The preparation and structures of three diborane(4) compounds are described. The compound B
2(3,4-S
2C
4H
2-1-S)
2 [2,2′-bi(1,3,5,2-trithiaborapentalene), C
8H
4B
2S
6] is planar and lies at a crystallographic inversion centre. The amine adducts [B
2(C
3S
5)
2(NHMe
2)
2] [2,2′-bis(dimethylamino)-2,2′-bi(1,3,4,6,2-tetrathiaborapentalene-5-thione), C
10H
14B
2N
2S
10] and [B
2(1,2-S
2C
2H
4)
2(NHMe
2)
2]·0.33CH
2Cl
2 [1,2-bis(di-methylamino)-1,1:2,2-bis(dimethylenedithioxy)diborane(4) dichloromethane solvate, C
8H
22B
2N
2S
4·0.33CH
2Cl
2] contain dimethylamine ligands bound to each boron in an
anti conformation about the B—B bond, with tetrahedral geometry at the B atoms. The crystal structures display a number of S
S interactions, which appear to dictate the packing arrangements.
Supporting information
CCDC references: 144622; 144623; 144624
For (I), a solution of n-BuLi (2.8 ml of a 1.6 M solution in hexanes) was
added to a cooled solution (195 K) of 3,4-dibromothiophene (1.0 g, 4.5 mmol)
in Et2O (10 ml) and the reaction was stirred for 30 min, after which time
elemental S (0.144 g, 4.5 mmol) was added. The reaction was then stirred at
195 K for 1 h, after which time the addition of n-BuLi and elemental S was
repeated. The reaction was then allowed to warm to room temperature and was
stirred for a further 30 min. After this time the reaction was recooled to 195 K and HCl (10 ml of a 1.0 M solution in Et2O) was added. Upon warming
to room temperature a precipitate formed and the solution became yellow.
Filtration afforded a yellow solution which was reduced in volume to ca
10 ml, which also removed any unreacted HCl. The filtrate was then cooled to
273 K and B2(NMe2)4 (0.5 ml, 2.5 mmol; Brotherton et al., 1960)
was added, resulting in the immediate formation of a yellow precipitate. The
reaction was stirred for 12 h, after which time the Et2O was removed by
syringe and the solid washed with hexane (5 × 5 ml) to give the crude
bis-amine adduct [B2(3,4-S2C4H2-1-S)2(NHMe2)2]. To a suspension
of [B2(3,4-S2C4H2-1-S)2(NHMe2)2] (0.15 g, 0.37 mmol) in Et2O
(5 ml) HCl (1 ml of a 1.0 M solution in Et2O) was added and the
reaction stirred for 3 h. After this time the solid was removed by filtration
and washed with Et2O (2 × 5 ml). Combination and evaporation of the
Et2O fractions gave compound (I) as a yellow solid, and this was
recrystallized by dissolving in toluene and layering with hexane (yield: 0.8 g, 69%). 1H NMR (CDCl3) δ 7.37p.p.m.; 11B {1H} NMR (CDCl3) δ
62.7p.p.m. For (IV), B2(NMe2)4 (0.3 ml, 1.5 mmol) was added to a
solution of 1,2-ethanedithiol (0.28 g, 3.0 mmol) in hexane (20 ml) and the
solution refluxed for 5 h, after which it was allowed to cool to room
temperature and then refrigerated at 243 K overnight. The solvent was then
removed by syringe, affording (IV) as a white crystalline solid (yield: 0.36 g, 81%). 11B {1H} NMR (CDCl3) δ 5.8p.p.m. Addition of HCl affords
B2(1,2-S2C2H4)2 in solution; 11B{1H} NMR (CDCl3) δ 65.8p.p.m.
For (V), a solution of [B2Cl4(NHMe2)2] (0.26 g, 1.0 mmol; Lawlor et
al., 1998) in tetrahydrofuran (2 ml) was added to a stirred suspension of
[NEt4]2[Zn(C3S5)2] (0.50 g, 21 mmol) in tetrahydrofuran (10 ml),
resulting in a colour change from dark red to light yellow. Crystals of (V)
were isolated by layering this solution with toluene (2 ml), CH2Cl2
(volume?) and hexane (10 ml). 11B {1H} NMR (CDCl3) δ 41.8p.p.m.
H atoms were constrained to idealized geometries and assigned isotropic
displacement parameters 1.2 times the Uiso value of their attached C
(1.5 Uiso for methyl groups), with the exception of H1 and H2 in (IV)
which were located from the electron density difference map. During refinement
of (I), high residual electron density, poor agreement factors (R1 = 0.240 and
wR2 = 0.586), a β angle close to 90° and unusual shapes of the diffraction
peaks all suggested non-merohedral twinning. Addition of the
pseudo-orthorhombic twin law (100, 010, 001) improved convergence and
greatly reduced the agreement factors and the features in the final difference
map. The volume fraction of one of the twin components was found to be
0.383 (3). The twinning is presumably responsible for the rather high electron
density residuals (highest peak 1.12 e Å3, 0.81 Å from S2; deepest
trough -0.71 e Å3, 0.85 Å from S1). The good agreement between the
chemcially equivalent bond lengths and angles and the reasonable ellipsoids
suggests that the model is satisfactory. In (V), the Cl atoms of the
dichloromethane molecule were located on a threefold axis with the C atom
disordered over two sets of three sites, each with an occupancy of about 1/6.
The atoms C9 [occupancy factor 3*0.178 (8)] and C9' were refined isotropically.
Attached H atoms were not included.
For all compounds, data collection: SMART (Siemens, 1995a); cell refinement: SAINT (Siemens, 1995a); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Siemens, 1995b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
(I) 2,2'-bi(1,3,5,2-trithiaborapentalene)
top
Crystal data top
C8H4B2S6 | F(000) = 316 |
Mr = 314.10 | Dx = 1.737 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.549 (2) Å | Cell parameters from 62 reflections |
b = 7.525 (2) Å | θ = 5–50° |
c = 5.891 (4) Å | µ = 1.10 mm−1 |
β = 90.04 (3)° | T = 173 K |
V = 600.6 (4) Å3 | Plate, colourless |
Z = 2 | 0.55 × 0.40 × 0.01 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 1383 independent reflections |
Radiation source: fine-focus sealed tube | 1150 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 60 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ω rotation with narrow frame scans | h = −13→17 |
Absorption correction: SADABS (sheldrick, 1996) ? | k = −9→9 |
Tmin = 0.37, Tmax = 0.88 | l = −7→7 |
3856 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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 0.98 | Calculated w = 1/[σ2(Fo2) + (0.0882P)2] where P = [max(Fo2,0) + 2Fc2]/3 |
1382 reflections | (Δ/σ)max = 0.001 |
74 parameters | Δρmax = 1.12 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
Crystal data top
C8H4B2S6 | V = 600.6 (4) Å3 |
Mr = 314.10 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.549 (2) Å | µ = 1.10 mm−1 |
b = 7.525 (2) Å | T = 173 K |
c = 5.891 (4) Å | 0.55 × 0.40 × 0.01 mm |
β = 90.04 (3)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 1383 independent reflections |
Absorption correction: SADABS (sheldrick, 1996) ? | 1150 reflections with I > 2σ(I) |
Tmin = 0.37, Tmax = 0.88 | Rint = 0.047 |
3856 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 0.98 | Δρmax = 1.12 e Å−3 |
1382 reflections | Δρmin = −0.71 e Å−3 |
74 parameters | |
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 on F2 for ALL reflections except for 1 with very negative
F2 or flagged by the user for potential systematic errors. Weighted
R-factors wR and all goodnesses of fit S are based on
F2, conventional R-factors R are based on F,
with F set to zero for negative F2. The observed criterion of
F2 > σ(F2) is used only for calculating R factor obs
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. Unit-cell dimensions were determined from reflections taken from three sets of
30 frames (at 0.3° steps in ω), typically at 10–30 s. A full hemisphere of
reciprocal space was scanned by 0.3° ω steps at ϕ 0, 90 and 180° with the
area detector held at 2θ = -29° for (I) and (V); for (IV) a full
sphere of reciprocal space was scanned. The crystal-to-detector distance was
4.974 cm. Crystal decay was monitored by repeating the initial 50 frames at
the end of data collection and analysing the duplicate reflections. No decay
was observed in any data set. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
B1 | 0.9409 (5) | 0.4994 (7) | 0.4593 (10) | 0.0167 (11) | |
S1 | 0.90031 (10) | 0.5845 (2) | 0.1893 (2) | 0.0184 (3) | |
S2 | 0.84291 (11) | 0.4094 (2) | 0.6327 (2) | 0.0196 (3) | |
S3 | 0.58766 (11) | 0.5154 (2) | 0.2313 (3) | 0.0287 (4) | |
C1 | 0.7475 (4) | 0.4611 (7) | 0.4425 (9) | 0.0200 (11) | |
C2 | 0.7746 (4) | 0.5453 (7) | 0.2345 (9) | 0.0194 (11) | |
C3 | 0.6950 (4) | 0.5837 (7) | 0.1018 (10) | 0.0239 (12) | |
H3 | 0.6983 | 0.6403 | −0.0422 | 0.029* | |
C4 | 0.6481 (4) | 0.4350 (7) | 0.4660 (9) | 0.0242 (12) | |
H4 | 0.6172 | 0.3807 | 0.5930 | 0.029* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
B1 | 0.028 (3) | 0.005 (2) | 0.017 (2) | 0.000 (2) | −0.001 (2) | 0.002 (2) |
S1 | 0.0223 (6) | 0.0135 (6) | 0.0195 (6) | −0.0002 (5) | 0.0011 (5) | 0.0022 (4) |
S2 | 0.0249 (7) | 0.0140 (6) | 0.0200 (6) | −0.0006 (5) | 0.0012 (6) | 0.0026 (4) |
S3 | 0.0226 (6) | 0.0281 (8) | 0.0353 (7) | 0.0037 (6) | 0.0002 (7) | −0.0014 (6) |
C1 | 0.026 (3) | 0.010 (3) | 0.023 (3) | 0.003 (2) | 0.002 (2) | −0.001 (2) |
C2 | 0.025 (3) | 0.014 (2) | 0.020 (3) | 0.003 (2) | 0.000 (2) | −0.005 (2) |
C3 | 0.029 (3) | 0.018 (3) | 0.025 (3) | 0.000 (2) | −0.001 (2) | 0.000 (2) |
C4 | 0.026 (3) | 0.023 (3) | 0.024 (3) | 0.001 (2) | 0.005 (3) | −0.001 (2) |
Geometric parameters (Å, º) top
B1—B1i | 1.672 (12) | S3—C4 | 1.717 (6) |
B1—S1 | 1.800 (6) | S3—C3 | 1.722 (6) |
B1—S2 | 1.807 (6) | S3—S3iv | 3.621 (4) |
S1—C2 | 1.749 (5) | C1—C4 | 1.368 (8) |
S2—C1 | 1.753 (6) | C1—C2 | 1.428 (8) |
S2—S1ii | 3.618 (3) | C2—C3 | 1.362 (7) |
S2—S2iii | 3.799 (2) | | |
| | | |
B1i—B1—S1 | 122.9 (5) | C4—S3—C3 | 93.4 (3) |
B1i—B1—S2 | 123.0 (5) | C4—S3—S3iv | 153.7 (2) |
S1—B1—S2 | 114.1 (3) | C3—S3—S3iv | 103.9 (2) |
C2—S1—B1 | 95.9 (3) | C4—C1—C2 | 113.8 (5) |
C2—S1—S1v | 89.6 (2) | C4—C1—S2 | 129.0 (4) |
B1—S1—S1v | 63.6 (2) | C2—C1—S2 | 117.2 (4) |
C1—S2—B1 | 95.6 (3) | C3—C2—C1 | 112.5 (5) |
C1—S2—S1ii | 131.0 (2) | C3—C2—S1 | 130.3 (4) |
B1—S2—S1ii | 102.6 (2) | C1—C2—S1 | 117.1 (4) |
C1—S2—S2iii | 129.4 (2) | C2—C3—S3 | 110.5 (4) |
B1—S2—S2iii | 132.5 (2) | C1—C4—S3 | 109.7 (4) |
S1ii—S2—S2iii | 61.80 (4) | | |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y, z+1; (iii) x, −y+1/2, z+1/2; (iv) −x+1, −y+1, −z; (v) x, −y+3/2, z+1/2. |
(IV) 2,2'-bis(dimethylamino)-2,2'-bi(1,3,4,6,2-tetrathiaborapentalene-
S-thione
top
Crystal data top
C10H14B2N2S10 | Z = 2 |
Mr = 504.45 | F(000) = 516 |
Triclinic, P1 | Dx = 1.629 Mg m−3 |
a = 9.578 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.686 (2) Å | Cell parameters from 132 reflections |
c = 12.172 (3) Å | θ = 5–50° |
α = 95.56 (2)° | µ = 1.07 mm−1 |
β = 91.99 (2)° | T = 123 K |
γ = 113.349 (12)° | Needle, orange |
V = 1028.5 (4) Å3 | 0.5 × 0.1 × 0.1 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 4654 independent reflections |
Radiation source: fine-focus sealed tube | 3579 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 60 pixels mm-1 | θmax = 27.5°, θmin = 1.7° |
ω rotation with narrow frame scans | h = −12→12 |
Absorption correction: SADABS (sheldrick, 1996) ? | k = −12→12 |
Tmin = 0.70, Tmax = 0.92 | l = −15→15 |
10786 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) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Calculated w = 1/[σ2(Fo2) + (0.0385P)2] where P = [max(Fo2,0) + 2Fc2]/3 |
4654 reflections | (Δ/σ)max = 0.001 |
224 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
Crystal data top
C10H14B2N2S10 | γ = 113.349 (12)° |
Mr = 504.45 | V = 1028.5 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.578 (2) Å | Mo Kα radiation |
b = 9.686 (2) Å | µ = 1.07 mm−1 |
c = 12.172 (3) Å | T = 123 K |
α = 95.56 (2)° | 0.5 × 0.1 × 0.1 mm |
β = 91.99 (2)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 4654 independent reflections |
Absorption correction: SADABS (sheldrick, 1996) ? | 3579 reflections with I > 2σ(I) |
Tmin = 0.70, Tmax = 0.92 | Rint = 0.028 |
10786 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.41 e Å−3 |
4654 reflections | Δρmin = −0.41 e Å−3 |
224 parameters | |
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 on F2 for ALL reflections except for 0 with very negative
F2 or flagged by the user for potential systematic errors. Weighted
R-factors wR and all goodnesses of fit S are based on
F2, conventional R-factors R are based on F,
with F set to zero for negative F2. The observed criterion of
F2 > σ(F2) is used only for calculating R factor obs
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 | |
B1 | 0.5772 (3) | 0.5840 (3) | 0.2826 (2) | 0.0125 (5) | |
B2 | 0.4094 (3) | 0.4217 (3) | 0.2492 (2) | 0.0118 (5) | |
S1 | 0.73855 (6) | 0.59055 (7) | 0.18881 (5) | 0.01337 (13) | |
S2 | 0.65921 (6) | 0.58975 (7) | 0.43303 (5) | 0.01503 (14) | |
S3 | 1.07636 (6) | 0.72149 (7) | 0.27398 (5) | 0.01448 (13) | |
S4 | 1.00500 (7) | 0.72002 (7) | 0.50245 (5) | 0.01757 (14) | |
S5 | 1.33093 (7) | 0.83799 (7) | 0.45365 (5) | 0.01808 (14) | |
S6 | 0.36083 (7) | 0.36325 (7) | 0.09138 (5) | 0.01564 (14) | |
S7 | 0.23644 (6) | 0.45438 (6) | 0.30383 (5) | 0.01306 (13) | |
S8 | 0.02887 (7) | 0.19494 (7) | −0.00892 (5) | 0.01986 (15) | |
S9 | −0.08678 (7) | 0.28016 (7) | 0.19093 (5) | 0.02042 (15) | |
S10 | −0.30664 (8) | 0.07809 (8) | 0.00505 (6) | 0.0291 (2) | |
N1 | 0.4151 (2) | 0.2758 (2) | 0.3029 (2) | 0.0150 (4) | |
H1 | 0.424 (4) | 0.298 (4) | 0.365 (3) | 0.050* | |
N2 | 0.5539 (2) | 0.7410 (2) | 0.2777 (2) | 0.0152 (4) | |
H2 | 0.489 (4) | 0.737 (4) | 0.324 (3) | 0.050* | |
C1 | 0.8838 (3) | 0.6555 (3) | 0.2962 (2) | 0.0138 (5) | |
C2 | 0.8498 (3) | 0.6543 (3) | 0.4032 (2) | 0.0149 (5) | |
C3 | 1.1456 (3) | 0.7627 (3) | 0.4116 (2) | 0.0149 (5) | |
C4 | 0.1651 (3) | 0.3081 (3) | 0.0972 (2) | 0.0165 (5) | |
C5 | 0.1105 (3) | 0.3478 (3) | 0.1900 (2) | 0.0164 (5) | |
C6 | −0.1313 (3) | 0.1788 (3) | 0.0592 (2) | 0.0204 (5) | |
C7 | 0.5408 (3) | 0.2327 (3) | 0.2667 (2) | 0.0210 (5) | |
H7A | 0.6369 | 0.3230 | 0.2747 | 0.032* | |
H7B | 0.5183 | 0.1882 | 0.1889 | 0.032* | |
H7C | 0.5500 | 0.1585 | 0.3126 | 0.032* | |
C8 | 0.2700 (3) | 0.1360 (3) | 0.2898 (2) | 0.0213 (6) | |
H8A | 0.1859 | 0.1623 | 0.3132 | 0.032* | |
H8B | 0.2804 | 0.0623 | 0.3355 | 0.032* | |
H8C | 0.2488 | 0.0920 | 0.2119 | 0.032* | |
C9 | 0.6915 (3) | 0.8832 (3) | 0.3116 (2) | 0.0233 (6) | |
H9A | 0.7377 | 0.8766 | 0.3830 | 0.035* | |
H9B | 0.6619 | 0.9694 | 0.3187 | 0.035* | |
H9C | 0.7653 | 0.8971 | 0.2555 | 0.035* | |
C10 | 0.4849 (3) | 0.7528 (3) | 0.1689 (2) | 0.0212 (6) | |
H10A | 0.3941 | 0.6597 | 0.1458 | 0.032* | |
H10B | 0.5593 | 0.7670 | 0.1133 | 0.032* | |
H10C | 0.4559 | 0.8394 | 0.1764 | 0.032* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
B1 | 0.0100 (13) | 0.0162 (13) | 0.0115 (12) | 0.0060 (11) | 0.0002 (10) | −0.0012 (10) |
B2 | 0.0072 (12) | 0.0154 (13) | 0.0118 (12) | 0.0044 (10) | −0.0003 (9) | −0.0014 (10) |
S1 | 0.0079 (3) | 0.0201 (3) | 0.0105 (3) | 0.0046 (2) | −0.0005 (2) | −0.0006 (2) |
S2 | 0.0071 (3) | 0.0236 (3) | 0.0105 (3) | 0.0025 (2) | −0.0003 (2) | −0.0002 (2) |
S3 | 0.0075 (3) | 0.0195 (3) | 0.0140 (3) | 0.0034 (2) | 0.0003 (2) | 0.0001 (2) |
S4 | 0.0085 (3) | 0.0257 (3) | 0.0136 (3) | 0.0026 (2) | −0.0015 (2) | −0.0007 (2) |
S5 | 0.0076 (3) | 0.0225 (3) | 0.0198 (3) | 0.0035 (2) | −0.0026 (2) | −0.0048 (2) |
S6 | 0.0100 (3) | 0.0228 (3) | 0.0114 (3) | 0.0047 (2) | −0.0007 (2) | −0.0017 (2) |
S7 | 0.0073 (3) | 0.0167 (3) | 0.0132 (3) | 0.0038 (2) | −0.0008 (2) | −0.0022 (2) |
S8 | 0.0144 (3) | 0.0234 (3) | 0.0149 (3) | 0.0015 (3) | −0.0026 (2) | −0.0016 (2) |
S9 | 0.0096 (3) | 0.0263 (3) | 0.0211 (3) | 0.0040 (3) | −0.0014 (2) | −0.0017 (3) |
S10 | 0.0135 (3) | 0.0354 (4) | 0.0258 (4) | −0.0017 (3) | −0.0055 (3) | −0.0011 (3) |
N1 | 0.0126 (10) | 0.0155 (10) | 0.0150 (10) | 0.0044 (8) | 0.0001 (8) | −0.0009 (8) |
N2 | 0.0112 (10) | 0.0161 (10) | 0.0169 (10) | 0.0044 (8) | 0.0030 (8) | −0.0003 (8) |
C1 | 0.0082 (11) | 0.0158 (11) | 0.0159 (11) | 0.0039 (9) | −0.0017 (9) | −0.0006 (9) |
C2 | 0.0086 (11) | 0.0182 (12) | 0.0155 (12) | 0.0036 (9) | −0.0016 (9) | −0.0010 (10) |
C3 | 0.0102 (12) | 0.0153 (11) | 0.0174 (12) | 0.0040 (9) | −0.0012 (9) | −0.0011 (9) |
C4 | 0.0118 (12) | 0.0186 (12) | 0.0154 (12) | 0.0027 (10) | −0.0026 (9) | 0.0003 (10) |
C5 | 0.0093 (12) | 0.0182 (12) | 0.0193 (12) | 0.0039 (10) | −0.0026 (9) | 0.0000 (10) |
C6 | 0.0149 (13) | 0.0205 (13) | 0.0206 (13) | 0.0017 (10) | −0.0011 (10) | 0.0033 (10) |
C7 | 0.0199 (13) | 0.0218 (13) | 0.0275 (14) | 0.0148 (11) | 0.0015 (11) | 0.0034 (11) |
C8 | 0.0176 (13) | 0.0137 (12) | 0.0283 (14) | 0.0017 (10) | 0.0008 (11) | 0.0026 (10) |
C9 | 0.0162 (13) | 0.0131 (12) | 0.036 (2) | 0.0025 (10) | 0.0000 (11) | −0.0021 (11) |
C10 | 0.0247 (14) | 0.0232 (13) | 0.0198 (13) | 0.0129 (11) | 0.0035 (11) | 0.0070 (11) |
Geometric parameters (Å, º) top
B1—N2 | 1.628 (3) | S5—S5iv | 3.5518 (14) |
B1—B2 | 1.746 (4) | S5—S5iv | 3.5518 (14) |
B1—S1 | 1.938 (3) | S6—C4 | 1.739 (2) |
B1—S2 | 1.954 (3) | S6—S1i | 3.6257 (11) |
B2—N1 | 1.632 (3) | S6—S6i | 3.8768 (15) |
B2—S7 | 1.933 (3) | S7—C5 | 1.749 (2) |
B2—S6 | 1.935 (3) | S7—S4ii | 3.4373 (11) |
S1—C1 | 1.749 (2) | S8—C6 | 1.729 (3) |
S1—S8i | 3.4095 (11) | S8—C4 | 1.745 (2) |
S1—S6i | 3.6257 (11) | S8—S1i | 3.4095 (11) |
S2—C2 | 1.744 (2) | S8—S3i | 3.6067 (11) |
S2—S2ii | 3.4165 (14) | S9—C5 | 1.739 (2) |
S2—S7ii | 3.4383 (11) | S9—C6 | 1.741 (3) |
S3—C3 | 1.728 (2) | S10—C6 | 1.645 (2) |
S3—C1 | 1.737 (2) | S10—S10v | 3.393 (2) |
S3—S7iii | 3.5305 (10) | N1—C7 | 1.489 (3) |
S4—C3 | 1.720 (2) | N1—C8 | 1.497 (3) |
S4—C2 | 1.746 (2) | N2—C9 | 1.489 (3) |
S4—S7ii | 3.4373 (11) | N2—C10 | 1.494 (3) |
S4—S9ii | 3.7871 (12) | C1—C2 | 1.354 (3) |
S4—S6ii | 6.091 (2) | C4—C5 | 1.347 (3) |
S5—C3 | 1.668 (2) | | |
| | | |
N2—B1—B2 | 113.5 (2) | C4—S6—S1i | 80.54 (8) |
N2—B1—S1 | 107.4 (2) | B2—S6—S1i | 155.55 (8) |
B2—B1—S1 | 113.1 (2) | C4—S6—S6i | 129.84 (9) |
N2—B1—S2 | 106.84 (15) | B2—S6—S6i | 114.69 (8) |
B2—B1—S2 | 110.2 (2) | S1i—S6—S6i | 55.43 (2) |
S1—B1—S2 | 105.29 (13) | C5—S7—B2 | 94.74 (11) |
N1—B2—B1 | 112.3 (2) | C5—S7—S4ii | 94.69 (9) |
N1—B2—S7 | 107.2 (2) | B2—S7—S4ii | 129.99 (8) |
B1—B2—S7 | 110.7 (2) | C6—S8—C4 | 97.48 (12) |
N1—B2—S6 | 107.35 (15) | C6—S8—S1i | 140.34 (9) |
B1—B2—S6 | 113.4 (2) | C4—S8—S1i | 87.24 (8) |
S7—B2—S6 | 105.57 (12) | C6—S8—S3i | 100.01 (9) |
C1—S1—B1 | 95.48 (11) | C4—S8—S3i | 131.16 (9) |
C1—S1—S8i | 92.71 (8) | S1i—S8—S3i | 51.76 (2) |
B1—S1—S8i | 141.84 (8) | C5—S9—C6 | 97.19 (12) |
C1—S1—S6i | 144.30 (8) | C6—S10—S10v | 156.98 (10) |
B1—S1—S6i | 110.12 (8) | C7—N1—C8 | 108.3 (2) |
S8i—S1—S6i | 51.83 (2) | C7—N1—B2 | 114.1 (2) |
C2—S2—B1 | 95.99 (11) | C8—N1—B2 | 116.2 (2) |
C2—S2—S2ii | 158.25 (9) | C9—N2—C10 | 108.8 (2) |
B1—S2—S2ii | 103.42 (8) | C9—N2—B1 | 115.8 (2) |
C2—S2—S7ii | 89.44 (8) | C10—N2—B1 | 114.1 (2) |
B1—S2—S7ii | 171.47 (8) | C2—C1—S3 | 116.1 (2) |
S2ii—S2—S7ii | 70.20 (3) | C2—C1—S1 | 120.6 (2) |
C3—S3—C1 | 97.13 (11) | S3—C1—S1 | 123.28 (14) |
C3—S3—S7iii | 77.32 (8) | C1—C2—S2 | 119.1 (2) |
C1—S3—S7iii | 113.85 (8) | C1—C2—S4 | 116.1 (2) |
C3—S4—C2 | 97.00 (11) | S2—C2—S4 | 124.76 (14) |
C3—S4—S7ii | 161.74 (9) | S5—C3—S4 | 122.63 (14) |
C2—S4—S7ii | 89.44 (8) | S5—C3—S3 | 123.72 (14) |
C3—S4—S9ii | 122.45 (8) | S4—C3—S3 | 113.65 (13) |
C2—S4—S9ii | 139.36 (8) | C5—C4—S6 | 119.7 (2) |
S7ii—S4—S9ii | 50.03 (2) | C5—C4—S8 | 116.0 (2) |
C3—S4—S6ii | 165.99 (8) | S6—C4—S8 | 124.29 (14) |
C2—S4—S6ii | 96.97 (8) | C4—C5—S9 | 116.6 (2) |
S7ii—S4—S6ii | 19.683 (13) | C4—C5—S7 | 119.9 (2) |
S9ii—S4—S6ii | 44.09 (2) | S9—C5—S7 | 123.44 (14) |
C3—S5—S5iv | 149.56 (9) | S10—C6—S8 | 123.42 (15) |
C3—S5—S5iv | 149.56 (9) | S10—C6—S9 | 123.8 (2) |
S5iv—S5—S5iv | 0.00 (4) | S8—C6—S9 | 112.74 (14) |
C4—S6—B2 | 95.13 (11) | | |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) −x+3, −y+2, −z+1; (v) −x−1, −y, −z. |
(V) 1,2-bis(dimethylamino)-1,1:2,2-bis(dimethylenedithioxy)diborane(4)
dichloromethane solvate
top
Crystal data top
C8H22B2N2S4·0.33CH2Cl2 | Dx = 1.351 Mg m−3 |
Mr = 324.53 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 273 reflections |
a = 29.629 (3) Å | θ = 5–50° |
c = 9.438 (2) Å | µ = 0.69 mm−1 |
V = 7175.6 (17) Å3 | T = 173 K |
Z = 18 | Needle, colourless |
F(000) = 3006 | 0.4 × 0.1 × 0.1 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 2888 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.038 |
Graphite monochromator | θmax = 27.5°, θmin = 1.4° |
Detector resolution: 60 pixels mm-1 | h = −34→38 |
ω rotation with narrow frame scans | k = −38→35 |
15138 measured reflections | l = −12→11 |
3658 independent 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.30 | w = 1/[σ2(Fo2) + (0.044P)2 + 20.867P] where P = [max(Fo2,0) + 2Fc2]/3 |
3658 reflections | (Δ/σ)max = 0.001 |
157 parameters | Δρmax = 1.27 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
Crystal data top
C8H22B2N2S4·0.33CH2Cl2 | Z = 18 |
Mr = 324.53 | Mo Kα radiation |
Trigonal, R3 | µ = 0.69 mm−1 |
a = 29.629 (3) Å | T = 173 K |
c = 9.438 (2) Å | 0.4 × 0.1 × 0.1 mm |
V = 7175.6 (17) Å3 | |
Data collection top
Siemens SMART CCD area detector diffractometer | 2888 reflections with I > 2σ(I) |
15138 measured reflections | Rint = 0.038 |
3658 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.30 | Δρmax = 1.27 e Å−3 |
3658 reflections | Δρmin = −0.66 e Å−3 |
157 parameters | |
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 on F2 for ALL reflections except for 0 with very negative
F2 or flagged by the user for potential systematic errors. Weighted
R-factors wR and all goodnesses of fit S are based on
F2, conventional R-factors R are based on F,
with F set to zero for negative F2. The observed criterion of
F2 > σ(F2) is used only for calculating R factor obs
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 | Occ. (<1) |
B1 | 0.20685 (12) | −0.02069 (12) | 0.4514 (3) | 0.0192 (6) | |
B2 | 0.20020 (12) | −0.01816 (12) | 0.2670 (3) | 0.0197 (6) | |
S1 | 0.27421 (3) | −0.01263 (3) | 0.49095 (8) | 0.02416 (18) | |
S2 | 0.15851 (3) | −0.08274 (3) | 0.55607 (8) | 0.02427 (18) | |
S3 | 0.13218 (3) | −0.03911 (3) | 0.19478 (8) | 0.02757 (19) | |
S4 | 0.24342 (3) | 0.05338 (3) | 0.20414 (8) | 0.0285 (2) | |
N1 | 0.20302 (10) | 0.02798 (9) | 0.5250 (3) | 0.0228 (5) | |
H1C | 0.2234 | 0.0571 | 0.4694 | 0.027* | |
N2 | 0.22223 (9) | −0.05292 (9) | 0.1847 (3) | 0.0231 (5) | |
H2C | 0.2566 | −0.0395 | 0.2138 | 0.028* | |
C1 | 0.25751 (13) | −0.04940 (13) | 0.6567 (4) | 0.0321 (7) | |
H1A | 0.2842 | −0.0592 | 0.6792 | 0.039* | |
H1B | 0.2566 | −0.0277 | 0.7351 | 0.039* | |
C2 | 0.20473 (13) | −0.09792 (12) | 0.6409 (4) | 0.0331 (7) | |
H2A | 0.1914 | −0.1133 | 0.7354 | 0.040* | |
H2B | 0.2082 | −0.1239 | 0.5832 | 0.040* | |
C3 | 0.15038 (16) | 0.01010 (15) | 0.0581 (4) | 0.0438 (9) | |
H3A | 0.1621 | −0.0004 | −0.0277 | 0.053* | |
H3B | 0.1199 | 0.0136 | 0.0323 | 0.053* | |
C4 | 0.19386 (17) | 0.06166 (15) | 0.1125 (4) | 0.0481 (10) | |
H4A | 0.1793 | 0.0771 | 0.1782 | 0.058* | |
H4B | 0.2100 | 0.0859 | 0.0320 | 0.058* | |
C5 | 0.19398 (13) | −0.10876 (12) | 0.2266 (4) | 0.0321 (7) | |
H5A | 0.1928 | −0.1114 | 0.3302 | 0.048* | |
H5B | 0.2121 | −0.1261 | 0.1882 | 0.048* | |
H5C | 0.1584 | −0.1256 | 0.1891 | 0.048* | |
C6 | 0.22322 (13) | −0.05051 (14) | 0.0267 (3) | 0.0314 (7) | |
H6A | 0.2416 | −0.0140 | −0.0038 | 0.047* | |
H6B | 0.1874 | −0.0678 | −0.0095 | 0.047* | |
H6C | 0.2413 | −0.0682 | −0.0103 | 0.047* | |
C7 | 0.22376 (14) | 0.04256 (13) | 0.6722 (3) | 0.0316 (7) | |
H7A | 0.2589 | 0.0473 | 0.6764 | 0.047* | |
H7B | 0.2009 | 0.0148 | 0.7378 | 0.047* | |
H7C | 0.2251 | 0.0751 | 0.6990 | 0.047* | |
C8 | 0.14942 (13) | 0.02106 (14) | 0.5234 (4) | 0.0334 (7) | |
H8A | 0.1348 | 0.0114 | 0.4277 | 0.050* | |
H8B | 0.1512 | 0.0538 | 0.5513 | 0.050* | |
H8C | 0.1271 | −0.0066 | 0.5900 | 0.050* | |
C9 | 0.0424 | 0.0509 | 0.7322 | 0.062 (4)* | 0.156 (8) |
Cl1 | 0 | 0 | 0.6474 | 1.00 (2)* | 0.47 (2) |
Cl2 | 0 | 0 | 0.8258 | 1.00 (2)* | 0.47 (2) |
C9' | 0.0525 | 0.0085 | 0.7668 | 0.084 (3)* | 0.178 (8) |
Cl1' | 0 | 0 | 0.6474 | 1.00 (2)* | 0.53 (2) |
Cl2' | 0 | 0 | 0.8258 | 1.00 (2)* | 0.53 (2) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
B1 | 0.0201 (15) | 0.0169 (14) | 0.0193 (16) | 0.0082 (12) | 0.0014 (12) | −0.0010 (12) |
B2 | 0.0198 (15) | 0.0185 (15) | 0.0180 (15) | 0.0075 (13) | 0.0019 (12) | 0.0002 (12) |
S1 | 0.0210 (4) | 0.0267 (4) | 0.0232 (4) | 0.0107 (3) | −0.0012 (3) | −0.0022 (3) |
S2 | 0.0235 (4) | 0.0199 (4) | 0.0245 (4) | 0.0071 (3) | 0.0022 (3) | 0.0041 (3) |
S3 | 0.0242 (4) | 0.0343 (4) | 0.0231 (4) | 0.0138 (3) | −0.0018 (3) | −0.0003 (3) |
S4 | 0.0329 (4) | 0.0209 (4) | 0.0253 (4) | 0.0087 (3) | 0.0069 (3) | 0.0042 (3) |
N1 | 0.0280 (13) | 0.0200 (12) | 0.0204 (12) | 0.0119 (10) | 0.0023 (10) | −0.0004 (9) |
N2 | 0.0222 (12) | 0.0234 (12) | 0.0215 (13) | 0.0097 (10) | −0.0002 (10) | −0.0044 (10) |
C1 | 0.0337 (17) | 0.0316 (17) | 0.0312 (17) | 0.0164 (15) | −0.0077 (14) | 0.0021 (13) |
C2 | 0.0389 (19) | 0.0261 (16) | 0.0312 (18) | 0.0140 (14) | −0.0083 (14) | 0.0051 (13) |
C3 | 0.050 (2) | 0.054 (2) | 0.0322 (19) | 0.030 (2) | −0.0050 (16) | 0.0078 (17) |
C4 | 0.064 (3) | 0.039 (2) | 0.042 (2) | 0.027 (2) | −0.0070 (19) | 0.0127 (17) |
C5 | 0.0394 (18) | 0.0240 (16) | 0.0321 (18) | 0.0153 (14) | 0.0035 (14) | −0.0046 (13) |
C6 | 0.0328 (17) | 0.0415 (19) | 0.0184 (15) | 0.0175 (15) | 0.0017 (13) | −0.0070 (13) |
C7 | 0.0436 (19) | 0.0300 (17) | 0.0209 (16) | 0.0182 (15) | −0.0023 (14) | −0.0076 (13) |
C8 | 0.0340 (18) | 0.0354 (18) | 0.0366 (19) | 0.0218 (15) | 0.0004 (14) | −0.0059 (14) |
Geometric parameters (Å, º) top
B1—N1 | 1.655 (4) | N1—C8 | 1.496 (4) |
B1—B2 | 1.758 (5) | N2—C5 | 1.487 (4) |
B1—S1 | 1.924 (3) | N2—C6 | 1.492 (4) |
B1—S2 | 1.943 (3) | C1—C2 | 1.512 (4) |
B2—N2 | 1.662 (4) | C3—C4 | 1.513 (6) |
B2—S3 | 1.913 (3) | C9—Cl1 | 1.6120 (2) |
B2—S4 | 1.942 (3) | C9—Cl2 | 1.6548 (2) |
S1—C1 | 1.827 (3) | Cl1—C9i | 1.6120 (2) |
S2—C2 | 1.826 (3) | Cl1—C9ii | 1.6120 (2) |
S3—C3 | 1.815 (4) | Cl2—C9i | 1.6548 (2) |
S4—C4 | 1.823 (4) | Cl2—C9ii | 1.6548 (2) |
N1—C7 | 1.492 (4) | | |
| | | |
N1—B1—B2 | 108.7 (2) | C7—N1—B1 | 116.4 (2) |
N1—B1—S1 | 109.22 (19) | C8—N1—B1 | 114.0 (2) |
B2—B1—S1 | 108.56 (19) | C5—N2—C6 | 107.8 (2) |
N1—B1—S2 | 105.77 (18) | C5—N2—B2 | 112.8 (2) |
B2—B1—S2 | 119.9 (2) | C6—N2—B2 | 116.2 (2) |
S1—B1—S2 | 104.30 (15) | C2—C1—S1 | 109.0 (2) |
N2—B2—B1 | 110.4 (2) | C1—C2—S2 | 110.8 (2) |
N2—B2—S3 | 107.99 (19) | C4—C3—S3 | 109.3 (2) |
B1—B2—S3 | 117.5 (2) | C3—C4—S4 | 111.2 (3) |
N2—B2—S4 | 106.54 (18) | Cl1—C9—Cl2 | 62.012 (12) |
B1—B2—S4 | 108.80 (19) | C9—Cl1—C9i | 97.487 (8) |
S3—B2—S4 | 104.97 (16) | C9—Cl1—C9ii | 97.487 (7) |
C1—S1—B1 | 97.89 (14) | C9i—Cl1—C9ii | 97.489 (7) |
C2—S2—B1 | 99.62 (14) | C9—Cl2—C9i | 94.185 (9) |
C3—S3—B2 | 98.67 (16) | C9—Cl2—C9ii | 94.185 (8) |
C4—S4—B2 | 98.96 (16) | C9i—Cl2—C9ii | 94.188 (8) |
C7—N1—C8 | 107.7 (2) | | |
Symmetry codes: (i) −x+y, −x, z; (ii) −y, x−y, z. |
Experimental details
| (I) | (IV) | (V) |
Crystal data |
Chemical formula | C8H4B2S6 | C10H14B2N2S10 | C8H22B2N2S4·0.33CH2Cl2 |
Mr | 314.10 | 504.45 | 324.53 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 | Trigonal, R3 |
Temperature (K) | 173 | 123 | 173 |
a, b, c (Å) | 13.549 (2), 7.525 (2), 5.891 (4) | 9.578 (2), 9.686 (2), 12.172 (3) | 29.629 (3), 29.629 (3), 9.438 (2) |
α, β, γ (°) | 90, 90.04 (3), 90 | 95.56 (2), 91.99 (2), 113.349 (12) | 90, 90, 120 |
V (Å3) | 600.6 (4) | 1028.5 (4) | 7175.6 (17) |
Z | 2 | 2 | 18 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.10 | 1.07 | 0.69 |
Crystal size (mm) | 0.55 × 0.40 × 0.01 | 0.5 × 0.1 × 0.1 | 0.4 × 0.1 × 0.1 |
|
Data collection |
Diffractometer | Siemens SMART CCD area detector diffractometer | Siemens SMART CCD area detector diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | SADABS (Sheldrick, 1996) | SADABS (Sheldrick, 1996) | – |
Tmin, Tmax | 0.37, 0.88 | 0.70, 0.92 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3856, 1383, 1150 | 10786, 4654, 3579 | 15138, 3658, 2888 |
Rint | 0.047 | 0.028 | 0.038 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.135, 0.98 | 0.031, 0.072, 0.97 | 0.046, 0.129, 1.30 |
No. of reflections | 1382 | 4654 | 3658 |
No. of parameters | 74 | 224 | 157 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
| Calculated w = 1/[σ2(Fo2) + (0.0882P)2] where P = [max(Fo2,0) + 2Fc2]/3 | Calculated w = 1/[σ2(Fo2) + (0.0385P)2] where P = [max(Fo2,0) + 2Fc2]/3 | w = 1/[σ2(Fo2) + (0.044P)2 + 20.867P] where P = [max(Fo2,0) + 2Fc2]/3 |
Δρmax, Δρmin (e Å−3) | 1.12, −0.71 | 0.41, −0.41 | 1.27, −0.66 |
Selected geometric parameters (Å, º) for (I) topB1—B1i | 1.672 (12) | S2—C1 | 1.753 (6) |
B1—S1 | 1.800 (6) | S3—C4 | 1.717 (6) |
B1—S2 | 1.807 (6) | S3—C3 | 1.722 (6) |
| | | |
B1i—B1—S1 | 122.9 (5) | C4—C1—C2 | 113.8 (5) |
B1i—B1—S2 | 123.0 (5) | C4—C1—S2 | 129.0 (4) |
S1—B1—S2 | 114.1 (3) | C2—C1—S2 | 117.2 (4) |
C2—S1—B1 | 95.9 (3) | C3—C2—C1 | 112.5 (5) |
B1—S1—S1ii | 63.6 (2) | C3—C2—S1 | 130.3 (4) |
C1—S2—B1 | 95.6 (3) | C1—C2—S1 | 117.1 (4) |
C4—S3—C3 | 93.4 (3) | C2—C3—S3 | 110.5 (4) |
C4—S3—S3iii | 153.7 (2) | C1—C4—S3 | 109.7 (4) |
C3—S3—S3iii | 103.9 (2) | | |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z. |
Selected geometric parameters (Å, º) for (IV) topB1—N2 | 1.628 (3) | S4—C3 | 1.720 (2) |
B1—B2 | 1.746 (4) | S4—C2 | 1.746 (2) |
B1—S1 | 1.938 (3) | S5—C3 | 1.668 (2) |
B1—S2 | 1.954 (3) | S6—C4 | 1.739 (2) |
B2—N1 | 1.632 (3) | S7—C5 | 1.749 (2) |
B2—S7 | 1.933 (3) | S8—C6 | 1.729 (3) |
B2—S6 | 1.935 (3) | S8—C4 | 1.745 (2) |
S1—C1 | 1.749 (2) | S9—C5 | 1.739 (2) |
S2—C2 | 1.744 (2) | S9—C6 | 1.741 (3) |
S3—C3 | 1.728 (2) | S10—C6 | 1.645 (2) |
S3—C1 | 1.737 (2) | | |
| | | |
N2—B1—B2 | 113.5 (2) | N1—B2—S6 | 107.35 (15) |
N2—B1—S1 | 107.4 (2) | B1—B2—S6 | 113.4 (2) |
B2—B1—S1 | 113.1 (2) | S7—B2—S6 | 105.57 (12) |
N2—B1—S2 | 106.84 (15) | C7—N1—C8 | 108.3 (2) |
B2—B1—S2 | 110.2 (2) | C7—N1—B2 | 114.1 (2) |
S1—B1—S2 | 105.29 (13) | C8—N1—B2 | 116.2 (2) |
N1—B2—B1 | 112.3 (2) | C9—N2—C10 | 108.8 (2) |
N1—B2—S7 | 107.2 (2) | C9—N2—B1 | 115.8 (2) |
B1—B2—S7 | 110.7 (2) | C10—N2—B1 | 114.1 (2) |
Selected geometric parameters (Å, º) for (V) topB1—N1 | 1.655 (4) | S1—C1 | 1.827 (3) |
B1—B2 | 1.758 (5) | S2—C2 | 1.826 (3) |
B1—S1 | 1.924 (3) | S3—C3 | 1.815 (4) |
B1—S2 | 1.943 (3) | S4—C4 | 1.823 (4) |
B2—N2 | 1.662 (4) | C1—C2 | 1.512 (4) |
B2—S3 | 1.913 (3) | C3—C4 | 1.513 (6) |
B2—S4 | 1.942 (3) | | |
| | | |
N1—B1—B2 | 108.7 (2) | N2—B2—S4 | 106.54 (18) |
N1—B1—S1 | 109.22 (19) | B1—B2—S4 | 108.80 (19) |
B2—B1—S1 | 108.56 (19) | S3—B2—S4 | 104.97 (16) |
N1—B1—S2 | 105.77 (18) | C7—N1—C8 | 107.7 (2) |
B2—B1—S2 | 119.9 (2) | C7—N1—B1 | 116.4 (2) |
S1—B1—S2 | 104.30 (15) | C8—N1—B1 | 114.0 (2) |
N2—B2—B1 | 110.4 (2) | C5—N2—C6 | 107.8 (2) |
N2—B2—S3 | 107.99 (19) | C5—N2—B2 | 112.8 (2) |
B1—B2—S3 | 117.5 (2) | C6—N2—B2 | 116.2 (2) |
The number of diborane(4) compounds containing the B2E4 (E = O or S) central core that have been structurally characterized continues to grow (Clegg et al., 1998), especially for E = O, largely as a result of interest in these compounds as reagents in metal catalysed diboration reactions (Marder & Norman, 1998). Here, we report some novel sulfur-containing diborane(4) compounds, 2,2'-bi(1,3,5,2-trithiaborapentalene), (I), 2,2'-bis(dimethylamino)-2,2'-bi(1,3,4,6,2-tetrathiaborapentalene-S-thione), (IV) and 1,2-bis(dimethylamino)-1,1:2,2-bis(dimethylenedithioxy)diborane(4) dichloromethane solvate, (V). \scheme
Molecules of (I) (Fig. 1) lie at an inversion centre and have approximate D2 h symmetry. The B—B bond length in (I) is 1.672 (12) Å, cf. 1.675 (5) Å in B2(1,2-S2C6H4)2, (II) and 1.680 (4) Å in B2(1,2-S2-4-MeC6H3)2 (III) (Clegg et al., 1998). Molecules of (II) and (III), like (I), are planar in the solid state, presumably to allow closer packing. The two independent B—S bonds in (I) are 1.800 (6) and 1.807 (6) Å, cf. 1.788 (2) and 1.796 (2) Å in (II), and 1.790 (2) and 1.788 (2) Å in (III). Angles around the boron centre range from 114.1 (3)–123.0 (5)°, as expected for an sp2 hybridized boron centre, with the smaller angle caused by the chelating ring.
Compounds (IV) (Fig. 2) and (V) (Fig. 3) are Lewis base adducts of diborane(4) compounds, in which the amines bind to the Lewis acidic boron centres. The amines are arranged in an anti conformation relative to the B—B bond [N1—B2—B1—N2 = -155.69 (18) and 161.91 (17)° for (IV) and (V), respectively]. The molecules are staggered, rather than eclipsed, about the B—B bond [S2—B1—B2—S6 = -157.83 (12), S1—B1—B2—S6 = -40.3 (2), S2—B1—B2—S7 = 83.79 (18) and S1—B1—B2—S7 = -158.66 (13)° in (IV), and S3—B2—B1—S1 = 167.64 (12), S3—B2—B1—S2 = 48.1 (2), S4—B2—B1—S1 = -73.49 (17) and S4—B2—B1—S2 = 166.93 (13)° in (V)]. A number of similar adducts of diborane(4) compounds have been structurally characterized (Clegg et al., 1997). The B—B lengths in (IV) and (V) are 1.746 (4) and 1.758 (5) Å, respectively, markedly longer than in the Bsp2—Bsp2 cases highlighted above and consistent with a change in hybridization and a higher coordination number at the boron. The B—B bond lengths in [B2(1,2-S2C6H4)2(4-pic)2] (4-pic = 4-picoline) and [B2(1,2-S2C6H4)2(PMe2Ph)2] are 1.715 (1) and 1.750 (4) Å, whilst in the mono-adducts [B2(1,2-S2C6H4)2(4-pic)] and [B2(1,2-S2C6H4)2(PEt3)] the B—B bond lengths are 1.701 (7) and 1.707 (3) Å, respectively (Clegg et al., 1997?), intermediate between Bsp2—Bsp2 and Bsp3—Bsp3 bonds. Interestingly, molecules of (VI) (C2(S3C3H2)2; Rovira et al., 1994?) and (VII) (please define) lie over an inversion centre and a C2 axis respectively; whilst similar symmetries are possible for (IV) and (V), neither exhibit exact symmetry in the solid state.
Angles around the B atoms [105.29 (13)–113.5 (2)° in (IV) and 104.30 (15)–119.9 (2)° in (V)] are consistent with tetrahedral geometry. The B—S bonds in (IV) [1.933 (3)–1.954 (3) Å] and (V) [1.913 (3)–1.943 (3) Å] are longer by ca 0.1 Å than those in (I)-(III), for similar reasons as referred to above, together with the fact that any B—S π-bonding present in (II) is likely to be reduced in (IV) and (V). The BS2C2 rings in (IV) display an envelope conformation, with B1 and B2 lying 0.14 and 0.17 Å, respectively, out of the mean plane of their respective five-membered rings. Similar deviations are observed in (VI) and (VII). In (V), the BS2C2 rings are puckered, with the S—C—C—S torsion angles being -45.0 (3) and 44.4 (4)° for S1—C1—C2—S2 and S3—C3—C4—S4, respectively.
A packing diagram of the molecules of (I) is shown in Fig. 4. The molecules adopt a modified herring-bone packing motif where there is no ring-ring overlap between molecules in the `stacks', such that the distance between planes of molecules in the stacks is 2.44 Å. The angle between the direction of different stacks in the c direction is 51.6°. The packing in (II) differs from that of (I) in that molecules of (II) form planar sheets utilizing inter- and intrastack S···S interactions. In (I), exocyclic S···S interactions are present [S3···S3v = 3.621 (4) Å; symmetry code: (v) 1 - x, 1 - y, -z] (van der Waals radius of S = 1.8 Å), approximately parallel to the crystallographic a axis. There are also interactions between adjacent molecules in stacks [S2···S1iii = 3.618 (3) Å; symmetry code: (iii) x, y, 1 + z]. π-stacking appears to have been precluded by the formation of S···S interactions, since these interactions are formed in the direction of the S lone pairs, resulting in a herring-bone arrangement of molecules with no π interactions and short intra-stack distances. There are also possible S···S interactions between molecules in stacks in different directions [S2···S2iv = 3.799 (2) and S1···S1ii = 3.857 (2) Å; symmetry codes: (iv) x, 1/2 - y, 1/2 + z; (ii) x, 3/2 - y, 1/2 + z].
The carbon analogue of (I), C2(S3C3H2)2, (VI), has been structurally characterized (Rovira et al., 1994) in space group P21/a with molecules of (VI) also lying at inversion centres, and whilst there are no striking structural differences in the molecular structure other than those expected, the packing arrangement is slightly different. Although the classic herring-bone packing is observed, the exact arrangement of molecules is different to that of (I), due to the different S···S interactions (Fig. 5). The angle between the direction of non-parallel stacks in (VI) is 65.6° and there are no short intrastack S···S interactions (the shortest S···S contacts are 3.991 Å), but there are reasonable ring-ring interactions: the π-stacking distance is 3.62 Å. There are, however, two unique sets of S···S contacts between adjacent molecules in differently directed stacks [S2···S1i = 3.546 and S2···S1ii = 3.606 Å; symmetry codes: (i) x - 1/2, -1/2 - y, z; (ii) x - 1/2, 1/2 - y, z]. Again, there are interactions between the terminal S atoms of adjacent molecules [3.531 (1) Å].
The crystal structures of (I) and (VI) demonstrate that with a minimal number of hydrogen atoms, S···S interactions efficiently mimic hydrogen bonds in playing an important role in the association of molecules.
Fig. 6 shows the packing of molecules of (IV) in the crystal structure, with the NHMe2 groups omitted. The packing of the molecules of is best described as ruffled chains propagating in the a direction [S10i···S10iii = 3.393 (2) and S5···S5ii = 3.552 (1) Å; symmetry codes: (i) 1 - x, 1 - y, -z; (ii) 3 - x, 2 - y, 1 - z; (iii) 2 + x, 1 + y, z], and interactions of S atoms in adjacent chains [S4iii···S9ii = 3.787 (1), S4iii···S7ii 3.437 (1), S2ii···S2iii = 3.417 (1), S2ii···S7iii = 3.438 (1), S3···S8i = 3.607 (1), S1···S8i = 3.410 (1), S1···S6i = 3.626 (1) and S6i···S6 = 3.877 (1) Å.] create an infinite ruffled sheet. Sheets are stacked in the b direction with one close contact [S3···S7iv 3.531 (1) Å; symmetry code: (iv) x + 1, y, z].
In addition to the S···S interactions in the crystal structures of (I?) and (IV), there are a number of S···H hydrogen bonds, though these are long and at the sum of the van der Waals radii of S and H atoms (3.0 Å). In (V), in the absence of S···S contacts, there are a number of (long) S···H hydrogen bonds. Please check ALL symmetry codes in the preceding paragraphs.