) |
O9 | 0.037 (2) | 0.037 (2) | 0.021 (2) | 0.027 (2) | −0.002 (1) | 0.002 (1) |
O10 | 0.011 (2) | 0.015 (2) | 0.015 (2) | 0.006 (1) | −0.001 (2) | −0.001 (1) |
O11 | 0.011 (2) | 0.011 (2) | 0.011 (3) | 0.006 (1) | 0.000 | 0.000 |
N1 | 0.038 (3) | 0.026 (3) | 0.021 (3) | 0.013 (2) | 0.004 (1) | 0.008 (2) |
C1 | 0.045 (4) | 0.025 (4) | 0.037 (4) | 0.012 (2) | 0.001 (2) | 0.001 (3) |
C2 | 0.055 (4) | 0.035 (4) | 0.023 (4) | 0.017 (2) | 0.000 (2) | 0.000 (3) |
Geometric parameters (Å, º) top
Mo1—O1 | 1.680 (4) | Mo3—O8iv | 1.927 (2) |
Mo1—O2 | 1.910 (1) | Mo3—O9 | 1.676 (4) |
Mo1—O2i | 1.910 (1) | Mo3—O11 | 2.443 (4) |
Mo1—O3 | 1.922 (3) | P1—O11 | 1.525 (7) |
Mo1—O3ii | 1.922 (3) | P1—O10iii | 1.531 (4) |
Mo1—O10 | 2.423 (4) | P1—O10 | 1.531 (4) |
Mo2—O3 | 1.907 (3) | P1—O10iv | 1.531 (4) |
Mo2—O4 | 1.909 (1) | N1—C1 | 1.475 (9) |
Mo2—O5 | 1.922 (2) | N1—C2 | 1.476 (9) |
Mo2—O6 | 1.687 (3) | N1—H1 | 0.90 |
Mo2—O7 | 1.926 (3) | C1—H1a | 0.96 |
Mo2—O10 | 2.450 (3) | C1—H1b | 0.96 |
Mo3—O7 | 1.913 (3) | C2—H2a | 0.96 |
Mo3—O7iii | 1.913 (3) | C2—H2b | 0.96 |
Mo3—O8 | 1.927 (2) | | |
| | | |
O1—Mo1—O2 | 101.8 (2) | O8—Mo3—O8iv | 87.8 (2) |
O1—Mo1—O2i | 101.8 (2) | O8—Mo3—O9 | 100.7 (2) |
O1—Mo1—O3 | 102.0 (1) | O8—Mo3—O11 | 72.9 (1) |
O1—Mo1—O3ii | 102.0 (1) | O8iv—Mo3—O9 | 100.7 (2) |
O1—Mo1—O10 | 173.4 (2) | O8iv—Mo3—O11 | 72.9 (1) |
O2—Mo1—O2i | 85.1 (2) | O9—Mo3—O11 | 170.9 (2) |
O2—Mo1—O3 | 156.2 (2) | O11—P1—O10iii | 109.4 (2) |
O2—Mo1—O3ii | 89.0 (2) | O11—P1—O10 | 109.4 (2) |
O2—Mo1—O10 | 83.0 (1) | O10iii—P1—O10 | 109.6 (2) |
O2i—Mo1—O3 | 89.0 (2) | O11—P1—O10iv | 109.4 (2) |
O2i—Mo1—O3ii | 156.2 (2) | O10iii—P1—O10iv | 109.6 (2) |
O2i—Mo1—O10 | 83.0 (1) | O10—P1—O10iv | 109.6 (2) |
O3—Mo1—O3ii | 87.2 (2) | Mo1iv—O2—Mo1 | 152.4 (2) |
O3—Mo1—O10 | 73.3 (1) | Mo2—O3—Mo1 | 125.2 (2) |
O3ii—Mo1—O10 | 73.3 (1) | Mo2—O4—Mo2iii | 153.2 (2) |
O3—Mo2—O4 | 89.9 (2) | Mo2—O5—Mo2ii | 126.6 (2) |
O3—Mo2—O5 | 87.4 (2) | Mo3—O7—Mo2 | 150.8 (2) |
O3—Mo2—O6 | 101.5 (1) | Mo3—O8—Mo3i | 125.2 (2) |
O3—Mo2—O7 | 156.2 (1) | P1—O10—Mo1 | 126.1 (2) |
O3—Mo2—O10 | 72.9 (1) | P1—O10—Mo2ii | 126.3 (1) |
O4—Mo2—O5 | 155.1 (2) | Mo1—O10—Mo2ii | 88.5 (1) |
O4—Mo2—O6 | 103.8 (2) | P1—O10—Mo2 | 126.3 (1) |
O4—Mo2—O7 | 85.0 (2) | Mo1—O10—Mo2 | 88.5 (1) |
O4—Mo2—O10 | 83.4 (1) | Mo2ii—O10—Mo2 | 89.0 (1) |
O5—Mo2—O6 | 101.0 (2) | P1—O11—Mo3iv | 126.1 (1) |
O5—Mo2—O7 | 87.7 (2) | P1—O11—Mo3 | 126.1 (1) |
O5—Mo2—O10 | 72.1 (1) | Mo3iv—O11—Mo3 | 88.9 (2) |
O6—Mo2—O7 | 102.3 (1) | P1—O11—Mo3i | 126.1 (1) |
O6—Mo2—O10 | 171.0 (1) | Mo3iv—O11—Mo3i | 88.9 (2) |
O7—Mo2—O10 | 83.4 (1) | Mo3—O11—Mo3i | 88.9 (2) |
O7—Mo3—O7iii | 86.3 (2) | C1—N1—C2 | 113.9 (6) |
O7—Mo3—O8 | 156.7 (1) | C1—N1—H1 | 108.8 |
O7—Mo3—O8iv | 88.3 (2) | C2—N1—H1 | 108.8 |
O7—Mo3—O9 | 102.6 (1) | N1—C1—H1a | 109.5 |
O7—Mo3—O11 | 84.0 (1) | N1—C1—H1b | 109.5 |
O7iii—Mo3—O8 | 88.3 (2) | H1a—C1—H1b | 109.5 |
O7iii—Mo3—O8iv | 156.7 (1) | N1—C2—H2a | 109.5 |
O7iii—Mo3—O9 | 102.6 (1) | N1—C2—H2b | 109.5 |
O7iii—Mo3—O11 | 84.0 (1) | H2a—C2—H2b | 109.5 |
| | | |
O1—Mo1—O2—Mo1iv | 128.2 (5) | O11—P1—O10—Mo2ii | −60.4 (2) |
O2i—Mo1—O2—Mo1iv | 27.2 (6) | O10iii—P1—O10—Mo2ii | 179.7 (1) |
O3ii—Mo1—O2—Mo1iv | −129.7 (5) | O10iv—P1—O10—Mo2ii | 59.5 (4) |
O3—Mo1—O2—Mo1iv | −49.0 (8) | O11—P1—O10—Mo2 | 60.4 (2) |
O10—Mo1—O2—Mo1iv | −56.4 (5) | O10iii—P1—O10—Mo2 | −59.5 (4) |
O6—Mo2—O3—Mo1 | −170.4 (2) | O10iv—P1—O10—Mo2 | −179.7 (1) |
O4—Mo2—O3—Mo1 | 85.5 (2) | O2i—Mo1—O10—P1 | −42.9 (1) |
O5—Mo2—O3—Mo1 | −69.7 (2) | O2—Mo1—O10—P1 | 42.9 (1) |
O7—Mo2—O3—Mo1 | 8.4 (4) | O3ii—Mo1—O10—P1 | 134.0 (1) |
O10—Mo2—O3—Mo1 | 2.3 (2) | O3—Mo1—O10—P1 | −134.0 (1) |
O1—Mo1—O3—Mo2 | 172.8 (2) | O2i—Mo1—O10—Mo2ii | −178.4 (1) |
O2i—Mo1—O3—Mo2 | −85.4 (2) | O2—Mo1—O10—Mo2ii | −92.6 (1) |
O2—Mo1—O3—Mo2 | −10.0 (5) | O3ii—Mo1—O10—Mo2ii | −1.5 (1) |
O3ii—Mo1—O3—Mo2 | 71.1 (2) | O3—Mo1—O10—Mo2ii | 90.6 (1) |
O10—Mo1—O3—Mo2 | −2.4 (2) | O2i—Mo1—O10—Mo2 | 92.6 (1) |
O6—Mo2—O4—Mo2iii | 131.6 (5) | O2—Mo1—O10—Mo2 | 178.4 (1) |
O3—Mo2—O4—Mo2iii | −126.6 (5) | O3ii—Mo1—O10—Mo2 | −90.6 (1) |
O5—Mo2—O4—Mo2iii | −43.2 (8) | O3—Mo1—O10—Mo2 | 1.5 (1) |
O7—Mo2—O4—Mo2iii | 30.1 (5) | O3—Mo2—O10—P1 | 133.8 (3) |
O10—Mo2—O4—Mo2iii | −53.8 (5) | O4—Mo2—O10—P1 | 42.0 (2) |
O6—Mo2—O5—Mo2ii | 169.7 (3) | O5—Mo2—O10—P1 | −133.4 (3) |
O3—Mo2—O5—Mo2ii | 68.5 (3) | O7—Mo2—O10—P1 | −43.7 (2) |
O4—Mo2—O5—Mo2ii | −15.4 (6) | O3—Mo2—O10—Mo1 | −1.5 (1) |
O7—Mo2—O5—Mo2ii | −88.2 (3) | O4—Mo2—O10—Mo1 | −93.4 (1) |
O10—Mo2—O5—Mo2ii | −4.4 (2) | O5—Mo2—O10—Mo1 | 91.3 (2) |
O9—Mo3—O7—Mo2 | 131.1 (3) | O7—Mo2—O10—Mo1 | −179.1 (1) |
O7iii—Mo3—O7—Mo2 | 29.0 (4) | O3—Mo2—O10—Mo2ii | −90.0 (1) |
O8—Mo3—O7—Mo2 | −47.8 (6) | O4—Mo2—O10—Mo2ii | 178.1 (2) |
O8iv—Mo3—O7—Mo2 | −128.3 (4) | O5—Mo2—O10—Mo2ii | 2.8 (2) |
O11—Mo3—O7—Mo2 | −55.3 (3) | O7—Mo2—O10—Mo2ii | 92.4 (1) |
O6—Mo2—O7—Mo3 | −131.7 (3) | O7iii—Mo3—O11—P1 | −43.43 (9) |
O3—Mo2—O7—Mo3 | 49.4 (5) | O7—Mo3—O11—P1 | 43.43 (9) |
O4—Mo2—O7—Mo3 | −28.6 (4) | O8—Mo3—O11—P1 | −133.5 (1) |
O5—Mo2—O7—Mo3 | 127.5 (4) | O8iv—Mo3—O11—P1 | 133.5 (1) |
O10—Mo2—O7—Mo3 | 55.3 (3) | O7iii—Mo3—O11—Mo3iv | −179.0 (1) |
O9—Mo3—O8—Mo3i | 170.1 (2) | O7—Mo3—O11—Mo3iv | −92.1 (1) |
O7iii—Mo3—O8—Mo3i | −87.4 (3) | O8—Mo3—O11—Mo3iv | 91.0 (2) |
O7—Mo3—O8—Mo3i | −10.9 (6) | O8iv—Mo3—O11—Mo3iv | −2.1 (1) |
O8iv—Mo3—O8—Mo3i | 69.6 (3) | O7iii—Mo3—O11—Mo3i | 92.1 (1) |
O11—Mo3—O8—Mo3i | −3.2 (2) | O7—Mo3—O11—Mo3i | 179.0 (1) |
O10iii—P1—O10—Mo1 | 60.1 (2) | O8—Mo3—O11—Mo3i | 2.1 (1) |
O10iv—P1—O10—Mo1 | −60.1 (2) | O8iv—Mo3—O11—Mo3i | −91.0 (2) |
Symmetry codes: (i) −x+y, −x, z; (ii) x, x−y, z; (iii) −y, −x, z; (iv) −y, x−y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O6 | 0.90 | 2.38 | 3.035 (3) | 130 |
N1—H1···O7v | 0.90 | 2.31 | 3.112 (5) | 149 |
Symmetry code: (v) y+1/3, x−1/3, −z+2/3. |