Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806005423/om6287sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806005423/om6287Isup2.hkl |
CCDC reference: 601228
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1995); software used to prepare material for publication: SHELXL97.
[V(C9H10BN6)Cl2(C3H6NO)][V(C9H10BN6)ClO(C3H6NO)] | Dx = 1.517 Mg m−3 |
Mr = 797.66 | Melting point: 456(1) K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5892 reflections |
a = 8.6005 (5) Å | θ = 4.1–27.5° |
b = 13.7002 (10) Å | µ = 0.82 mm−1 |
c = 14.8204 (13) Å | T = 100 K |
V = 1746.3 (2) Å3 | Prism, light green |
Z = 2 | 0.19 × 0.12 × 0.06 mm |
F(000) = 815 |
Oxford Diffraction Xcalibur3 diffractometer equipped with a CCD detector | 3987 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3370 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Detector resolution: 15.9890 pixels mm-1 | θmax = 27.5°, θmin = 4.4° |
φ and ω scans | h = −11→11 |
Absorption correction: numerical (Clark & Reid, 1995) | k = −16→17 |
Tmin = 0.812, Tmax = 0.901 | l = −19→19 |
15979 measured reflections |
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)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.134 | w = 1/[σ2(Fo2) + (0.0723P)2 + 0.5753P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
3987 reflections | Δρmax = 0.29 e Å−3 |
229 parameters | Δρmin = −0.58 e Å−3 |
0 restraints | Absolute structure: 1714 Friedel pairs (Flack, 1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (3) |
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. The structure can be modeled with the appropriate molecular formula TpVCl2(DMF), but both Cl atoms were modeled for disorder with an O atom, using PARTs and a separate FVAR (e.g. 21/-21). Each Cl/O disorder was given its own FVAR and allowed to refine. The occupancies of one Cl/O pair refined to 92/8 and, as such, were modeled as 100% Cl in future refinements. The remaining Cl/O pair occupancies were allowed to continue to freely vary and settled at the 53/47 ratio reported in the comment. We had considered fixing the value at 0.5/0.5, but we had no chemical justification for doing so. We have collected data on more than one of these ?green? crystals and note some variability to the O percentage, but it does seem to be a co-crystallization. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.0733 (4) | 0.3920 (3) | −0.1179 (3) | 0.0440 (9) | |
H1 | 0.1358 | 0.4299 | −0.1575 | 0.053* | |
C1S | 0.4331 (4) | 0.5640 (3) | −0.0296 (2) | 0.0335 (7) | |
H1S | 0.4261 | 0.6296 | −0.0095 | 0.040* | |
C2 | −0.0025 (4) | 0.3072 (3) | −0.1422 (3) | 0.0449 (9) | |
H2 | −0.0022 | 0.2765 | −0.1996 | 0.054* | |
C2S | 0.6679 (4) | 0.6115 (3) | −0.1073 (3) | 0.0482 (10) | |
H2S1 | 0.6447 | 0.6743 | −0.0788 | 0.072* | |
H2S2 | 0.6692 | 0.6194 | −0.1730 | 0.072* | |
H2S3 | 0.7699 | 0.5883 | −0.0868 | 0.072* | |
C3 | −0.0789 (4) | 0.2764 (3) | −0.0652 (3) | 0.0414 (8) | |
H3 | −0.1421 | 0.2198 | −0.0599 | 0.050* | |
C3S | 0.5612 (5) | 0.4430 (3) | −0.1198 (3) | 0.0576 (11) | |
H3S1 | 0.4688 | 0.4049 | −0.1039 | 0.086* | |
H3S2 | 0.6541 | 0.4109 | −0.0955 | 0.086* | |
H3S3 | 0.5697 | 0.4474 | −0.1856 | 0.086* | |
C4 | 0.2606 (4) | 0.4071 (3) | 0.2140 (2) | 0.0379 (8) | |
H4 | 0.3478 | 0.4486 | 0.2228 | 0.045* | |
C5 | 0.2237 (4) | 0.3273 (3) | 0.2688 (3) | 0.0425 (8) | |
H5 | 0.2785 | 0.3044 | 0.3203 | 0.051* | |
C6 | 0.0903 (4) | 0.2892 (3) | 0.2313 (3) | 0.0403 (8) | |
H6 | 0.0355 | 0.2336 | 0.2527 | 0.048* | |
C7 | −0.2107 (4) | 0.5978 (3) | 0.1185 (2) | 0.0366 (7) | |
H7 | −0.1907 | 0.6656 | 0.1118 | 0.044* | |
C8 | −0.3498 (4) | 0.5595 (3) | 0.1484 (2) | 0.0408 (8) | |
H8 | −0.4407 | 0.5941 | 0.1660 | 0.049* | |
C9 | −0.3274 (4) | 0.4592 (3) | 0.1471 (2) | 0.0382 (8) | |
H9 | −0.4016 | 0.4113 | 0.1641 | 0.046* | |
B1 | −0.0976 (4) | 0.3435 (3) | 0.1004 (3) | 0.0367 (9) | |
H1B | −0.1664 | 0.2869 | 0.1155 | 0.044* | |
Cl1 | 0.0599 (2) | 0.65803 (16) | −0.04142 (14) | 0.0351 (4) | 0.53 |
O1A | 0.0664 (8) | 0.6100 (6) | −0.0391 (5) | 0.0467 (17) | 0.47 |
Cl2 | 0.21846 (11) | 0.63759 (7) | 0.15529 (8) | 0.0552 (3) | |
N1 | 0.0471 (3) | 0.4138 (2) | −0.0314 (2) | 0.0350 (6) | |
N1S | 0.5482 (3) | 0.5400 (2) | −0.08221 (19) | 0.0366 (6) | |
N2 | 0.1565 (3) | 0.41708 (19) | 0.1475 (2) | 0.0332 (6) | |
N3 | −0.1088 (3) | 0.5285 (2) | 0.10031 (19) | 0.0333 (6) | |
N4 | −0.0477 (3) | 0.3410 (2) | 0.0011 (2) | 0.0351 (6) | |
N5 | 0.0504 (3) | 0.3438 (2) | 0.1596 (2) | 0.0346 (6) | |
N6 | −0.1811 (3) | 0.4416 (2) | 0.1174 (2) | 0.0352 (6) | |
O1S | 0.3310 (3) | 0.50463 (18) | −0.00430 (17) | 0.0401 (6) | |
V1 | 0.11994 (6) | 0.53328 (5) | 0.04922 (6) | 0.0467 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0365 (18) | 0.053 (2) | 0.0419 (19) | 0.0069 (17) | −0.0034 (16) | 0.0064 (17) |
C1S | 0.0243 (14) | 0.0401 (18) | 0.0363 (16) | −0.0032 (13) | −0.0030 (13) | 0.0044 (14) |
C2 | 0.0380 (18) | 0.054 (2) | 0.043 (2) | 0.0113 (17) | −0.0111 (16) | −0.0032 (18) |
C2S | 0.0382 (19) | 0.062 (3) | 0.044 (2) | −0.0153 (18) | 0.0022 (17) | 0.0134 (18) |
C3 | 0.0310 (16) | 0.0381 (18) | 0.055 (2) | 0.0016 (14) | −0.0083 (16) | −0.0080 (16) |
C3S | 0.049 (2) | 0.050 (2) | 0.074 (3) | 0.0025 (19) | 0.019 (2) | −0.004 (2) |
C4 | 0.0272 (16) | 0.0363 (17) | 0.050 (2) | −0.0008 (14) | 0.0030 (15) | −0.0048 (15) |
C5 | 0.0363 (17) | 0.042 (2) | 0.049 (2) | 0.0068 (16) | 0.0046 (16) | 0.0074 (16) |
C6 | 0.0372 (19) | 0.0360 (18) | 0.048 (2) | −0.0007 (15) | 0.0105 (16) | 0.0070 (15) |
C7 | 0.0325 (16) | 0.0378 (17) | 0.0396 (18) | 0.0046 (15) | −0.0015 (15) | −0.0071 (14) |
C8 | 0.0297 (16) | 0.052 (2) | 0.0411 (18) | 0.0055 (15) | 0.0006 (14) | −0.0086 (16) |
C9 | 0.0233 (14) | 0.0465 (19) | 0.0449 (18) | −0.0027 (15) | 0.0035 (14) | −0.0045 (16) |
B1 | 0.0268 (18) | 0.0300 (18) | 0.053 (2) | −0.0032 (16) | 0.0044 (16) | 0.0013 (16) |
Cl1 | 0.0289 (7) | 0.0347 (10) | 0.0417 (9) | −0.0017 (8) | 0.0033 (7) | 0.0064 (10) |
O1A | 0.044 (3) | 0.035 (3) | 0.061 (4) | −0.001 (4) | 0.007 (3) | 0.012 (4) |
Cl2 | 0.0402 (5) | 0.0381 (5) | 0.0874 (8) | 0.0018 (4) | 0.0067 (5) | −0.0105 (5) |
N1 | 0.0259 (13) | 0.0339 (14) | 0.0453 (16) | −0.0051 (12) | 0.0042 (12) | 0.0039 (12) |
N1S | 0.0254 (12) | 0.0466 (17) | 0.0378 (14) | −0.0031 (13) | −0.0007 (11) | 0.0042 (13) |
N2 | 0.0227 (12) | 0.0270 (13) | 0.0500 (16) | −0.0007 (10) | 0.0050 (12) | −0.0002 (12) |
N3 | 0.0224 (12) | 0.0313 (13) | 0.0462 (15) | −0.0026 (13) | 0.0024 (11) | −0.0007 (12) |
N4 | 0.0253 (13) | 0.0304 (14) | 0.0497 (16) | −0.0009 (11) | −0.0002 (12) | 0.0002 (13) |
N5 | 0.0253 (12) | 0.0311 (14) | 0.0475 (16) | −0.0033 (11) | 0.0026 (12) | 0.0016 (13) |
N6 | 0.0214 (12) | 0.0364 (15) | 0.0477 (16) | −0.0043 (12) | 0.0034 (12) | −0.0025 (12) |
O1S | 0.0249 (11) | 0.0392 (13) | 0.0564 (15) | −0.0004 (10) | 0.0032 (11) | 0.0085 (11) |
V1 | 0.0225 (3) | 0.0317 (3) | 0.0860 (5) | −0.0003 (2) | 0.0117 (3) | 0.0049 (3) |
C1—N1 | 1.334 (5) | C6—N5 | 1.344 (5) |
C1—C2 | 1.380 (6) | C6—H6 | 0.9500 |
C1—H1 | 0.9500 | C7—N3 | 1.319 (4) |
C1S—O1S | 1.254 (4) | C7—C8 | 1.380 (5) |
C1S—N1S | 1.302 (4) | C7—H7 | 0.9500 |
C1S—H1S | 0.9500 | C8—C9 | 1.387 (6) |
C2—C3 | 1.383 (6) | C8—H8 | 0.9500 |
C2—H2 | 0.9500 | C9—N6 | 1.355 (4) |
C2S—N1S | 1.469 (4) | C9—H9 | 0.9500 |
C2S—H2S1 | 0.9800 | B1—N4 | 1.534 (5) |
C2S—H2S2 | 0.9800 | B1—N6 | 1.545 (5) |
C2S—H2S3 | 0.9800 | B1—N5 | 1.546 (5) |
C3—N4 | 1.349 (5) | B1—H1B | 1.0000 |
C3—H3 | 0.9500 | Cl1—V1 | 2.234 (2) |
C3S—N1S | 1.446 (5) | O1A—V1 | 1.741 (8) |
C3S—H3S1 | 0.9800 | Cl2—V1 | 2.2872 (13) |
C3S—H3S2 | 0.9800 | N1—N4 | 1.375 (4) |
C3S—H3S3 | 0.9800 | N1—V1 | 2.121 (3) |
C4—N2 | 1.339 (5) | N2—N5 | 1.369 (4) |
C4—C5 | 1.398 (5) | N2—V1 | 2.181 (3) |
C4—H4 | 0.9500 | N3—N6 | 1.366 (4) |
C5—C6 | 1.377 (5) | N3—V1 | 2.109 (3) |
C5—H5 | 0.9500 | O1S—V1 | 2.019 (2) |
N1—C1—C2 | 111.1 (4) | N6—B1—H1B | 111.3 |
N1—C1—H1 | 124.5 | N5—B1—H1B | 111.3 |
C2—C1—H1 | 124.5 | C1—N1—N4 | 105.9 (3) |
O1S—C1S—N1S | 123.3 (3) | C1—N1—V1 | 131.6 (3) |
O1S—C1S—H1S | 118.4 | N4—N1—V1 | 122.5 (2) |
N1S—C1S—H1S | 118.4 | C1S—N1S—C3S | 121.4 (3) |
C1—C2—C3 | 105.4 (3) | C1S—N1S—C2S | 121.1 (3) |
C1—C2—H2 | 127.3 | C3S—N1S—C2S | 117.4 (3) |
C3—C2—H2 | 127.3 | C4—N2—N5 | 105.9 (3) |
N1S—C2S—H2S1 | 109.5 | C4—N2—V1 | 131.6 (2) |
N1S—C2S—H2S2 | 109.5 | N5—N2—V1 | 121.8 (2) |
H2S1—C2S—H2S2 | 109.5 | C7—N3—N6 | 106.7 (3) |
N1S—C2S—H2S3 | 109.5 | C7—N3—V1 | 132.1 (2) |
H2S1—C2S—H2S3 | 109.5 | N6—N3—V1 | 121.19 (19) |
H2S2—C2S—H2S3 | 109.5 | C3—N4—N1 | 109.8 (3) |
N4—C3—C2 | 107.8 (3) | C3—N4—B1 | 131.1 (3) |
N4—C3—H3 | 126.1 | N1—N4—B1 | 119.1 (3) |
C2—C3—H3 | 126.1 | C6—N5—N2 | 110.0 (3) |
N1S—C3S—H3S1 | 109.5 | C6—N5—B1 | 131.1 (3) |
N1S—C3S—H3S2 | 109.5 | N2—N5—B1 | 118.5 (3) |
H3S1—C3S—H3S2 | 109.5 | C9—N6—N3 | 109.1 (3) |
N1S—C3S—H3S3 | 109.5 | C9—N6—B1 | 129.7 (3) |
H3S1—C3S—H3S3 | 109.5 | N3—N6—B1 | 121.1 (2) |
H3S2—C3S—H3S3 | 109.5 | C1S—O1S—V1 | 128.4 (2) |
N2—C4—C5 | 110.8 (3) | O1A—V1—O1S | 93.4 (3) |
N2—C4—H4 | 124.6 | O1A—V1—N3 | 92.4 (3) |
C5—C4—H4 | 124.6 | O1S—V1—N3 | 166.77 (11) |
C6—C5—C4 | 104.6 (3) | O1A—V1—N1 | 88.0 (3) |
C6—C5—H5 | 127.7 | O1S—V1—N1 | 83.92 (10) |
C4—C5—H5 | 127.7 | N3—V1—N1 | 84.43 (11) |
N5—C6—C5 | 108.7 (3) | O1A—V1—N2 | 168.9 (3) |
N5—C6—H6 | 125.7 | O1S—V1—N2 | 89.47 (10) |
C5—C6—H6 | 125.7 | N3—V1—N2 | 82.65 (10) |
N3—C7—C8 | 111.6 (3) | N1—V1—N2 | 81.71 (11) |
N3—C7—H7 | 124.2 | O1A—V1—Cl1 | 12.8 (3) |
C8—C7—H7 | 124.2 | O1S—V1—Cl1 | 96.90 (9) |
C7—C8—C9 | 104.6 (3) | N3—V1—Cl1 | 91.38 (9) |
C7—C8—H8 | 127.7 | N1—V1—Cl1 | 100.56 (10) |
C9—C8—H8 | 127.7 | N2—V1—Cl1 | 173.41 (9) |
N6—C9—C8 | 108.0 (3) | O1A—V1—Cl2 | 103.7 (3) |
N6—C9—H9 | 126.0 | O1S—V1—Cl2 | 93.35 (8) |
C8—C9—H9 | 126.0 | N3—V1—Cl2 | 96.79 (8) |
N4—B1—N6 | 107.8 (3) | N1—V1—Cl2 | 168.16 (9) |
N4—B1—N5 | 108.3 (3) | N2—V1—Cl2 | 86.76 (8) |
N6—B1—N5 | 106.7 (3) | Cl1—V1—Cl2 | 91.20 (7) |
N4—B1—H1B | 111.3 | ||
N1—C1—C2—C3 | 0.0 (4) | N1S—C1S—O1S—V1 | −163.1 (2) |
C1—C2—C3—N4 | −0.2 (4) | C1S—O1S—V1—O1A | 53.2 (4) |
N2—C4—C5—C6 | 0.0 (4) | C1S—O1S—V1—N3 | 169.2 (4) |
C4—C5—C6—N5 | −0.6 (4) | C1S—O1S—V1—N1 | 140.8 (3) |
N3—C7—C8—C9 | −0.3 (4) | C1S—O1S—V1—N2 | −137.5 (3) |
C7—C8—C9—N6 | −0.1 (4) | C1S—O1S—V1—Cl1 | 40.8 (3) |
C2—C1—N1—N4 | 0.2 (4) | C1S—O1S—V1—Cl2 | −50.8 (3) |
C2—C1—N1—V1 | −178.1 (2) | C7—N3—V1—O1A | −49.2 (4) |
O1S—C1S—N1S—C3S | 3.7 (5) | N6—N3—V1—O1A | 127.8 (4) |
O1S—C1S—N1S—C2S | −177.8 (3) | C7—N3—V1—O1S | −165.3 (4) |
C5—C4—N2—N5 | 0.5 (4) | N6—N3—V1—O1S | 11.7 (7) |
C5—C4—N2—V1 | 170.5 (2) | C7—N3—V1—N1 | −136.9 (3) |
C8—C7—N3—N6 | 0.6 (4) | N6—N3—V1—N1 | 40.1 (3) |
C8—C7—N3—V1 | 177.9 (2) | C7—N3—V1—N2 | 140.8 (3) |
C2—C3—N4—N1 | 0.3 (4) | N6—N3—V1—N2 | −42.3 (2) |
C2—C3—N4—B1 | −178.7 (3) | C7—N3—V1—Cl1 | −36.4 (3) |
C1—N1—N4—C3 | −0.3 (4) | N6—N3—V1—Cl1 | 140.5 (2) |
V1—N1—N4—C3 | 178.2 (2) | C7—N3—V1—Cl2 | 55.0 (3) |
C1—N1—N4—B1 | 178.9 (3) | N6—N3—V1—Cl2 | −128.1 (2) |
V1—N1—N4—B1 | −2.6 (4) | C1—N1—V1—O1A | 46.1 (4) |
N6—B1—N4—C3 | −123.5 (4) | N4—N1—V1—O1A | −132.0 (3) |
N5—B1—N4—C3 | 121.4 (4) | C1—N1—V1—O1S | −47.6 (3) |
N6—B1—N4—N1 | 57.5 (4) | N4—N1—V1—O1S | 134.4 (2) |
N5—B1—N4—N1 | −57.6 (4) | C1—N1—V1—N3 | 138.7 (3) |
C5—C6—N5—N2 | 0.9 (4) | N4—N1—V1—N3 | −39.3 (2) |
C5—C6—N5—B1 | −171.0 (3) | C1—N1—V1—N2 | −137.9 (3) |
C4—N2—N5—C6 | −0.9 (4) | N4—N1—V1—N2 | 44.0 (2) |
V1—N2—N5—C6 | −172.1 (2) | C1—N1—V1—Cl1 | 48.3 (3) |
C4—N2—N5—B1 | 172.2 (3) | N4—N1—V1—Cl1 | −129.7 (2) |
V1—N2—N5—B1 | 1.0 (4) | C1—N1—V1—Cl2 | −124.8 (4) |
N4—B1—N5—C6 | −131.0 (4) | N4—N1—V1—Cl2 | 57.2 (5) |
N6—B1—N5—C6 | 113.2 (4) | C4—N2—V1—O1A | 169.6 (13) |
N4—B1—N5—N2 | 57.7 (4) | N5—N2—V1—O1A | −21.7 (14) |
N6—B1—N5—N2 | −58.1 (4) | C4—N2—V1—O1S | 64.2 (3) |
C8—C9—N6—N3 | 0.5 (4) | N5—N2—V1—O1S | −127.1 (2) |
C8—C9—N6—B1 | −178.0 (3) | C4—N2—V1—N3 | −126.5 (3) |
C7—N3—N6—C9 | −0.7 (4) | N5—N2—V1—N3 | 42.2 (2) |
V1—N3—N6—C9 | −178.3 (2) | C4—N2—V1—N1 | 148.1 (3) |
C7—N3—N6—B1 | 177.9 (3) | N5—N2—V1—N1 | −43.2 (2) |
V1—N3—N6—B1 | 0.3 (4) | C4—N2—V1—Cl1 | −101.3 (8) |
N4—B1—N6—C9 | 121.3 (4) | N5—N2—V1—Cl1 | 67.4 (9) |
N5—B1—N6—C9 | −122.5 (4) | C4—N2—V1—Cl2 | −29.2 (3) |
N4—B1—N6—N3 | −57.0 (4) | N5—N2—V1—Cl2 | 139.5 (2) |
N5—B1—N6—N3 | 59.2 (4) |