1,1′,1′′-{[4-(3,4-Ethyl­ene­dioxy­thio­phen-2-yl)phen­yl]methane­tri­yl}tris­(1H-pyra­zole)

Chen, X.-Y.; Yang, X.; Holliday, B.J.

doi:10.1107/S160053681104253X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3021

doi:10.1107/S160053681104253X

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1,1′,1′′-{[4-(3,4-Ethylenedioxythiophen-2-yl)phenyl]methanetriyl}tris(1H-pyrazole)

Xiao-Yan Chen,^a Xiaoping Yang ^a and Bradley J. Holliday ^a ^*

^aDepartment of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station, A5300, Austin, Texas 78712, USA
^*Correspondence e-mail: bholliday@cm.utexas.edu

(Received 8 August 2011; accepted 14 October 2011; online 22 October 2011)

In the title complex, C₂₂H₁₈N₆O₂S, two of the pyrazole rings are disordered over two sets of sites with ratios of refined occupancies of 0.58 (2):0.42 (2) and 0.517 (12):0.483 (12). The dioxane ring is in a half-chair conformation and the two –CH₂– groups of this ring are disordered over two sets of sites, the ratio of refined occupancies being 0.855 (19):0.145 (19). The essentially planar thiophene ring [largest deviation = 0.0444 (2) Å] forms a dihedral angle of 19.59 (3)° with the benzene ring.

Related literature

For the preparation and coordination chemistry of tris(pyrazolyl)borates and tris(pyrazolyl)methanes, see: Trofimenko (1999 ); Pettinari & Pettinari (2005 ); Reger et al. (2000 ). For the chemistry of tris(pyrazolyl)methane derivatives, see: Humphrey et al. (1999 ). For a general Stille coupling procedure, see: Sankaran et al. (2001 ). For similar structures, see: Liddle & Gardinier (2007 ).

Experimental

Crystal data

C₂₂H₁₈N₆O₂S
M_r = 430.48
Triclinic, $[P \overline 1]$
a = 7.2356 (14) Å
b = 8.1104 (16) Å
c = 18.626 (4) Å
α = 95.05 (3)°
β = 99.20 (2)°
γ = 112.14 (3)°
V = 986.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 153 K
0.16 × 0.15 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: gaussian (SHELXTL; Sheldrick, 2008 ) T_min = 0.969, T_max = 0.979
5461 measured reflections
3466 independent reflections
2749 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.148
S = 1.12
3466 reflections
294 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ); cell refinement: COLLECT; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ) within WinGX (Farrugia, 1999 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and POV-RAY (Persistence of Vision, 2004 ); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681104253X/lh5310sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104253X/lh5310Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681104253X/lh5310Isup3.cml

checkCIF report

Comment top

The coordination chemistry of tris(pyrazolyl)borates has been investigated for decades, with variations on the ligand having been widely studied (Trofimenko, 1999; Pettinari & Pettinari, 2005; Reger et al., 2000). However, the isoelectronic tris(pyrazolyl)methanes (Humphrey et al., 1999) have received less attention and there exists a disparity in the chemistry of certain third generation scorpionates (ligands functionalized at the back methine position). Herein, we demonstrate the preparation of a new tris-(pyrazolyl)methane derivative, 1,1',1''-((4-(3,4-(ethylenedioxy)thien-2-yl)phenyl)methanetriyl) tris(1H-pyrazole), via a Stille coupling (Sankaran et al., 2001). The molecular structure of the title compound is shown in Figure 1. The thiophene ring is essentially planar, with the largest deviation measured as 0.0444 (2) Å. The six-membered dioxane ring exists in a half-chair conformation. The dihedral angle between the benzene and thiophene rings is 19.59 (3) °. This geometry is similar to other scorpionates reported in literature (Liddle & Gardinier, 2007).

Related literature top

For the preparation and coordination chemistry of tris(pyrazolyl)borates and tris(pyrazolyl)methanes, see: Trofimenko (1999); Pettinari & Pettinari (2005); Reger et al. (2000). For the chemistry of tris(pyrazolyl)methane derivatives, see: Humphrey et al. (1999). For a general Stille coupling procedure, see: Sankaran et al. (2001). For similar structures, see: Liddle & Gardinier (2007).

Experimental top

The title compound was synthesized from the Stille coupling of 4-(tri(1H-pyrazol-1-yl)methyl)phenyl trifluoromethanesulfonate and 2-(tributylstannyl)-3,4-(ethylenedioxy)thiophene. The starting compound, 4-(tri(1Hpyrazol- 1-yl)methyl)phenol, was prepared by the condensation of 4-(trifluoromethyl)phenol and sodium pyrazol-1-ide in a yield of 58%. Treatment of 4-(tri(1H-pyrazol-1-yl)methyl)phenol with trifluoromethane sulfonic acid anhydride in pyridine at 273 K under argon resulted in 4-(tri(1H-pyrazol-1-yl)methyl)phenyl trifluoromethanesulfonate in a yield of 97%. The resulting aryl trifluoromethanesulfonate was subsequently coupled with 2-(tributylstannyl)- 3,4-(ethylenedioxy)thiophene in the presence of tetrakis(triphenylphosphine)palladium(0) in 1,4-dioxane to produce the desired compound in a yield of 54%. X-ray quality crystals were grown by slow evaporation of a methanol solution of the title compound.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT (Nonius, 1998); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999) within WinGX (Farrugia, 1999); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and POV-RAY (Persistence of Vision, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure showing 30% probability ellipsoids. Hydrogen atoms are omitted for clarity. The disorder is not shown but disordered atoms can been seen as isotropic spheres.

1-[bis(1H-imidazol-1-yl)(4-{2H,3H- thieno[3,4-b][1,4]dioxin-5-yl}phenyl)methyl]-1H-imidazole top

Crystal data top

C₂₂H₁₈N₆O₂S	Z = 2
M_r = 430.48	F(000) = 448
Triclinic, P1	D_x = 1.450 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2356 (14) Å	Cell parameters from 3640 reflections
b = 8.1104 (16) Å	θ = 2.9–30.5°
c = 18.626 (4) Å	µ = 0.20 mm⁻¹
α = 95.05 (3)°	T = 153 K
β = 99.20 (2)°	Block, colourless
γ = 112.14 (3)°	0.16 × 0.15 × 0.11 mm
V = 986.2 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	3466 independent reflections
Radiation source: fine-focus sealed tube	2749 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: gaussian (SHELXTL; Sheldrick, 2008)	h = −8→8
T_min = 0.969, T_max = 0.979	k = −8→9
5461 measured reflections	l = −22→22

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0645P)² + 1.0306P] where P = (F_o² + 2F_c²)/3
3466 reflections	(Δ/σ)_max < 0.001
294 parameters	Δρ_max = 0.43 e Å⁻³
9 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₂₂H₁₈N₆O₂S	γ = 112.14 (3)°
M_r = 430.48	V = 986.2 (3) Å³
Triclinic, P1	Z = 2
a = 7.2356 (14) Å	Mo Kα radiation
b = 8.1104 (16) Å	µ = 0.20 mm⁻¹
c = 18.626 (4) Å	T = 153 K
α = 95.05 (3)°	0.16 × 0.15 × 0.11 mm
β = 99.20 (2)°

Data collection top

Nonius KappaCCD diffractometer	3466 independent reflections
Absorption correction: gaussian (SHELXTL; Sheldrick, 2008)	2749 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.979	R_int = 0.025
5461 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	9 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.12	Δρ_max = 0.43 e Å⁻³
3466 reflections	Δρ_min = −0.46 e Å⁻³
294 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 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	U_iso*/U_eq	Occ. (<1)
S1	0.70254 (12)	0.81579 (11)	0.44453 (4)	0.0321 (2)
O1	0.5573 (3)	0.7026 (3)	0.63060 (11)	0.0330 (5)
O2	0.2139 (3)	0.6959 (3)	0.52420 (11)	0.0270 (5)
N4	−0.3420 (4)	0.5741 (3)	0.20905 (14)	0.0304 (6)
N5	−0.1013 (3)	0.9898 (3)	0.19286 (12)	0.0211 (5)
N6	−0.2521 (4)	1.0130 (4)	0.14646 (14)	0.0353 (7)
C1	0.7421 (5)	0.7770 (4)	0.53348 (17)	0.0316 (7)
H1	0.8682	0.7828	0.5604	0.038*
C2	0.5699 (5)	0.7370 (4)	0.56037 (15)	0.0243 (7)
C3	0.3742 (8)	0.7069 (13)	0.6507 (3)	0.0310 (15)	0.855 (19)
H3A	0.3921	0.8339	0.6635	0.037*	0.855 (19)
H3B	0.3511	0.6484	0.6948	0.037*	0.855 (19)
C4	0.1914 (9)	0.6121 (11)	0.5890 (3)	0.0289 (15)	0.855 (19)
H4A	0.1721	0.4846	0.5768	0.035*	0.855 (19)
H4B	0.0682	0.6137	0.6052	0.035*	0.855 (19)
C3A	0.359 (5)	0.615 (6)	0.6379 (19)	0.039 (9)	0.145 (19)
H3C	0.3554	0.6129	0.6907	0.047*	0.145 (19)
H3D	0.3040	0.4890	0.6122	0.047*	0.145 (19)
C4A	0.232 (5)	0.709 (7)	0.6058 (15)	0.032 (8)	0.145 (19)
H4C	0.2937	0.8381	0.6288	0.038*	0.145 (19)
H4D	0.0938	0.6549	0.6168	0.038*	0.145 (19)
C5	0.4023 (4)	0.7346 (3)	0.50830 (15)	0.0195 (6)
C6	0.4478 (4)	0.7732 (4)	0.44105 (15)	0.0210 (6)
C7	0.3179 (4)	0.7824 (3)	0.37400 (15)	0.0208 (6)
C8	0.3706 (5)	0.7717 (4)	0.30513 (16)	0.0265 (7)
H8A	0.4919	0.7548	0.3015	0.032*
C9	0.2494 (5)	0.7853 (4)	0.24205 (15)	0.0250 (7)
H9A	0.2896	0.7797	0.1961	0.030*
C10	0.0697 (4)	0.8068 (3)	0.24590 (15)	0.0213 (6)
C11	0.0162 (4)	0.8172 (4)	0.31440 (15)	0.0236 (6)
H11A	−0.1064	0.8321	0.3178	0.028*
C12	0.1377 (4)	0.8061 (4)	0.37725 (15)	0.0224 (6)
H12	0.0985	0.8147	0.4233	0.027*
C13	−0.0677 (4)	0.8237 (4)	0.17826 (15)	0.0234 (7)
C14	0.1425 (4)	0.9858 (4)	0.09120 (15)	0.0242 (7)
H14A	0.1559	1.1045	0.1082	0.029*
N1	0.0423 (14)	0.8309 (8)	0.1170 (4)	0.012 (3)*	0.42 (2)
N2	0.0684 (18)	0.6899 (7)	0.0800 (3)	0.018 (2)*	0.42 (2)
C15	0.180 (2)	0.7485 (7)	0.0295 (4)	0.028 (3)*	0.42 (2)
H15A	0.2229	0.6793	−0.0028	0.033*	0.42 (2)
N1A	0.0096 (11)	0.8381 (6)	0.1101 (3)	0.019 (2)*	0.58 (2)
N2A	−0.0119 (14)	0.6789 (6)	0.0712 (3)	0.0246 (17)*	0.58 (2)
C15A	0.1144 (15)	0.7421 (5)	0.0252 (3)	0.0270 (19)*	0.58 (2)
H15B	0.1313	0.6633	−0.0116	0.032*	0.58 (2)
C16	0.2206 (5)	0.9305 (4)	0.03417 (16)	0.0307 (7)
H16A	0.2915	1.0069	0.0030	0.037*
N3	−0.2502 (8)	0.6548 (7)	0.1554 (3)	0.0144 (16)*	0.483 (12)
C17	−0.3761 (10)	0.6025 (8)	0.0880 (3)	0.0231 (19)*	0.483 (12)
H17A	−0.3440	0.6460	0.0439	0.028*	0.483 (12)
C18	−0.5556 (11)	0.4771 (9)	0.0952 (4)	0.030 (2)*	0.483 (12)
H18A	−0.6694	0.4060	0.0568	0.036*	0.483 (12)
C19	−0.5387 (17)	0.4739 (15)	0.1706 (5)	0.029 (4)*	0.483 (12)
H19A	−0.6490	0.4107	0.1927	0.035*	0.483 (12)
N3A	−0.2799 (7)	0.6848 (8)	0.1619 (3)	0.0165 (16)*	0.517 (12)
C17A	−0.4363 (10)	0.6444 (9)	0.1030 (4)	0.036 (2)*	0.517 (12)
H17B	−0.4336	0.7065	0.0620	0.043*	0.517 (12)
C18A	−0.5959 (10)	0.5005 (7)	0.1130 (4)	0.0243 (17)*	0.517 (12)
H18B	−0.7279	0.4424	0.0821	0.029*	0.517 (12)
C19A	−0.5217 (15)	0.4570 (14)	0.1794 (4)	0.026 (3)*	0.517 (12)
H19B	−0.5945	0.3545	0.1999	0.032*	0.517 (12)
C20	0.0224 (4)	1.1452 (4)	0.24024 (15)	0.0228 (6)
H20A	0.1386	1.1618	0.2767	0.027*
C21	−0.2231 (6)	1.1819 (5)	0.16671 (19)	0.0413 (9)
H21A	−0.3072	1.2373	0.1445	0.050*
C22	−0.0533 (5)	1.2711 (4)	0.22500 (18)	0.0331 (8)
H22A	−0.0025	1.3930	0.2486	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0269 (4)	0.0472 (5)	0.0283 (4)	0.0194 (4)	0.0107 (3)	0.0060 (3)
O1	0.0304 (12)	0.0432 (13)	0.0218 (11)	0.0125 (10)	−0.0015 (9)	0.0090 (9)
O2	0.0222 (11)	0.0382 (12)	0.0208 (11)	0.0095 (9)	0.0063 (8)	0.0138 (9)
N4	0.0240 (14)	0.0293 (14)	0.0288 (14)	−0.0008 (11)	0.0073 (11)	0.0075 (11)
N5	0.0183 (12)	0.0281 (13)	0.0142 (12)	0.0065 (10)	0.0032 (10)	0.0032 (10)
N6	0.0291 (15)	0.0603 (19)	0.0214 (14)	0.0252 (14)	0.0003 (11)	0.0054 (13)
C1	0.0266 (17)	0.0429 (18)	0.0266 (17)	0.0178 (14)	0.0005 (13)	0.0041 (14)
C2	0.0296 (17)	0.0216 (14)	0.0192 (15)	0.0102 (12)	−0.0007 (12)	0.0010 (11)
C3	0.031 (3)	0.036 (4)	0.022 (2)	0.009 (3)	0.006 (2)	0.010 (2)
C4	0.030 (3)	0.035 (3)	0.021 (3)	0.011 (3)	0.005 (2)	0.012 (3)
C3A	0.045 (17)	0.014 (16)	0.042 (17)	−0.007 (14)	0.013 (12)	0.007 (13)
C4A	0.025 (14)	0.04 (2)	0.020 (14)	0.005 (14)	0.002 (11)	−0.004 (13)
C5	0.0222 (15)	0.0149 (13)	0.0209 (15)	0.0073 (11)	0.0035 (12)	0.0021 (11)
C6	0.0219 (15)	0.0197 (13)	0.0239 (15)	0.0102 (11)	0.0077 (12)	0.0023 (11)
C7	0.0262 (16)	0.0152 (13)	0.0196 (14)	0.0067 (12)	0.0049 (12)	0.0032 (11)
C8	0.0320 (17)	0.0284 (15)	0.0236 (15)	0.0157 (13)	0.0100 (13)	0.0026 (12)
C9	0.0371 (18)	0.0235 (15)	0.0154 (14)	0.0113 (13)	0.0106 (13)	0.0023 (11)
C10	0.0267 (16)	0.0151 (13)	0.0180 (14)	0.0033 (11)	0.0055 (12)	0.0035 (11)
C11	0.0236 (15)	0.0301 (15)	0.0195 (15)	0.0107 (12)	0.0085 (12)	0.0088 (12)
C12	0.0256 (16)	0.0262 (15)	0.0161 (14)	0.0082 (12)	0.0093 (12)	0.0073 (11)
C13	0.0281 (16)	0.0201 (14)	0.0134 (14)	0.0005 (12)	0.0032 (12)	0.0030 (11)
C14	0.0272 (16)	0.0226 (14)	0.0236 (15)	0.0090 (12)	0.0089 (12)	0.0065 (12)
C16	0.0335 (18)	0.0406 (18)	0.0229 (16)	0.0177 (15)	0.0096 (14)	0.0099 (13)
C20	0.0225 (15)	0.0240 (15)	0.0204 (14)	0.0068 (12)	0.0058 (12)	0.0045 (11)
C21	0.047 (2)	0.065 (2)	0.0311 (18)	0.0402 (19)	0.0115 (16)	0.0143 (17)
C22	0.043 (2)	0.0348 (17)	0.0298 (17)	0.0202 (15)	0.0160 (15)	0.0096 (14)

Geometric parameters (Å, º) top

S1—C1	1.713 (3)	C10—C13	1.526 (4)
S1—C6	1.732 (3)	C11—C12	1.378 (4)
O1—C2	1.371 (4)	C11—H11A	0.9500
O1—C3A	1.37 (3)	C12—H12	0.9500
O1—C3	1.445 (5)	C13—N1A	1.463 (4)
O2—C5	1.366 (3)	C13—N3	1.468 (4)
O2—C4	1.439 (4)	C13—N3A	1.485 (4)
O2—C4A	1.50 (3)	C13—N1	1.486 (5)
N4—C19A	1.283 (10)	C14—N1A	1.341 (5)
N4—N3A	1.320 (5)	C14—N1	1.366 (6)
N4—N3	1.366 (6)	C14—C16	1.396 (3)
N4—C19	1.378 (11)	C14—H14A	0.9500
N5—N6	1.362 (3)	N1—N2	1.372 (5)
N5—C20	1.367 (4)	N2—C15	1.340 (6)
N5—C13	1.466 (4)	C15—C16	1.385 (5)
N6—C21	1.316 (5)	C15—H15A	0.9500
C1—C2	1.354 (4)	N1A—N2A	1.366 (5)
C1—H1	0.9500	N2A—C15A	1.344 (6)
C2—C5	1.420 (4)	C15A—C16	1.408 (5)
C3—C4	1.501 (11)	C15A—H15B	0.9500
C3—H3A	0.9900	C16—H16A	0.9500
C3—H3B	0.9900	N3—C17	1.355 (5)
C4—H4A	0.9900	C17—C18	1.350 (7)
C4—H4B	0.9900	C17—H17A	0.9500
C3A—C4A	1.49 (7)	C18—C19	1.394 (7)
C3A—H3C	0.9900	C18—H18A	0.9500
C3A—H3D	0.9900	C19—H19A	0.9500
C4A—H4C	0.9900	N3A—C17A	1.361 (5)
C4A—H4D	0.9900	C17A—C18A	1.350 (6)
C5—C6	1.378 (4)	C17A—H17B	0.9500
C6—C7	1.463 (4)	C18A—C19A	1.396 (7)
C7—C12	1.398 (4)	C18A—H18B	0.9500
C7—C8	1.400 (4)	C19A—H19B	0.9500
C8—C9	1.388 (4)	C20—C22	1.359 (4)
C8—H8A	0.9500	C20—H20A	0.9500
C9—C10	1.387 (4)	C21—C22	1.406 (5)
C9—H9A	0.9500	C21—H21A	0.9500
C10—C11	1.396 (4)	C22—H22A	0.9500

C1—S1—C6	93.25 (15)	N1A—C13—N3	100.5 (4)
C2—O1—C3A	112.4 (13)	N5—C13—N3	116.8 (4)
C2—O1—C3	112.3 (3)	N1A—C13—N3A	108.9 (4)
C5—O2—C4	112.3 (3)	N5—C13—N3A	101.5 (4)
C5—O2—C4A	109.3 (11)	N5—C13—N1	110.7 (4)
C19A—N4—N3A	108.0 (4)	N3—C13—N1	104.0 (4)
C19A—N4—N3	109.2 (4)	N3A—C13—N1	114.7 (4)
N3A—N4—C19	98.7 (5)	N1A—C13—C10	117.0 (4)
N3—N4—C19	101.9 (4)	N5—C13—C10	109.3 (2)
N6—N5—C20	111.7 (2)	N3—C13—C10	109.2 (3)
N6—N5—C13	118.9 (2)	N3A—C13—C10	114.4 (3)
C20—N5—C13	128.3 (2)	N1—C13—C10	106.2 (5)
C21—N6—N5	104.4 (3)	N1A—C14—C16	108.1 (3)
C2—C1—S1	111.0 (2)	N1—C14—C16	104.5 (3)
C2—C1—H1	124.5	N1A—C14—H14A	123.1
S1—C1—H1	124.5	N1—C14—H14A	127.8
C1—C2—O1	123.9 (3)	C16—C14—H14A	127.8
C1—C2—C5	113.0 (3)	C14—N1—N2	109.4 (4)
O1—C2—C5	123.1 (3)	C14—N1—C13	123.8 (4)
O1—C3—C4	111.5 (6)	N2—N1—C13	126.8 (6)
O1—C3—H3A	109.3	C15—N2—N1	109.8 (5)
C4—C3—H3A	109.3	N2—C15—C16	105.8 (5)
O1—C3—H3B	109.3	N2—C15—H15A	127.1
C4—C3—H3B	109.3	C16—C15—H15A	127.1
H3A—C3—H3B	108.0	C14—N1A—N2A	114.6 (3)
O2—C4—C3	111.7 (6)	C14—N1A—C13	127.5 (4)
O2—C4—H4A	109.3	N2A—N1A—C13	115.4 (4)
C3—C4—H4A	109.3	C15A—N2A—N1A	99.8 (4)
O2—C4—H4B	109.3	N2A—C15A—C16	116.9 (5)
C3—C4—H4B	109.3	N2A—C15A—H15B	121.5
H4A—C4—H4B	108.0	C16—C15A—H15B	121.5
O1—C3A—C4A	110 (3)	C15—C16—C14	110.3 (4)
O1—C3A—H3C	109.7	C14—C16—C15A	100.5 (4)
C4A—C3A—H3C	109.7	C14—C16—H16A	124.9
O1—C3A—H3D	109.7	C15A—C16—H16A	132.0
C4A—C3A—H3D	109.7	C17—N3—N4	113.1 (4)
H3C—C3A—H3D	108.2	C17—N3—C13	125.0 (4)
C3A—C4A—O2	111 (4)	N4—N3—C13	118.0 (4)
C3A—C4A—H4C	109.4	C18—C17—N3	107.2 (5)
O2—C4A—H4C	109.4	C18—C17—H17A	126.4
C3A—C4A—H4D	109.4	N3—C17—H17A	126.4
O2—C4A—H4D	109.4	C17—C18—C19	105.6 (7)
H4C—C4A—H4D	108.0	C17—C18—H18A	127.2
O2—C5—C6	123.9 (3)	C19—C18—H18A	127.2
O2—C5—C2	122.4 (2)	N4—C19—C18	111.4 (8)
C6—C5—C2	113.7 (3)	N4—C19—H19A	124.3
C5—C6—C7	130.1 (3)	C18—C19—H19A	124.3
C5—C6—S1	109.0 (2)	N4—N3A—C17A	108.9 (4)
C7—C6—S1	120.9 (2)	N4—N3A—C13	120.0 (3)
C12—C7—C8	117.7 (3)	C17A—N3A—C13	131.1 (4)
C12—C7—C6	120.5 (2)	C18A—C17A—N3A	108.0 (5)
C8—C7—C6	121.8 (3)	C18A—C17A—H17B	126.0
C9—C8—C7	121.5 (3)	N3A—C17A—H17B	126.0
C9—C8—H8A	119.3	C17A—C18A—C19A	103.9 (6)
C7—C8—H8A	119.3	C17A—C18A—H18B	128.1
C10—C9—C8	120.2 (3)	C19A—C18A—H18B	128.1
C10—C9—H9A	119.9	N4—C19A—C18A	110.8 (7)
C8—C9—H9A	119.9	N4—C19A—H19B	124.6
C9—C10—C11	118.6 (3)	C18A—C19A—H19B	124.6
C9—C10—C13	122.2 (2)	C22—C20—N5	106.7 (3)
C11—C10—C13	119.2 (3)	C22—C20—H20A	126.7
C12—C11—C10	121.3 (3)	N5—C20—H20A	126.7
C12—C11—H11A	119.4	N6—C21—C22	112.3 (3)
C10—C11—H11A	119.4	N6—C21—H21A	123.9
C11—C12—C7	120.7 (3)	C22—C21—H21A	123.9
C11—C12—H12	119.6	C20—C22—C21	105.0 (3)
C7—C12—H12	119.6	C20—C22—H22A	127.5
N1A—C13—N5	104.1 (3)	C21—C22—H22A	127.5

C20—N5—N6—C21	−1.4 (3)	C10—C13—N1—N2	73.6 (8)
C13—N5—N6—C21	−170.4 (2)	C14—N1—N2—C15	−1.1 (10)
C6—S1—C1—C2	−1.3 (3)	C13—N1—N2—C15	−178.4 (8)
S1—C1—C2—O1	−178.9 (2)	N1—N2—C15—C16	−1.5 (10)
S1—C1—C2—C5	0.9 (3)	N1—C14—N1A—N2A	−73.0 (14)
C3A—O1—C2—C1	−162 (2)	C16—C14—N1A—N2A	0.8 (6)
C3—O1—C2—C1	166.0 (5)	N1—C14—N1A—C13	88.3 (16)
C3A—O1—C2—C5	18 (2)	C16—C14—N1A—C13	162.1 (6)
C3—O1—C2—C5	−13.8 (5)	N5—C13—N1A—C14	40.3 (8)
C2—O1—C3—C4	42.9 (8)	N3—C13—N1A—C14	161.6 (7)
C3A—O1—C3—C4	−54 (3)	N3A—C13—N1A—C14	147.9 (7)
C5—O2—C4—C3	45.3 (8)	N1—C13—N1A—C14	−88 (2)
C4A—O2—C4—C3	−45 (2)	C10—C13—N1A—C14	−80.5 (8)
O1—C3—C4—O2	−61.0 (9)	N5—C13—N1A—N2A	−158.6 (5)
C2—O1—C3A—C4A	−49 (4)	N3—C13—N1A—N2A	−37.3 (6)
C3—O1—C3A—C4A	47 (4)	N3A—C13—N1A—N2A	−50.9 (7)
O1—C3A—C4A—O2	66 (5)	N1—C13—N1A—N2A	72.8 (19)
C5—O2—C4A—C3A	−46 (4)	C10—C13—N1A—N2A	80.7 (6)
C4—O2—C4A—C3A	55 (4)	C14—N1A—N2A—C15A	−1.9 (7)
C4—O2—C5—C6	163.5 (4)	C13—N1A—N2A—C15A	−165.5 (6)
C4A—O2—C5—C6	−165 (2)	N1A—N2A—C15A—C16	2.3 (7)
C4—O2—C5—C2	−16.0 (5)	N2—C15—C16—C14	3.5 (8)
C4A—O2—C5—C2	15 (2)	N2—C15—C16—C15A	−57.3 (11)
C1—C2—C5—O2	179.5 (3)	N1A—C14—C16—C15	−15.9 (6)
O1—C2—C5—O2	−0.7 (4)	N1—C14—C16—C15	−4.1 (7)
C1—C2—C5—C6	0.0 (4)	N1A—C14—C16—C15A	0.6 (5)
O1—C2—C5—C6	179.8 (2)	N1—C14—C16—C15A	12.3 (5)
O2—C5—C6—C7	0.0 (5)	N2A—C15A—C16—C15	121.7 (15)
C2—C5—C6—C7	179.4 (3)	N2A—C15A—C16—C14	−1.9 (7)
O2—C5—C6—S1	179.5 (2)	C19A—N4—N3—C17	5.3 (8)
C2—C5—C6—S1	−1.0 (3)	N3A—N4—N3—C17	−83.7 (10)
C1—S1—C6—C5	1.3 (2)	C19—N4—N3—C17	−3.0 (8)
C1—S1—C6—C7	−179.1 (2)	C19A—N4—N3—C13	164.3 (7)
C5—C6—C7—C12	20.3 (4)	N3A—N4—N3—C13	75.3 (8)
S1—C6—C7—C12	−159.3 (2)	C19—N4—N3—C13	156.0 (7)
C5—C6—C7—C8	−161.1 (3)	N1A—C13—N3—C17	−37.6 (8)
S1—C6—C7—C8	19.4 (4)	N5—C13—N3—C17	74.2 (7)
C12—C7—C8—C9	0.4 (4)	N3A—C13—N3—C17	86.6 (13)
C6—C7—C8—C9	−178.3 (2)	N1—C13—N3—C17	−48.1 (8)
C7—C8—C9—C10	−1.1 (4)	C10—C13—N3—C17	−161.2 (6)
C8—C9—C10—C11	0.9 (4)	N1A—C13—N3—N4	166.1 (6)
C8—C9—C10—C13	179.5 (2)	N5—C13—N3—N4	−82.1 (6)
C9—C10—C11—C12	−0.1 (4)	N3A—C13—N3—N4	−69.7 (12)
C13—C10—C11—C12	−178.7 (2)	N1—C13—N3—N4	155.6 (6)
C10—C11—C12—C7	−0.6 (4)	C10—C13—N3—N4	42.6 (7)
C8—C7—C12—C11	0.5 (4)	N4—N3—C17—C18	−2.7 (9)
C6—C7—C12—C11	179.2 (3)	C13—N3—C17—C18	−159.9 (7)
N6—N5—C13—N1A	67.9 (4)	N3—C17—C18—C19	7.0 (10)
C20—N5—C13—N1A	−99.1 (4)	C19A—N4—C19—C18	−126 (4)
N6—N5—C13—N3	−41.8 (4)	N3A—N4—C19—C18	24.6 (9)
C20—N5—C13—N3	151.2 (3)	N3—N4—C19—C18	7.5 (9)
N6—N5—C13—N3A	−45.2 (3)	C17—C18—C19—N4	−9.4 (11)
C20—N5—C13—N3A	147.8 (3)	C19A—N4—N3A—C17A	5.9 (8)
N6—N5—C13—N1	76.9 (5)	N3—N4—N3A—C17A	102.7 (10)
C20—N5—C13—N1	−90.1 (5)	C19—N4—N3A—C17A	0.4 (7)
N6—N5—C13—C10	−166.4 (2)	C19A—N4—N3A—C13	−173.8 (7)
C20—N5—C13—C10	26.6 (4)	N3—N4—N3A—C13	−77.0 (8)
C9—C10—C13—N1A	−7.2 (4)	C19—N4—N3A—C13	−179.3 (7)
C11—C10—C13—N1A	171.4 (3)	N1A—C13—N3A—N4	141.0 (6)
C9—C10—C13—N5	−125.1 (3)	N5—C13—N3A—N4	−109.6 (6)
C11—C10—C13—N5	53.5 (3)	N3—C13—N3A—N4	81.7 (13)
C9—C10—C13—N3	106.0 (4)	N1—C13—N3A—N4	131.0 (7)
C11—C10—C13—N3	−75.4 (4)	C10—C13—N3A—N4	8.0 (8)
C9—C10—C13—N3A	121.9 (4)	N1A—C13—N3A—C17A	−38.7 (9)
C11—C10—C13—N3A	−59.5 (5)	N5—C13—N3A—C17A	70.8 (8)
C9—C10—C13—N1	−5.6 (4)	N3—C13—N3A—C17A	−98.0 (14)
C11—C10—C13—N1	173.0 (3)	N1—C13—N3A—C17A	−48.6 (9)
N1A—C14—N1—N2	112.6 (17)	C10—C13—N3A—C17A	−171.6 (6)
C16—C14—N1—N2	3.2 (7)	N4—N3A—C17A—C18A	−2.4 (8)
N1A—C14—N1—C13	−70.0 (13)	C13—N3A—C17A—C18A	177.2 (7)
C16—C14—N1—C13	−179.4 (7)	N3A—C17A—C18A—C19A	−1.7 (9)
N1A—C13—N1—C14	69.4 (19)	N3A—N4—C19A—C18A	−7.1 (9)
N5—C13—N1—C14	15.3 (10)	N3—N4—C19A—C18A	−25.2 (9)
N3—C13—N1—C14	141.6 (8)	C19—N4—C19A—C18A	23 (3)
N3A—C13—N1—C14	129.4 (8)	C17A—C18A—C19A—N4	5.5 (10)
C10—C13—N1—C14	−103.3 (8)	N6—N5—C20—C22	1.3 (3)
N1A—C13—N1—N2	−114 (2)	C13—N5—C20—C22	169.0 (3)
N5—C13—N1—N2	−167.8 (7)	N5—N6—C21—C22	1.0 (4)
N3—C13—N1—N2	−41.5 (9)	N5—C20—C22—C21	−0.6 (3)
N3A—C13—N1—N2	−53.7 (10)	N6—C21—C22—C20	−0.2 (4)

Experimental details

Crystal data
Chemical formula	C₂₂H₁₈N₆O₂S
M_r	430.48
Crystal system, space group	Triclinic, P1
Temperature (K)	153
a, b, c (Å)	7.2356 (14), 8.1104 (16), 18.626 (4)
α, β, γ (°)	95.05 (3), 99.20 (2), 112.14 (3)
V (Å³)	986.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.16 × 0.15 × 0.11

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Gaussian (SHELXTL; Sheldrick, 2008)
T_min, T_max	0.969, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5461, 3466, 2749
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.148, 1.12
No. of reflections	3466
No. of parameters	294
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.46

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999) within WinGX (Farrugia, 1999), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and POV-RAY (Persistence of Vision, 2004), SHELXL97 (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge the Robert A. Welch Foundation (F-1631), the National Science Foundation (CHE-0741973 and CHE-0847763), the Advanced Research Program of the Texas Higher Education Coordinating Board (01916–090-2010) and UT-Austin for financial support of this research.

References

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