Crystal structure, synthesis and thermal properties of bis-(aceto-nitrile-κN)bis-(4-benzoyl-pyridine-κN)bis-(iso-thio-cyanato-κN)nickel(II).

In the crystal structure of the title com-pound, [Ni(NCS)2(CH3CN)2(C12H9NO)2] or Ni(NCS)2(4-benzoyl-pyridine)2(aceto-nitrile)2, the NiII ions are octa-hedrally coordinated by the N atoms of two thio-cyanate anions, two 4-benzoyl-pyridine ligands and two aceto-nitrile mol-ecules into discrete com-plexes that are located on centres of inversion. In the crystal, the discrete com-plexes are linked by centrosymmetric pairs of weak C-H⋯S hydrogen bonds into chains. Thermogravimetric measurements prove that, upon heating, the title com-plex loses the two aceto-nitrile ligands and transforms into a new crystalline modification of the chain com-pound [Ni(NCS)2(4-benzoyl-pyridine)2], which is different from that of the corresponding CoII, NiII and CdII coordination polymers reported in the literature. IR spectroscopic investigations indicate the presence of bridging thio-cyanate anions but the powder pattern cannot be indexed and, therefore, this structure is unknown. © Wellm and Näther 2019.

Chemical context

In most cases, the synthesis of new coordination com­pounds is performed in solution, which in some cases leads to inhomogenous samples or some, e.g. metastable com­pounds, formed by kinetic control which can easily be overlooked. There are, however, some alternative routes, like synthesis via mol­ecular milling, molten flux synthesis, solid-gas reactions or thermal decom­position of suitable precursor com­pounds (Braga et al., 2005 ▸, 2006 ▸; Näther et al., 2013 ▸; Zurawski et al., 2012 ▸; Höller et al., 2008 ▸; Den et al., 2019 ▸). These methods can have several advantages because, in most cases, they are irreversible, the products are obtained in qu­anti­tative yield, no solvent is needed and sometimes metastable isomeric or polymorphic modifications can be obtained. This is especially the case for thio­cyanate coordination polymers prepared by thermal decom­position of suitable precursor com­pounds that consist of com­plexes in which the anionic ligands are only terminally bonded and additionally coordinated by neutral N-donor co-ligands (Wöhlert et al., 2014 ▸; Werner et al., 2015 ▸). Upon heating, the co-ligands are stepwise removed, leading to new com­pounds in which the metal cations are linked by thio­cyanate anions into chains or layers (Neumann et al., 2019 ▸). In this context, we have reported on coordination polymers based on 4-benzoyl­pyridine. In [M(NCS)2(4-benzoyl­pyri­dine)2] (M = Co and Ni) prepared in solution, a rare cis–cis–trans coordination is observed, in which the thio­cyanate N and S atoms are each in cis positions, whereas the co-ligand is trans (Rams et al., 2017 ▸; Jochim et al., 2018 ▸). This is in contrast to all other linear chain com­pounds, in which the coordinating atoms always show an all-trans coordination. Surprisingly, this coordination is found in [Cd(NCS)2(4-benzoyl­pyridine)2] (Neumann et al., 2018 ▸). Therefore, the question arose if this form can be prepared with Ni by thermal decom­position using a suitable NiII precursor com­pound. One discrete com­plex with methanol has already been reported in the literature, but this com­pound cannot be prepared pure (Wellm & Näther, 2019a ▸). In the course of this project, we were able to prepare crystals from aceto­nitrile, which were characterized by single-crystal structure analysis, which proves that the title com­pound consists of discrete com­plexes with the com­position Ni(NCS)2(4-benzoyl­pyridine)2(aceto­nitrile)2. This com­pound can be prepared pure and is a promising precursor to prepare an NiII com­pound with bridging thio­cyanate anions (Fig. S1 in the supporting information). Measurements using differential thermoanalysis and thermogravimetry (DTA–TG) prove that on heating two mass steps are observed that are accom­panied by endothermic events in the DTA curve (Fig. 1 ▸). The experimental mass loss of 12.8% in the first step is in reasonable agreement with that calculated for the removal of two aceto­nitrile mol­ecules of 13.1%, indicating the formation of a com­pound with the desired com­position (Fig. 1 ▸). If the X-ray powder diffraction pattern of the residue formed after the first mass loss is com­pared with that calculated for [Ni(NCS)2(4-benzoyl­pyridine)2] reported in the literature, it is obvious that a crystalline phase has been formed (Fig. S1 in the supporting information). This new form is also different from [Cd(NCS)2(4-benzoyl­pyridine)2], indicating that a new isomeric or polymorphic form is obtained. The value of the CN stretching vibration of this form (2113 cm−1) is very different from that of the title com­pound (2080 cm−1) but com­parable to that observed in the known modification of [Ni(NCS)2(4-benzoyl­pyridine)2] (2121 cm−1) reported in the literature (Jochim et al., 2018 ▸), which indicates a similar thio­cyanate coordination (Figs. S2, S3 and S4 in the supporting information). However, this powder pattern cannot be indexed and thus the structure of this new form is unknown.

Figure 1

DTG, TG and DTA curve of the title com­pound with the experimental mass loss in % and the peak temperatures in °C. The calculated mass loss of two MeCN mol­ecules amounts to 13.2% and the loss of two 4-benzoyl­pyridine ligands corresponds to 58.8%.

Structural commentary

The asymmetric unit of the title com­pound consists of one NiII ion that is located on a centre of inversion, as well as one thio­cyanate anion, one 4-benzoyl­pyridine co-ligand and one aceto­nitrile ligand that occupy general positions (Fig. 2 ▸). The NiII ions are sixfold coordinated by the N atoms of two terminal thio­cyanate anions, two 4-benzoyl­pyridine and two aceto­nitrile ligands (Fig. 2 ▸). The Ni—NCS bond length to the negatively charged anionic ligands of 2.038 (3) Å is shorter than the Ni—N(pyridine) and Ni—NCMe bond lengths of 2.108 (2) and 2.108 (2) Å, respectively (Table 1 ▸). The bond angles deviate only slightly from ideal values, which shows that the octa­hedra are only slightly distorted (Table 1 ▸). This is also obvious from the octa­hedral angle variance of 0.71 and the quadratic elongation of 1.0006 calculated according to a procedure published by Robinson et al. (1971 ▸). The dihedral angle between the carbonyl plane (C13/C16/C17/O11) and that of the phenyl (C17–C22) ring is 22.2 (2)°, and that between the planes of the pyridine ring (N11/C11–15) and the carbonyl group (C13/C16/C17/O11) is 33.7 (2)°, which shows that the 4-benzoyl­pyridine ligand is not coplanar.

Figure 2

The mol­ecular structure of the title com­pound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x + 2, −y + 1, −z + 2.]

Table 1

Selected geometric parameters (Å, °)

Ni1—N1i	2.038 (3)	Ni1—N2i	2.093 (2)
Ni1—N1	2.038 (3)	Ni1—N11i	2.108 (2)
Ni1—N2	2.093 (2)	Ni1—N11	2.108 (2)
N1i—Ni1—N1	180.0	N1i—Ni1—N11	89.97 (9)
N1i—Ni1—N2	91.36 (9)	N1—Ni1—N11	90.03 (9)
N1—Ni1—N2	88.64 (9)	N2—Ni1—N11	89.69 (8)
N1i—Ni1—N2i	88.64 (9)	N2i—Ni1—N11	90.31 (8)
N1—Ni1—N2i	91.36 (9)	N11i—Ni1—N11	180.0
N2—Ni1—N2i	180.0	C1—N1—Ni1	163.8 (2)
N1i—Ni1—N11i	90.03 (9)	C15—N11—Ni1	121.05 (18)
N1—Ni1—N11i	89.97 (9)	C11—N11—Ni1	121.64 (17)
N2—Ni1—N11i	90.31 (8)	C2—N2—Ni1	171.5 (2)
N2i—Ni1—N11i	89.69 (8)

Symmetry code: (i) .

Supra­molecular features

The discrete com­plexes are arranged into columns that proceed along the crystallographic a axis (Fig. 3 ▸). Along the b axis they are linked into chains by centrosymmetric pairs of weak C—H⋯S hydrogen bonds between the aceto­nitrile H atoms and the thio­cyanate S atoms (Fig. 3 ▸ and Table 2 ▸).

Figure 3

Part of the crystal structure of the title com­pound, viewed along the crystallographic a axis, and with inter­molecular C—H⋯S hydrogen bonding shown as dashed lines.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯S1ii	0.98	2.98	3.662 (3)	127

Symmetry code: (ii) .

Database survey

There are already some com­pounds reported in the Cam­bridge Structural Database (Groom et al., 2016 ▸) that consist of transition-metal thio­cyanates and 4-benzoyl­pyridine ligands. These are Zn(NCS)2(4-benzoyl­pyridine)2 with tetra­hedrally coordinated ZnII cations (Neumann et al., 2018 ▸) and Cu(NCS)2(4-benzoyl­pyridine)2 in which the CuII cations are square-planar coordinated (Bai et al., 2011 ▸). There are also a number of discrete com­plexes with an octa­hedral metal coordination and terminal thio­cyanate anions (Drew et al., 1985 ▸; Soliman et al., 2014 ▸; Wellm & Näther, 2018 ▸, 2019a ▸,b ▸; Neumann et al., 2018 ▸; Suckert et al., 2017 ▸). Finally, there are several coordination polymers with the com­position [M(NCS)2(4-benzoyl­pyridine)2] (M = CdII, NiII and CoII), in which the cations are linked by pairs of μ-1,3-coordinating thio­cyanate anions into chains (Neumann et al., 2018 ▸; Rams et al., 2017 ▸; Jochim et al., 2018 ▸).

Synthesis and crystallization

Ba(SCN)2·3H2O and 4-benzoylpyridine were purchased from Alfa Aesar. Ni(SO4)·6H2O was purchased from Merck. All solvents and reactants were used without further purification.

Ni(NCS)2 was prepared by the reaction of equimolar amounts of Ni(SO4)·6H2O and Ba(SCN)2·3H2O in water. The resulting white precipitate of BaSO4 was filtered off, and the solvent was evaporated from the filtrate. The green solid was dried at room temperature.

Synthesis

Crystals of the title com­pound suitable for single-crystal X-ray diffraction were obtained by the reaction of Ni(NCS)2 (26.2 mg, 0.15 mmol) with 4-benzoyl­pyridine (27.5 mg, 0.15 mmol) in aceto­nitrile (1.5 ml) for 2 d at 354 K in a closed test tube. A polycrystalline powder was obtained by stirring a solution of Ni(NCS)2 (87.4 mg, 0.5 mmol) and 4-benzoyl­pyridine (183.2 mg, 1.0 mmol) in MeCN (3 ml) for 4 d.

Experimental details

Differential thermoanalysis and thermogravimetry (DTA–TG) were performed under a dynamic nitro­gen atmosphere in Al2O3 crucibles using an STA PT1600 thermobalance from Linseis. The XRPD measurements were performed using a Stoe Transmission Powder Diffraction System (STADI P) with Cu Kα radiation that was equipped with a linear position-sensitive MYTHEN detector from Stoe & Cie. The IR data were measured using a Bruker Alpha-P ATR–IR spectrometer.

Refinement

The C—H hydrogens were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and refined with U iso(H) = 1.2U eq(C) (1.5 for methyl H atoms) using a riding model. Crystal data, data collection and structure refinement details are summarized in Table 3 ▸.

Table 3

Experimental details

Crystal data
Chemical formula	[Ni(NCS)2(C2H2N21)2(C12H9NO)2]
M r	623.38
Crystal system, space group	Triclinic, P
Temperature (K)	200
a, b, c (Å)	7.2716 (5), 10.4868 (6), 10.8677 (6)
α, β, γ (°)	65.540 (4), 88.893 (5), 88.378 (5)
V (Å3)	754.02 (8)
Z	1
Radiation type	Mo Kα
μ (mm−1)	0.82
Crystal size (mm)	0.14 × 0.05 × 0.04
Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▸)
T min, T max	0.837, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	9692, 3283, 2634
R int	0.041
(sin θ/λ)max (Å−1)	0.639
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.046, 0.100, 1.06
No. of reflections	3283
No. of parameters	188
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.28, −0.40

Computer programs: X-AREA (Stoe & Cie, 2008 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸), XP in SHELXTL (Sheldrick, 2008 ▸) and DIAMOND (Brandenburg, 1999 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019013756/lh5928sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019013756/lh5928Isup2.hkl

Additional figures. DOI: 10.1107/S2056989019013756/lh5928sup3.pdf

CCDC references: 1958279, 1958279

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ni(NCS)2(C2H2N21)2(C12H9NO)2]	Z = 1
Mr = 623.38	F(000) = 322
Triclinic, P1	Dx = 1.373 Mg m−3
a = 7.2716 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4868 (6) Å	Cell parameters from 9692 reflections
c = 10.8677 (6) Å	θ = 2.1–25.2°
α = 65.540 (4)°	µ = 0.82 mm−1
β = 88.893 (5)°	T = 200 K
γ = 88.378 (5)°	Needle, blue
V = 754.02 (8) Å3	0.14 × 0.05 × 0.04 mm

Stoe IPDS-2 diffractometer	2634 reflections with I > 2σ(I)
ω scans	Rint = 0.041
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	θmax = 27.0°, θmin = 2.1°
Tmin = 0.837, Tmax = 0.966	h = −9→9
9692 measured reflections	k = −13→13
3283 independent reflections	l = −13→13

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H-atom parameters constrained
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0383P)2 + 0.2958P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
3283 reflections	Δρmax = 0.28 e Å−3
188 parameters	Δρmin = −0.40 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
Ni1	1.0000	0.5000	1.0000	0.04329 (15)
N1	1.1925 (3)	0.6472 (3)	0.9052 (2)	0.0544 (5)
C1	1.2695 (4)	0.7524 (3)	0.8535 (3)	0.0476 (6)
S1	1.38122 (12)	0.89701 (8)	0.77890 (9)	0.0675 (2)
N11	0.8623 (3)	0.5571 (2)	0.8151 (2)	0.0470 (5)
C11	0.9542 (4)	0.5796 (3)	0.6999 (3)	0.0511 (6)
H11	1.0844	0.5686	0.7029	0.061*
C12	0.8685 (4)	0.6177 (3)	0.5778 (3)	0.0516 (6)
H12	0.9387	0.6322	0.4987	0.062*
C13	0.6780 (4)	0.6350 (3)	0.5711 (3)	0.0476 (6)
C14	0.5829 (4)	0.6119 (3)	0.6894 (3)	0.0501 (6)
H14	0.4527	0.6230	0.6889	0.060*
C15	0.6789 (3)	0.5726 (3)	0.8082 (3)	0.0476 (6)
H15	0.6116	0.5558	0.8891	0.057*
C16	0.5863 (4)	0.6676 (3)	0.4381 (3)	0.0538 (6)
C17	0.4134 (4)	0.7550 (3)	0.4013 (3)	0.0553 (7)
C18	0.3648 (4)	0.8489 (3)	0.4564 (3)	0.0615 (7)
H18	0.4388	0.8554	0.5246	0.074*
C19	0.2080 (5)	0.9336 (4)	0.4122 (4)	0.0777 (10)
H19	0.1755	0.9989	0.4492	0.093*
C20	0.0997 (5)	0.9225 (4)	0.3144 (4)	0.0886 (12)
H20	−0.0074	0.9806	0.2840	0.106*
C21	0.1459 (5)	0.8281 (4)	0.2610 (4)	0.0868 (12)
H21	0.0694	0.8199	0.1949	0.104*
C22	0.3025 (5)	0.7452 (3)	0.3024 (3)	0.0700 (8)
H22	0.3350	0.6814	0.2637	0.084*
O11	0.6554 (3)	0.6210 (2)	0.3620 (2)	0.0687 (6)
N2	0.8453 (3)	0.6523 (2)	1.0367 (2)	0.0540 (6)
C2	0.7727 (4)	0.7466 (3)	1.0432 (3)	0.0518 (6)
C3	0.6820 (5)	0.8675 (3)	1.0510 (3)	0.0715 (9)
H3A	0.7191	0.9524	0.9733	0.107*
H3B	0.7171	0.8740	1.1348	0.107*
H3C	0.5484	0.8581	1.0501	0.107*

	U11	U22	U33	U12	U13	U23
Ni1	0.0442 (3)	0.0443 (3)	0.0446 (3)	0.00743 (19)	−0.00183 (19)	−0.0221 (2)
N1	0.0536 (13)	0.0556 (13)	0.0542 (14)	0.0029 (11)	−0.0014 (11)	−0.0230 (11)
C1	0.0488 (14)	0.0509 (15)	0.0481 (15)	0.0079 (12)	−0.0038 (12)	−0.0259 (12)
S1	0.0725 (5)	0.0514 (4)	0.0826 (6)	−0.0061 (4)	0.0032 (4)	−0.0317 (4)
N11	0.0465 (11)	0.0490 (12)	0.0479 (12)	0.0070 (9)	−0.0016 (9)	−0.0230 (10)
C11	0.0458 (13)	0.0620 (16)	0.0476 (15)	0.0031 (12)	0.0021 (11)	−0.0249 (13)
C12	0.0515 (14)	0.0575 (15)	0.0472 (15)	0.0018 (12)	0.0033 (12)	−0.0233 (12)
C13	0.0523 (14)	0.0456 (13)	0.0457 (14)	0.0028 (11)	−0.0034 (11)	−0.0199 (11)
C14	0.0475 (13)	0.0547 (15)	0.0508 (15)	0.0052 (11)	−0.0033 (12)	−0.0249 (12)
C15	0.0453 (13)	0.0539 (14)	0.0457 (14)	0.0072 (11)	−0.0006 (11)	−0.0234 (12)
C16	0.0590 (16)	0.0534 (15)	0.0479 (15)	−0.0010 (12)	−0.0051 (13)	−0.0197 (12)
C17	0.0565 (15)	0.0528 (15)	0.0472 (15)	−0.0032 (12)	−0.0049 (12)	−0.0110 (12)
C18	0.0587 (17)	0.0571 (16)	0.0586 (18)	0.0031 (13)	−0.0003 (14)	−0.0141 (14)
C19	0.069 (2)	0.066 (2)	0.080 (2)	0.0120 (16)	0.0040 (18)	−0.0139 (17)
C20	0.061 (2)	0.082 (2)	0.089 (3)	0.0105 (18)	−0.0111 (19)	−0.001 (2)
C21	0.068 (2)	0.089 (3)	0.076 (2)	−0.0072 (19)	−0.0239 (19)	−0.006 (2)
C22	0.074 (2)	0.0656 (19)	0.0601 (19)	−0.0066 (16)	−0.0159 (16)	−0.0149 (15)
O11	0.0799 (14)	0.0802 (14)	0.0541 (12)	0.0092 (11)	−0.0061 (11)	−0.0363 (11)
N2	0.0574 (13)	0.0568 (13)	0.0527 (13)	0.0123 (11)	−0.0055 (11)	−0.0282 (11)
C2	0.0606 (16)	0.0522 (15)	0.0468 (15)	0.0120 (13)	−0.0042 (12)	−0.0252 (12)
C3	0.093 (2)	0.0588 (17)	0.067 (2)	0.0288 (17)	−0.0073 (17)	−0.0328 (15)

Ni1—N1i	2.038 (3)	C16—O11	1.217 (3)
Ni1—N1	2.038 (3)	C16—C17	1.494 (4)
Ni1—N2	2.093 (2)	C17—C18	1.383 (4)
Ni1—N2i	2.093 (2)	C17—C22	1.395 (4)
Ni1—N11i	2.108 (2)	C18—C19	1.390 (4)
Ni1—N11	2.108 (2)	C18—H18	0.9500
N1—C1	1.164 (3)	C19—C20	1.379 (5)
C1—S1	1.626 (3)	C19—H19	0.9500
N11—C15	1.339 (3)	C20—C21	1.371 (6)
N11—C11	1.343 (3)	C20—H20	0.9500
C11—C12	1.373 (4)	C21—C22	1.376 (5)
C11—H11	0.9500	C21—H21	0.9500
C12—C13	1.391 (4)	C22—H22	0.9500
C12—H12	0.9500	N2—C2	1.135 (3)
C13—C14	1.381 (4)	C2—C3	1.445 (4)
C13—C16	1.505 (4)	C3—H3A	0.9800
C14—C15	1.380 (4)	C3—H3B	0.9800
C14—H14	0.9500	C3—H3C	0.9800
C15—H15	0.9500
N1i—Ni1—N1	180.0	N11—C15—C14	123.2 (2)
N1i—Ni1—N2	91.36 (9)	N11—C15—H15	118.4
N1—Ni1—N2	88.64 (9)	C14—C15—H15	118.4
N1i—Ni1—N2i	88.64 (9)	O11—C16—C17	121.0 (3)
N1—Ni1—N2i	91.36 (9)	O11—C16—C13	118.7 (2)
N2—Ni1—N2i	180.0	C17—C16—C13	120.3 (2)
N1i—Ni1—N11i	90.03 (9)	C18—C17—C22	119.4 (3)
N1—Ni1—N11i	89.97 (9)	C18—C17—C16	122.7 (3)
N2—Ni1—N11i	90.31 (8)	C22—C17—C16	117.9 (3)
N2i—Ni1—N11i	89.69 (8)	C17—C18—C19	120.1 (3)
N1i—Ni1—N11	89.97 (9)	C17—C18—H18	120.0
N1—Ni1—N11	90.03 (9)	C19—C18—H18	120.0
N2—Ni1—N11	89.69 (8)	C20—C19—C18	119.8 (4)
N2i—Ni1—N11	90.31 (8)	C20—C19—H19	120.1
N11i—Ni1—N11	180.0	C18—C19—H19	120.1
C1—N1—Ni1	163.8 (2)	C21—C20—C19	120.3 (3)
N1—C1—S1	178.2 (2)	C21—C20—H20	119.9
C15—N11—C11	117.3 (2)	C19—C20—H20	119.9
C15—N11—Ni1	121.05 (18)	C20—C21—C22	120.5 (4)
C11—N11—Ni1	121.64 (17)	C20—C21—H21	119.8
N11—C11—C12	123.0 (2)	C22—C21—H21	119.8
N11—C11—H11	118.5	C21—C22—C17	120.0 (4)
C12—C11—H11	118.5	C21—C22—H22	120.0
C11—C12—C13	119.4 (3)	C17—C22—H22	120.0
C11—C12—H12	120.3	C2—N2—Ni1	171.5 (2)
C13—C12—H12	120.3	N2—C2—C3	179.4 (4)
C14—C13—C12	117.8 (2)	C2—C3—H3A	109.5
C14—C13—C16	123.6 (2)	C2—C3—H3B	109.5
C12—C13—C16	118.4 (2)	H3A—C3—H3B	109.5
C15—C14—C13	119.3 (2)	C2—C3—H3C	109.5
C15—C14—H14	120.4	H3A—C3—H3C	109.5
C13—C14—H14	120.4	H3B—C3—H3C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···S1ii	0.98	2.98	3.662 (3)	127