The title compound, (C4H12N)4[V2O2(SO4)4], contains two independent tetramethylammonium cations, [N(CH3)4]+, and a centrosymmetric dimeric anion, [(VO)2(SO4)4]4−. The V5+ cation has a square-pyramidal environment with the oxo group at the apex.
Supporting information
CCDC reference: 242294
Key indicators
- Single-crystal X-ray study
- T = 295 K
- R factor = 0.031
- wR factor = 0.078
- Data-to-parameter ratio = 15.2
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.02
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) V1 - O1 .. 5.23 su
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... S1
PLAT244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors .... N1
PLAT244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors .... N2
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 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
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 1999); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 1990).
Tetrakis(tetramethylammonium) di-am-sulfato-bis[oxosulfatovanadium(V)]
top
Crystal data top
(C4H12N)4[V2O2(SO4)4] | F(000) = 852 |
Mr = 814.71 | Dx = 1.574 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2879 reflections |
a = 13.1346 (12) Å | θ = 2.6–28.5° |
b = 9.2316 (9) Å | µ = 0.86 mm−1 |
c = 14.2385 (14) Å | T = 295 K |
β = 95.171 (2)° | Prism, blue |
V = 1719.4 (3) Å3 | 0.38 × 0.36 × 0.15 mm |
Z = 2 | |
Data collection top
Bruker SMART APEX three-circle diffractometer | 3504 independent reflections |
Radiation source: fine-focus sealed tube | 3244 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 8.33 pixels mm-1 | θmax = 26.4°, θmin = 2.0° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (XPREP in SHELXL97; Sheldrick, 1997) | k = −11→11 |
Tmin = 0.758, Tmax = 0.879 | l = −17→17 |
18354 measured reflections | |
Refinement top
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | Only H-atom displacement parameters refined |
S = 1.00 | w = 1/[σ2(Fo2) + (0.04P)2 + 0.923P], P = (max(Fo2,0) + 2Fc2)/3 |
3504 reflections | (Δ/σ)max = 0.001 |
231 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
V1 | 0.14798 (2) | 0.55928 (3) | 0.44158 (2) | 0.03007 (10) | |
O1 | 0.13229 (12) | 0.44128 (16) | 0.36135 (10) | 0.0487 (4) | |
S1 | 0.08231 (3) | 0.33780 (5) | 0.59639 (3) | 0.03758 (13) | |
O2 | 0.10353 (11) | 0.48682 (16) | 0.55995 (9) | 0.0428 (3) | |
O3 | −0.02854 (10) | 0.31090 (15) | 0.57296 (13) | 0.0532 (4) | |
O4 | 0.10317 (15) | 0.3422 (2) | 0.69726 (12) | 0.0755 (6) | |
O5 | 0.13834 (14) | 0.2298 (2) | 0.55067 (15) | 0.0725 (5) | |
S2 | 0.33012 (3) | 0.67973 (5) | 0.44705 (3) | 0.03788 (13) | |
O6 | 0.29394 (10) | 0.54562 (16) | 0.49561 (10) | 0.0441 (3) | |
O7 | 0.40144 (11) | 0.64549 (18) | 0.38022 (12) | 0.0563 (4) | |
O8 | 0.22771 (10) | 0.72647 (15) | 0.39791 (10) | 0.0451 (3) | |
O9 | 0.36687 (12) | 0.7871 (2) | 0.51426 (13) | 0.0656 (5) | |
N1 | 0.36639 (11) | 0.15700 (17) | 0.37964 (11) | 0.0364 (3) | |
C1 | 0.44383 (17) | 0.0466 (2) | 0.35789 (17) | 0.0498 (5) | |
H1A | 0.4302 | −0.0428 | 0.3888 | 0.077 (9)* | |
H1B | 0.5109 | 0.0804 | 0.3799 | 0.071 (8)* | |
H1C | 0.4402 | 0.0312 | 0.2910 | 0.061 (7)* | |
C2 | 0.26219 (16) | 0.1066 (3) | 0.34473 (18) | 0.0564 (6) | |
H2A | 0.2125 | 0.1758 | 0.3618 | 0.076 (9)* | |
H2B | 0.2490 | 0.0145 | 0.3725 | 0.058 (7)* | |
H2C | 0.2578 | 0.0970 | 0.2773 | 0.076 (9)* | |
C3 | 0.37061 (17) | 0.1800 (3) | 0.48337 (15) | 0.0539 (6) | |
H3A | 0.3198 | 0.2497 | 0.4971 | 0.072 (8)* | |
H3B | 0.4371 | 0.2151 | 0.5060 | 0.060 (7)* | |
H3C | 0.3576 | 0.0900 | 0.5139 | 0.071 (8)* | |
C4 | 0.3898 (2) | 0.2950 (3) | 0.3322 (2) | 0.0631 (6) | |
H4A | 0.3872 | 0.2796 | 0.2653 | 0.090 (10)* | |
H4B | 0.4569 | 0.3275 | 0.3552 | 0.074 (9)* | |
H4C | 0.3403 | 0.3671 | 0.3454 | 0.096 (11)* | |
N2 | 0.10944 (12) | 0.87828 (19) | 0.70926 (11) | 0.0411 (4) | |
C5 | 0.13391 (19) | 0.9830 (3) | 0.78671 (17) | 0.0565 (6) | |
H5A | 0.1275 | 1.0799 | 0.7624 | 0.070 (8)* | |
H5B | 0.2027 | 0.9674 | 0.8137 | 0.076 (9)* | |
H5C | 0.0875 | 0.9697 | 0.8343 | 0.081 (9)* | |
C6 | 0.0064 (2) | 0.9132 (4) | 0.6624 (2) | 0.0757 (8) | |
H6A | −0.0438 | 0.9027 | 0.7069 | 0.086 (10)* | |
H6B | −0.0092 | 0.8484 | 0.6104 | 0.109 (12)* | |
H6C | 0.0059 | 1.0112 | 0.6398 | 0.110 (13)* | |
C7 | 0.1103 (3) | 0.7304 (3) | 0.7501 (2) | 0.0776 (9) | |
H7A | 0.0595 | 0.7239 | 0.7943 | 0.095 (10)* | |
H7B | 0.1765 | 0.7108 | 0.7818 | 0.121 (15)* | |
H7C | 0.0956 | 0.6609 | 0.7006 | 0.098 (11)* | |
C8 | 0.1873 (2) | 0.8882 (3) | 0.6402 (2) | 0.0689 (7) | |
H8A | 0.1707 | 0.8209 | 0.5897 | 0.111 (12)* | |
H8B | 0.2534 | 0.8652 | 0.6709 | 0.082 (9)* | |
H8C | 0.1881 | 0.9847 | 0.6153 | 0.085 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
V1 | 0.02584 (15) | 0.03179 (17) | 0.03249 (17) | −0.00425 (11) | 0.00205 (11) | 0.00219 (11) |
O1 | 0.0522 (9) | 0.0503 (8) | 0.0432 (8) | −0.0071 (7) | 0.0020 (6) | −0.0079 (6) |
S1 | 0.0268 (2) | 0.0433 (3) | 0.0429 (3) | 0.00368 (18) | 0.00449 (18) | 0.0134 (2) |
O2 | 0.0441 (7) | 0.0462 (8) | 0.0391 (7) | −0.0133 (6) | 0.0091 (6) | 0.0029 (6) |
O3 | 0.0305 (7) | 0.0386 (8) | 0.0894 (12) | −0.0017 (6) | −0.0003 (7) | 0.0088 (7) |
O4 | 0.0796 (12) | 0.0975 (15) | 0.0474 (9) | −0.0065 (11) | −0.0058 (9) | 0.0284 (9) |
O5 | 0.0594 (10) | 0.0584 (11) | 0.1040 (15) | 0.0205 (8) | 0.0316 (10) | 0.0115 (10) |
S2 | 0.0280 (2) | 0.0435 (3) | 0.0429 (3) | −0.00921 (18) | 0.00739 (18) | −0.0029 (2) |
O6 | 0.0289 (6) | 0.0549 (9) | 0.0475 (8) | −0.0043 (6) | −0.0015 (6) | 0.0143 (6) |
O7 | 0.0443 (8) | 0.0627 (10) | 0.0655 (10) | −0.0075 (7) | 0.0248 (7) | −0.0049 (8) |
O8 | 0.0358 (7) | 0.0418 (7) | 0.0574 (9) | −0.0067 (6) | 0.0031 (6) | 0.0153 (7) |
O9 | 0.0477 (9) | 0.0787 (12) | 0.0715 (11) | −0.0256 (8) | 0.0120 (8) | −0.0282 (9) |
N1 | 0.0317 (8) | 0.0384 (8) | 0.0391 (8) | 0.0006 (6) | 0.0022 (6) | −0.0020 (7) |
C1 | 0.0434 (11) | 0.0526 (13) | 0.0539 (13) | 0.0091 (9) | 0.0066 (9) | −0.0082 (10) |
C2 | 0.0372 (11) | 0.0626 (15) | 0.0672 (15) | −0.0057 (10) | −0.0083 (10) | −0.0047 (12) |
C3 | 0.0465 (12) | 0.0747 (16) | 0.0409 (11) | 0.0044 (11) | 0.0063 (9) | −0.0088 (11) |
C4 | 0.0752 (17) | 0.0463 (13) | 0.0685 (16) | −0.0074 (12) | 0.0108 (13) | 0.0067 (12) |
N2 | 0.0388 (8) | 0.0445 (9) | 0.0406 (9) | −0.0045 (7) | 0.0075 (7) | −0.0063 (7) |
C5 | 0.0561 (14) | 0.0554 (14) | 0.0567 (14) | 0.0012 (11) | −0.0023 (11) | −0.0166 (11) |
C6 | 0.0470 (14) | 0.111 (3) | 0.0663 (17) | −0.0128 (14) | −0.0095 (12) | −0.0036 (17) |
C7 | 0.103 (2) | 0.0459 (14) | 0.088 (2) | −0.0065 (14) | 0.0316 (19) | 0.0002 (14) |
C8 | 0.0629 (16) | 0.085 (2) | 0.0629 (16) | −0.0048 (14) | 0.0305 (13) | −0.0060 (15) |
Geometric parameters (Å, º) top
V1—O1 | 1.5785 (14) | C3—H3A | 0.9600 |
V1—O2 | 1.9509 (13) | C3—H3B | 0.9600 |
V1—O3i | 1.9702 (14) | C3—H3C | 0.9600 |
V1—O8 | 1.9957 (13) | C4—H4A | 0.9600 |
V1—O6 | 2.0043 (13) | C4—H4B | 0.9600 |
S1—O5 | 1.4305 (17) | C4—H4C | 0.9600 |
S1—O4 | 1.4382 (18) | N2—C5 | 1.480 (3) |
S1—O3 | 1.4850 (14) | N2—C7 | 1.483 (3) |
S1—O2 | 1.5052 (14) | N2—C8 | 1.484 (3) |
S2—O7 | 1.4296 (15) | N2—C6 | 1.489 (3) |
S2—O9 | 1.4314 (16) | C5—H5A | 0.9600 |
S2—O6 | 1.5151 (14) | C5—H5B | 0.9600 |
S2—O8 | 1.5216 (14) | C5—H5C | 0.9600 |
N1—C4 | 1.487 (3) | C6—H6A | 0.9600 |
N1—C2 | 1.488 (2) | C6—H6B | 0.9600 |
N1—C3 | 1.488 (3) | C6—H6C | 0.9600 |
N1—C1 | 1.492 (3) | C7—H7A | 0.9600 |
C1—H1A | 0.9600 | C7—H7B | 0.9600 |
C1—H1B | 0.9600 | C7—H7C | 0.9600 |
C1—H1C | 0.9600 | C8—H8A | 0.9600 |
C2—H2A | 0.9600 | C8—H8B | 0.9600 |
C2—H2B | 0.9600 | C8—H8C | 0.9600 |
C2—H2C | 0.9600 | | |
| | | |
O1—V1—O2 | 111.03 (7) | H2B—C2—H2C | 109.5 |
O1—V1—O3i | 107.03 (8) | N1—C3—H3A | 109.5 |
O2—V1—O3i | 90.11 (7) | N1—C3—H3B | 109.5 |
O1—V1—O8 | 110.26 (7) | H3A—C3—H3B | 109.5 |
O2—V1—O8 | 137.78 (6) | N1—C3—H3C | 109.5 |
O3i—V1—O8 | 86.11 (6) | H3A—C3—H3C | 109.5 |
O1—V1—O6 | 107.00 (7) | H3B—C3—H3C | 109.5 |
O2—V1—O6 | 89.84 (6) | N1—C4—H4A | 109.5 |
O3i—V1—O6 | 143.48 (6) | N1—C4—H4B | 109.5 |
O8—V1—O6 | 69.98 (6) | H4A—C4—H4B | 109.5 |
O5—S1—O4 | 114.49 (13) | N1—C4—H4C | 109.5 |
O5—S1—O3 | 108.38 (11) | H4A—C4—H4C | 109.5 |
O4—S1—O3 | 108.89 (11) | H4B—C4—H4C | 109.5 |
O5—S1—O2 | 111.19 (9) | C5—N2—C7 | 108.4 (2) |
O4—S1—O2 | 107.10 (10) | C5—N2—C8 | 109.72 (19) |
O3—S1—O2 | 106.48 (8) | C7—N2—C8 | 109.5 (2) |
S1—O2—V1 | 133.66 (9) | C5—N2—C6 | 108.64 (19) |
S1—O3—V1i | 132.62 (9) | C7—N2—C6 | 110.5 (2) |
O7—S2—O9 | 113.36 (10) | C8—N2—C6 | 110.0 (2) |
O7—S2—O6 | 111.99 (9) | N2—C5—H5A | 109.5 |
O9—S2—O6 | 111.21 (10) | N2—C5—H5B | 109.5 |
O7—S2—O8 | 111.20 (9) | H5A—C5—H5B | 109.5 |
O9—S2—O8 | 109.99 (10) | N2—C5—H5C | 109.5 |
O6—S2—O8 | 98.10 (7) | H5A—C5—H5C | 109.5 |
S2—O6—V1 | 95.85 (7) | H5B—C5—H5C | 109.5 |
S2—O8—V1 | 95.99 (7) | N2—C6—H6A | 109.5 |
C4—N1—C2 | 109.72 (18) | N2—C6—H6B | 109.5 |
C4—N1—C3 | 109.76 (18) | H6A—C6—H6B | 109.5 |
C2—N1—C3 | 109.09 (17) | N2—C6—H6C | 109.5 |
C4—N1—C1 | 108.55 (17) | H6A—C6—H6C | 109.5 |
C2—N1—C1 | 109.94 (17) | H6B—C6—H6C | 109.5 |
C3—N1—C1 | 109.78 (16) | N2—C7—H7A | 109.5 |
N1—C1—H1A | 109.5 | N2—C7—H7B | 109.5 |
N1—C1—H1B | 109.5 | H7A—C7—H7B | 109.5 |
H1A—C1—H1B | 109.5 | N2—C7—H7C | 109.5 |
N1—C1—H1C | 109.5 | H7A—C7—H7C | 109.5 |
H1A—C1—H1C | 109.5 | H7B—C7—H7C | 109.5 |
H1B—C1—H1C | 109.5 | N2—C8—H8A | 109.5 |
N1—C2—H2A | 109.5 | N2—C8—H8B | 109.5 |
N1—C2—H2B | 109.5 | H8A—C8—H8B | 109.5 |
H2A—C2—H2B | 109.5 | N2—C8—H8C | 109.5 |
N1—C2—H2C | 109.5 | H8A—C8—H8C | 109.5 |
H2A—C2—H2C | 109.5 | H8B—C8—H8C | 109.5 |
| | | |
O5—S1—O2—V1 | 25.30 (16) | O8—S2—O6—V1 | 2.39 (9) |
O4—S1—O2—V1 | 151.06 (13) | O1—V1—O6—S2 | 103.98 (9) |
O3—S1—O2—V1 | −92.57 (13) | O2—V1—O6—S2 | −144.04 (8) |
O1—V1—O2—S1 | 17.19 (15) | O3i—V1—O6—S2 | −54.08 (13) |
O3i—V1—O2—S1 | 125.53 (12) | O8—V1—O6—S2 | −1.92 (7) |
O8—V1—O2—S1 | −150.16 (10) | O7—S2—O8—V1 | 115.04 (9) |
O6—V1—O2—S1 | −90.99 (12) | O9—S2—O8—V1 | −118.55 (9) |
O5—S1—O3—V1i | −149.26 (14) | O6—S2—O8—V1 | −2.40 (9) |
O4—S1—O3—V1i | 85.61 (16) | O1—V1—O8—S2 | −99.46 (9) |
O2—S1—O3—V1i | −29.56 (17) | O2—V1—O8—S2 | 67.96 (11) |
O7—S2—O6—V1 | −114.45 (9) | O3i—V1—O8—S2 | 153.81 (9) |
O9—S2—O6—V1 | 117.58 (9) | O6—V1—O8—S2 | 1.91 (7) |
Symmetry code: (i) −x, −y+1, −z+1. |