metal-organic compounds
The title compound, (C16H36N)2[W2Br4(C2O4)O4], has a centrosymmetric dinuclear anion in which two tungsten(VI) centres, with distorted octahedral coordination, are bridged by an oxalate dianion, forming two five-membered chelate rings. All atoms of the complex anion, except for the Br atoms, lie essentially in a plane.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017102/sg2155sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017102/sg2155Isup2.hkl |
CCDC reference: 648087
Key indicators
- Single-crystal X-ray study
- T = 160 K
- Mean (C-C) = 0.006 Å
- R factor = 0.026
- wR factor = 0.063
- Data-to-parameter ratio = 20.3
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 .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.83 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.95 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.76 Ratio PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C1_a ... 1.55 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C16 H36 N
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 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 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Computing details top
Data collection: SMART (Bruker, 2001); cell refinement: local programs; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
Bis(tetrabutylammonium) µ-oxalato-bis[dibromidodioxidotungstate(VI)] top
Crystal data top
(C16H36N)2[W2Br4(C2O4)O4] | F(000) = 1284 |
Mr = 1324.28 | Dx = 1.850 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8891 (9) Å | Cell parameters from 10570 reflections |
b = 18.0806 (15) Å | θ = 1.1–26.3° |
c = 13.2945 (11) Å | µ = 8.24 mm−1 |
β = 90.905 (2)° | T = 160 K |
V = 2376.8 (4) Å3 | Block, colourless |
Z = 2 | 0.32 × 0.32 × 0.16 mm |
Data collection top
Bruker SMART 1K CCD diffractometer | 4689 independent reflections |
Radiation source: sealed tube | 4435 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.3°, θmin = 1.9° |
thin–slice ω scans | h = −6→12 |
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2001) | k = −21→20 |
Tmin = 0.075, Tmax = 0.270 | l = −15→16 |
12764 measured reflections |
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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0214P)2 + 4.8146P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max = 0.001 |
4689 reflections | Δρmax = 1.21 e Å−3 |
231 parameters | Δρmin = −1.18 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00108 (9) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
W1 | 0.399964 (14) | 0.076456 (8) | 0.677516 (11) | 0.02061 (7) | |
Br1 | 0.55009 (4) | 0.17320 (2) | 0.59921 (3) | 0.03541 (11) | |
Br2 | 0.27883 (4) | −0.04418 (2) | 0.70104 (3) | 0.03561 (11) | |
O1 | 0.2597 (3) | 0.13192 (16) | 0.6808 (2) | 0.0327 (6) | |
O2 | 0.4712 (3) | 0.08290 (15) | 0.7952 (2) | 0.0318 (6) | |
O3 | 0.5636 (2) | 0.00313 (15) | 0.62216 (19) | 0.0231 (5) | |
C1 | 0.5609 (3) | −0.01447 (19) | 0.5314 (3) | 0.0198 (7) | |
O4 | 0.6449 (2) | −0.05281 (15) | 0.4857 (2) | 0.0230 (5) | |
N1 | 0.4453 (3) | −0.28446 (16) | 1.0635 (2) | 0.0205 (6) | |
C2 | 0.4015 (4) | −0.2921 (2) | 1.1720 (3) | 0.0241 (8) | |
H2A | 0.3854 | −0.2419 | 1.1991 | 0.029* | |
H2B | 0.4775 | −0.3139 | 1.2113 | 0.029* | |
C3 | 0.2756 (4) | −0.3387 (2) | 1.1903 (3) | 0.0280 (8) | |
H3A | 0.1961 | −0.3155 | 1.1569 | 0.034* | |
H3B | 0.2876 | −0.3887 | 1.1614 | 0.034* | |
C4 | 0.2522 (5) | −0.3446 (3) | 1.3031 (3) | 0.0360 (10) | |
H4A | 0.3345 | −0.3651 | 1.3360 | 0.043* | |
H4B | 0.2376 | −0.2944 | 1.3306 | 0.043* | |
C5 | 0.1322 (5) | −0.3929 (3) | 1.3291 (4) | 0.0401 (11) | |
H5A | 0.1266 | −0.3977 | 1.4024 | 0.060* | |
H5B | 0.1435 | −0.4420 | 1.2992 | 0.060* | |
H5C | 0.0489 | −0.3703 | 1.3027 | 0.060* | |
C6 | 0.5677 (4) | −0.2341 (2) | 1.0609 (3) | 0.0228 (7) | |
H6A | 0.5426 | −0.1860 | 1.0909 | 0.027* | |
H6B | 0.5902 | −0.2249 | 0.9897 | 0.027* | |
C7 | 0.6938 (4) | −0.2622 (2) | 1.1149 (3) | 0.0280 (8) | |
H7A | 0.7189 | −0.3112 | 1.0874 | 0.034* | |
H7B | 0.6753 | −0.2683 | 1.1874 | 0.034* | |
C8 | 0.8105 (4) | −0.2084 (2) | 1.1017 (3) | 0.0295 (9) | |
H8A | 0.7850 | −0.1593 | 1.1285 | 0.035* | |
H8B | 0.8294 | −0.2027 | 1.0292 | 0.035* | |
C9 | 0.9377 (4) | −0.2362 (3) | 1.1569 (4) | 0.0403 (11) | |
H9A | 1.0105 | −0.1999 | 1.1500 | 0.060* | |
H9B | 0.9659 | −0.2835 | 1.1277 | 0.060* | |
H9C | 0.9182 | −0.2432 | 1.2283 | 0.060* | |
C10 | 0.4780 (4) | −0.3609 (2) | 1.0221 (3) | 0.0210 (7) | |
H10A | 0.5382 | −0.3865 | 1.0711 | 0.025* | |
H10B | 0.3929 | −0.3897 | 1.0172 | 0.025* | |
C11 | 0.5448 (4) | −0.3620 (2) | 0.9200 (3) | 0.0237 (8) | |
H11A | 0.6330 | −0.3362 | 0.9244 | 0.028* | |
H11B | 0.4870 | −0.3357 | 0.8702 | 0.028* | |
C12 | 0.5662 (4) | −0.4413 (2) | 0.8860 (3) | 0.0284 (8) | |
H12A | 0.6358 | −0.4648 | 0.9298 | 0.034* | |
H12B | 0.4808 | −0.4693 | 0.8937 | 0.034* | |
C13 | 0.6102 (5) | −0.4459 (3) | 0.7777 (3) | 0.0423 (11) | |
H13A | 0.6241 | −0.4978 | 0.7593 | 0.063* | |
H13B | 0.6950 | −0.4186 | 0.7698 | 0.063* | |
H13C | 0.5401 | −0.4244 | 0.7338 | 0.063* | |
C14 | 0.3329 (4) | −0.2505 (2) | 0.9990 (3) | 0.0244 (8) | |
H14A | 0.3643 | −0.2483 | 0.9287 | 0.029* | |
H14B | 0.2541 | −0.2842 | 1.0001 | 0.029* | |
C15 | 0.2849 (4) | −0.1738 (2) | 1.0283 (3) | 0.0309 (9) | |
H15A | 0.3628 | −0.1395 | 1.0314 | 0.037* | |
H15B | 0.2440 | −0.1756 | 1.0957 | 0.037* | |
C16 | 0.1813 (5) | −0.1461 (3) | 0.9517 (4) | 0.0398 (10) | |
H16A | 0.2224 | −0.1461 | 0.8842 | 0.048* | |
H16B | 0.1035 | −0.1806 | 0.9497 | 0.048* | |
C17 | 0.1309 (7) | −0.0691 (3) | 0.9751 (5) | 0.0624 (17) | |
H17A | 0.0589 | −0.0556 | 0.9270 | 0.094* | |
H17B | 0.2057 | −0.0338 | 0.9699 | 0.094* | |
H17C | 0.0955 | −0.0679 | 1.0435 | 0.094* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.02427 (9) | 0.02173 (10) | 0.01584 (10) | 0.00202 (5) | 0.00063 (6) | −0.00254 (5) |
Br1 | 0.0420 (2) | 0.0298 (2) | 0.0345 (2) | −0.01094 (17) | 0.00287 (18) | 0.00072 (17) |
Br2 | 0.0350 (2) | 0.0313 (2) | 0.0406 (3) | −0.00694 (17) | 0.00136 (18) | 0.00578 (18) |
O1 | 0.0365 (15) | 0.0335 (16) | 0.0281 (15) | 0.0096 (12) | 0.0037 (12) | 0.0016 (12) |
O2 | 0.0409 (16) | 0.0325 (16) | 0.0220 (15) | 0.0020 (12) | −0.0030 (12) | −0.0043 (12) |
O3 | 0.0253 (12) | 0.0286 (14) | 0.0153 (12) | 0.0038 (11) | −0.0035 (10) | −0.0046 (11) |
C1 | 0.0212 (17) | 0.0165 (17) | 0.0216 (18) | 0.0010 (13) | −0.0001 (14) | 0.0006 (14) |
O4 | 0.0222 (12) | 0.0266 (13) | 0.0202 (13) | 0.0035 (10) | −0.0025 (10) | −0.0046 (11) |
N1 | 0.0219 (14) | 0.0201 (15) | 0.0195 (16) | 0.0007 (12) | −0.0016 (12) | 0.0000 (12) |
C2 | 0.0292 (19) | 0.028 (2) | 0.0154 (18) | −0.0009 (15) | −0.0006 (15) | −0.0042 (15) |
C3 | 0.0250 (18) | 0.032 (2) | 0.027 (2) | −0.0030 (16) | 0.0024 (15) | −0.0038 (17) |
C4 | 0.044 (2) | 0.039 (2) | 0.025 (2) | −0.011 (2) | 0.0087 (18) | −0.0084 (18) |
C5 | 0.041 (2) | 0.045 (3) | 0.034 (2) | −0.012 (2) | 0.0104 (19) | −0.010 (2) |
C6 | 0.0255 (18) | 0.0204 (18) | 0.0225 (19) | −0.0018 (14) | 0.0004 (14) | −0.0016 (15) |
C7 | 0.0252 (18) | 0.030 (2) | 0.028 (2) | −0.0022 (16) | −0.0013 (15) | 0.0003 (17) |
C8 | 0.0261 (19) | 0.031 (2) | 0.031 (2) | −0.0045 (16) | 0.0057 (16) | −0.0080 (17) |
C9 | 0.029 (2) | 0.047 (3) | 0.045 (3) | −0.0041 (19) | −0.0029 (19) | −0.011 (2) |
C10 | 0.0217 (16) | 0.0192 (17) | 0.0221 (18) | 0.0000 (14) | −0.0018 (14) | −0.0021 (15) |
C11 | 0.0247 (18) | 0.0226 (19) | 0.0238 (19) | 0.0029 (14) | 0.0015 (14) | −0.0009 (15) |
C12 | 0.032 (2) | 0.025 (2) | 0.028 (2) | 0.0064 (16) | 0.0005 (16) | −0.0042 (17) |
C13 | 0.059 (3) | 0.039 (3) | 0.029 (2) | 0.018 (2) | 0.005 (2) | −0.006 (2) |
C14 | 0.0277 (18) | 0.0248 (19) | 0.0205 (19) | 0.0055 (15) | −0.0038 (15) | 0.0003 (15) |
C15 | 0.031 (2) | 0.030 (2) | 0.032 (2) | 0.0080 (17) | −0.0033 (17) | −0.0020 (18) |
C16 | 0.044 (2) | 0.039 (2) | 0.037 (3) | 0.015 (2) | 0.000 (2) | 0.003 (2) |
C17 | 0.077 (4) | 0.053 (3) | 0.057 (4) | 0.042 (3) | 0.004 (3) | 0.006 (3) |
Geometric parameters (Å, º) top
W1—Br1 | 2.5291 (4) | C7—C8 | 1.522 (5) |
W1—Br2 | 2.5103 (5) | C8—H8A | 0.990 |
W1—O1 | 1.712 (3) | C8—H8B | 0.990 |
W1—O2 | 1.710 (3) | C8—C9 | 1.532 (6) |
W1—O3 | 2.226 (2) | C9—H9A | 0.980 |
W1—O4i | 2.249 (3) | C9—H9B | 0.980 |
C1—O3 | 1.247 (4) | C9—H9C | 0.980 |
C1—O4 | 1.247 (4) | C10—H10A | 0.990 |
C1—C1i | 1.547 (7) | C10—H10B | 0.990 |
O4—W1i | 2.249 (3) | C10—C11 | 1.519 (5) |
N1—C2 | 1.520 (4) | C11—H11A | 0.990 |
N1—C6 | 1.516 (4) | C11—H11B | 0.990 |
N1—C10 | 1.524 (5) | C11—C12 | 1.519 (5) |
N1—C14 | 1.523 (5) | C12—H12A | 0.990 |
C2—H2A | 0.990 | C12—H12B | 0.990 |
C2—H2B | 0.990 | C12—C13 | 1.514 (6) |
C2—C3 | 1.526 (5) | C13—H13A | 0.980 |
C3—H3A | 0.990 | C13—H13B | 0.980 |
C3—H3B | 0.990 | C13—H13C | 0.980 |
C3—C4 | 1.525 (6) | C14—H14A | 0.990 |
C4—H4A | 0.990 | C14—H14B | 0.990 |
C4—H4B | 0.990 | C14—C15 | 1.517 (5) |
C4—C5 | 1.519 (6) | C15—H15A | 0.990 |
C5—H5A | 0.980 | C15—H15B | 0.990 |
C5—H5B | 0.980 | C15—C16 | 1.518 (6) |
C5—H5C | 0.980 | C16—H16A | 0.990 |
C6—H6A | 0.990 | C16—H16B | 0.990 |
C6—H6B | 0.990 | C16—C17 | 1.514 (7) |
C6—C7 | 1.517 (5) | C17—H17A | 0.980 |
C7—H7A | 0.990 | C17—H17B | 0.980 |
C7—H7B | 0.990 | C17—H17C | 0.980 |
Br1—W1—Br2 | 159.484 (16) | H7B—C7—C8 | 109.6 |
Br1—W1—O1 | 94.96 (10) | C7—C8—H8A | 109.5 |
Br1—W1—O2 | 95.35 (10) | C7—C8—H8B | 109.5 |
Br1—W1—O3 | 80.87 (7) | C7—C8—C9 | 110.7 (4) |
Br1—W1—O4i | 80.94 (7) | H8A—C8—H8B | 108.1 |
Br2—W1—O1 | 96.74 (10) | H8A—C8—C9 | 109.5 |
Br2—W1—O2 | 97.81 (10) | H8B—C8—C9 | 109.5 |
Br2—W1—O3 | 82.80 (7) | C8—C9—H9A | 109.5 |
Br2—W1—O4i | 82.40 (7) | C8—C9—H9B | 109.5 |
O1—W1—O2 | 105.00 (14) | C8—C9—H9C | 109.5 |
O1—W1—O3 | 161.90 (12) | H9A—C9—H9B | 109.5 |
O1—W1—O4i | 89.35 (12) | H9A—C9—H9C | 109.5 |
O2—W1—O3 | 92.96 (12) | H9B—C9—H9C | 109.5 |
O2—W1—O4i | 165.48 (12) | N1—C10—H10A | 108.4 |
O3—W1—O4i | 72.62 (9) | N1—C10—H10B | 108.4 |
W1—O3—C1 | 117.8 (2) | N1—C10—C11 | 115.6 (3) |
W1i—O4—C1 | 116.9 (2) | H10A—C10—H10B | 107.4 |
O3—C1—C1i | 116.1 (4) | H10A—C10—C11 | 108.4 |
O3—C1—O4 | 127.5 (3) | H10B—C10—C11 | 108.4 |
C1i—C1—O4 | 116.4 (4) | C10—C11—H11A | 109.7 |
C2—N1—C6 | 108.4 (3) | C10—C11—H11B | 109.7 |
C2—N1—C10 | 109.0 (3) | C10—C11—C12 | 110.0 (3) |
C2—N1—C14 | 110.8 (3) | H11A—C11—H11B | 108.2 |
C6—N1—C10 | 111.3 (3) | H11A—C11—C12 | 109.7 |
C6—N1—C14 | 108.7 (3) | H11B—C11—C12 | 109.7 |
C10—N1—C14 | 108.7 (3) | C11—C12—H12A | 109.2 |
N1—C2—H2A | 108.2 | C11—C12—H12B | 109.2 |
N1—C2—H2B | 108.2 | C11—C12—C13 | 112.2 (3) |
N1—C2—C3 | 116.5 (3) | H12A—C12—H12B | 107.9 |
H2A—C2—H2B | 107.3 | H12A—C12—C13 | 109.2 |
H2A—C2—C3 | 108.2 | H12B—C12—C13 | 109.2 |
H2B—C2—C3 | 108.2 | C12—C13—H13A | 109.5 |
C2—C3—H3A | 109.8 | C12—C13—H13B | 109.5 |
C2—C3—H3B | 109.8 | C12—C13—H13C | 109.5 |
C2—C3—C4 | 109.4 (3) | H13A—C13—H13B | 109.5 |
H3A—C3—H3B | 108.2 | H13A—C13—H13C | 109.5 |
H3A—C3—C4 | 109.8 | H13B—C13—H13C | 109.5 |
H3B—C3—C4 | 109.8 | N1—C14—H14A | 108.1 |
C3—C4—H4A | 108.9 | N1—C14—H14B | 108.1 |
C3—C4—H4B | 108.9 | N1—C14—C15 | 116.9 (3) |
C3—C4—C5 | 113.3 (4) | H14A—C14—H14B | 107.3 |
H4A—C4—H4B | 107.7 | H14A—C14—C15 | 108.1 |
H4A—C4—C5 | 108.9 | H14B—C14—C15 | 108.1 |
H4B—C4—C5 | 108.9 | C14—C15—H15A | 109.7 |
C4—C5—H5A | 109.5 | C14—C15—H15B | 109.7 |
C4—C5—H5B | 109.5 | C14—C15—C16 | 109.8 (4) |
C4—C5—H5C | 109.5 | H15A—C15—H15B | 108.2 |
H5A—C5—H5B | 109.5 | H15A—C15—C16 | 109.7 |
H5A—C5—H5C | 109.5 | H15B—C15—C16 | 109.7 |
H5B—C5—H5C | 109.5 | C15—C16—H16A | 109.0 |
N1—C6—H6A | 108.3 | C15—C16—H16B | 109.0 |
N1—C6—H6B | 108.3 | C15—C16—C17 | 112.7 (4) |
N1—C6—C7 | 116.0 (3) | H16A—C16—H16B | 107.8 |
H6A—C6—H6B | 107.4 | H16A—C16—C17 | 109.0 |
H6A—C6—C7 | 108.3 | H16B—C16—C17 | 109.0 |
H6B—C6—C7 | 108.3 | C16—C17—H17A | 109.5 |
C6—C7—H7A | 109.6 | C16—C17—H17B | 109.5 |
C6—C7—H7B | 109.6 | C16—C17—H17C | 109.5 |
C6—C7—C8 | 110.5 (3) | H17A—C17—H17B | 109.5 |
H7A—C7—H7B | 108.1 | H17A—C17—H17C | 109.5 |
H7A—C7—C8 | 109.6 | H17B—C17—H17C | 109.5 |
Br1—W1—O3—C1 | −80.5 (3) | C10—N1—C6—C7 | −55.8 (4) |
Br2—W1—O3—C1 | 87.0 (3) | C14—N1—C6—C7 | −175.5 (3) |
O1—W1—O3—C1 | −2.6 (5) | N1—C6—C7—C8 | 177.0 (3) |
O2—W1—O3—C1 | −175.5 (3) | C6—C7—C8—C9 | 179.5 (3) |
O4i—W1—O3—C1 | 2.8 (2) | C2—N1—C10—C11 | −170.6 (3) |
W1—O3—C1—C1i | −2.6 (5) | C6—N1—C10—C11 | −51.1 (4) |
W1—O3—C1—O4 | 177.6 (3) | C14—N1—C10—C11 | 68.6 (4) |
O3—C1—O4—W1i | 177.5 (3) | N1—C10—C11—C12 | −177.6 (3) |
C1i—C1—O4—W1i | −2.3 (5) | C10—C11—C12—C13 | 170.3 (4) |
C6—N1—C2—C3 | 177.7 (3) | C2—N1—C14—C15 | 60.0 (4) |
C10—N1—C2—C3 | −61.0 (4) | C6—N1—C14—C15 | −59.0 (4) |
C14—N1—C2—C3 | 58.5 (4) | C10—N1—C14—C15 | 179.7 (3) |
N1—C2—C3—C4 | 176.3 (3) | N1—C14—C15—C16 | 175.5 (3) |
C2—C3—C4—C5 | −177.5 (4) | C14—C15—C16—C17 | −178.8 (4) |
C2—N1—C6—C7 | 64.0 (4) |
Symmetry code: (i) −x+1, −y, −z+1. |