Indole-3-thio-uronium nitrate.

In the title compound, C(9)H(10)N(3)S(+)·NO(3) (-), the indole ring system and the thiouronium group are nearly perpendicular, with a dihedral angle of 88.62 (6)°. Hydrogen bonding generates two-dimensional networks which are linked to each other via π stacking inter-actions of the indole groups [average inter-planar ring-ring distance of 3.449 (2) Å].

Related literature

For reviews of the supra­molecular chemistry of thio­urea derivatives, see: Takemoto (2005 ▶); Fitzmaurice et al. (2002 ▶); Schmidtchen & Berger (1997 ▶). For anion recognition of thio­uronium salts, see: Esteban Gómez et al. (2005 ▶). For the synthesis of the title compound, see: Harris (1969 ▶); van der Geer et al. (2007 ▶). For thermal motion analysis, see: Schomaker & Trueblood (1998 ▶).

Experimental

Crystal data

C9H10N3S+·NO3 −

M = 254.27

Orthorhombic,

a = 12.0524 (2) Å

b = 8.7395 (1) Å

c = 21.1893 (3) Å

V = 2231.91 (5) Å3

Z = 8

Mo Kα radiation

μ = 0.29 mm−1

T = 150 (2) K

0.30 × 0.24 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: none

32180 measured reflections

2563 independent reflections

2120 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.089

S = 1.04

2563 reflections

194 parameters

All H-atom parameters refined

Δρmax = 0.26 e Å−3

Δρmin = −0.23 e Å−3

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ▶); data reduction: HKL-2000; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807064707/bt2657sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064707/bt2657Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C9H10N3S+·NO3–	F000 = 1056
Mr = 254.27	Dx = 1.513 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 44477 reflections
a = 12.0524 (2) Å	θ = 1.0–27.5º
b = 8.7395 (1) Å	µ = 0.29 mm−1
c = 21.1893 (3) Å	T = 150 (2) K
V = 2231.91 (5) Å3	Plate, colourless
Z = 8	0.30 × 0.24 × 0.06 mm

Nonius KappaCCD diffractometer	2120 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.048
Monochromator: graphite	θmax = 27.5º
T = 150(2) K	θmin = 1.9º
φ and ω scans	h = −15→15
Absorption correction: none	k = −11→11
32180 measured reflections	l = −27→27
2563 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	All H-atom parameters refined
wR(F2) = 0.089	w = 1/[σ2(Fo2) + (0.0479P)2 + 0.7806P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2563 reflections	Δρmax = 0.26 e Å−3
194 parameters	Δρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
S1	0.69778 (3)	0.42394 (4)	0.119223 (18)	0.02623 (13)
N1	0.37464 (10)	0.47136 (15)	0.12180 (6)	0.0261 (3)
H1N	0.3086 (14)	0.448 (2)	0.1367 (9)	0.034 (5)*
N2	0.67908 (11)	0.63413 (15)	0.21093 (6)	0.0247 (3)
H2N	0.7073 (14)	0.693 (2)	0.2402 (9)	0.036 (5)*
H3N	0.6067 (17)	0.642 (2)	0.2016 (8)	0.037 (5)*
N3	0.85228 (11)	0.53570 (16)	0.19399 (7)	0.0281 (3)
H4N	0.8814 (17)	0.598 (2)	0.2236 (10)	0.049 (6)*
H5N	0.9029 (17)	0.481 (2)	0.1728 (10)	0.048 (6)*
C1	0.47062 (12)	0.40523 (18)	0.14151 (7)	0.0263 (3)
H1	0.4724 (13)	0.320 (2)	0.1715 (8)	0.030 (4)*
C2	0.55884 (11)	0.47801 (17)	0.11306 (6)	0.0224 (3)
C3	0.56104 (12)	0.70408 (16)	0.03254 (7)	0.0241 (3)
H3	0.6404 (14)	0.7099 (18)	0.0278 (7)	0.025 (4)*
C4	0.49126 (14)	0.80176 (18)	0.00043 (7)	0.0283 (3)
H4	0.5191 (15)	0.876 (2)	−0.0291 (9)	0.037 (5)*
C5	0.37534 (13)	0.79541 (18)	0.00913 (7)	0.0296 (3)
H5	0.3302 (14)	0.868 (2)	−0.0129 (9)	0.040 (5)*
C6	0.32737 (12)	0.68900 (18)	0.04876 (7)	0.0267 (3)
H6	0.2499 (15)	0.6822 (18)	0.0556 (7)	0.028 (4)*
C7	0.39845 (11)	0.58860 (16)	0.08036 (6)	0.0222 (3)
C8	0.51463 (11)	0.59550 (15)	0.07326 (6)	0.0203 (3)
C9	0.74591 (11)	0.54277 (16)	0.18022 (6)	0.0219 (3)
O1	0.78687 (8)	0.82212 (13)	0.30339 (5)	0.0302 (3)
O2	0.95458 (8)	0.75180 (13)	0.27976 (5)	0.0308 (3)
O3	0.92651 (9)	0.94570 (13)	0.34188 (5)	0.0351 (3)
N4	0.88984 (10)	0.84099 (14)	0.30879 (6)	0.0240 (3)

	U11	U22	U33	U12	U13	U23
S1	0.0208 (2)	0.0269 (2)	0.0309 (2)	0.00496 (14)	−0.00216 (14)	−0.00352 (15)
N1	0.0191 (6)	0.0331 (7)	0.0262 (6)	−0.0050 (5)	0.0008 (5)	0.0028 (5)
N2	0.0174 (6)	0.0284 (7)	0.0284 (7)	0.0015 (5)	−0.0012 (5)	−0.0036 (6)
N3	0.0179 (6)	0.0306 (7)	0.0357 (7)	0.0028 (5)	−0.0010 (5)	−0.0007 (6)
C1	0.0244 (7)	0.0292 (8)	0.0253 (7)	−0.0031 (6)	−0.0015 (6)	0.0024 (6)
C2	0.0186 (6)	0.0248 (7)	0.0239 (7)	0.0001 (5)	−0.0017 (5)	−0.0015 (6)
C3	0.0212 (7)	0.0245 (7)	0.0265 (7)	−0.0034 (6)	0.0018 (6)	−0.0024 (6)
C4	0.0323 (8)	0.0253 (8)	0.0273 (8)	−0.0035 (6)	−0.0004 (6)	0.0022 (6)
C5	0.0311 (8)	0.0286 (8)	0.0291 (8)	0.0039 (6)	−0.0066 (6)	−0.0009 (6)
C6	0.0190 (7)	0.0326 (8)	0.0287 (8)	0.0008 (6)	−0.0038 (6)	−0.0048 (6)
C7	0.0198 (7)	0.0260 (7)	0.0207 (6)	−0.0029 (6)	−0.0005 (5)	−0.0030 (5)
C8	0.0178 (6)	0.0222 (7)	0.0209 (7)	−0.0010 (5)	−0.0001 (5)	−0.0029 (5)
C9	0.0175 (6)	0.0228 (7)	0.0255 (7)	−0.0004 (5)	−0.0009 (5)	0.0059 (6)
O1	0.0145 (5)	0.0416 (6)	0.0345 (6)	0.0011 (4)	0.0000 (4)	−0.0075 (5)
O2	0.0186 (5)	0.0431 (7)	0.0308 (6)	0.0075 (5)	0.0033 (4)	0.0002 (5)
O3	0.0293 (6)	0.0403 (7)	0.0358 (6)	−0.0102 (5)	0.0002 (5)	−0.0051 (5)
N4	0.0177 (6)	0.0309 (7)	0.0235 (6)	0.0003 (5)	0.0013 (5)	0.0042 (5)

S1—C2	1.7448 (14)	C3—C4	1.378 (2)
S1—C9	1.7566 (15)	C3—C8	1.399 (2)
N1—C1	1.359 (2)	C3—H3	0.963 (17)
N1—C7	1.3795 (19)	C4—C5	1.410 (2)
N1—H1N	0.880 (18)	C4—H4	0.963 (18)
N2—C9	1.3076 (19)	C5—C6	1.380 (2)
N2—H2N	0.87 (2)	C5—H5	0.955 (19)
N2—H3N	0.90 (2)	C6—C7	1.397 (2)
N3—C9	1.3162 (19)	C6—H6	0.946 (18)
N3—H4N	0.90 (2)	C7—C8	1.4096 (19)
N3—H5N	0.89 (2)	O1—N4	1.2572 (15)
C1—C2	1.378 (2)	O2—N4	1.2628 (16)
C1—H1	0.979 (18)	O3—N4	1.2348 (16)
C2—C8	1.432 (2)
C2—S1—C9	102.23 (7)	C3—C4—H4	121.7 (11)
C1—N1—C7	109.54 (12)	C5—C4—H4	117.2 (11)
C1—N1—H1N	124.0 (12)	C6—C5—C4	121.41 (14)
C7—N1—H1N	126.1 (12)	C6—C5—H5	120.3 (11)
C9—N2—H2N	118.1 (11)	C4—C5—H5	118.3 (11)
C9—N2—H3N	122.4 (11)	C5—C6—C7	117.25 (14)
H2N—N2—H3N	119.5 (16)	C5—C6—H6	123.3 (10)
C9—N3—H4N	120.3 (13)	C7—C6—H6	119.5 (10)
C9—N3—H5N	125.3 (13)	N1—C7—C6	130.09 (13)
H4N—N3—H5N	113.9 (18)	N1—C7—C8	107.84 (12)
N1—C1—C2	109.03 (13)	C6—C7—C8	122.07 (13)
N1—C1—H1	122.8 (10)	C3—C8—C7	119.47 (13)
C2—C1—H1	128.2 (10)	C3—C8—C2	134.50 (13)
C1—C2—C8	107.55 (12)	C7—C8—C2	106.03 (12)
C1—C2—S1	125.65 (12)	N2—C9—N3	121.22 (14)
C8—C2—S1	126.55 (11)	N2—C9—S1	121.59 (11)
C4—C3—C8	118.73 (14)	N3—C9—S1	117.19 (11)
C4—C3—H3	121.4 (10)	O3—N4—O1	120.15 (12)
C8—C3—H3	119.8 (10)	O3—N4—O2	120.86 (12)
C3—C4—C5	121.04 (15)	O1—N4—O2	118.99 (12)
C7—N1—C1—C2	−0.19 (17)	C4—C3—C8—C7	0.1 (2)
N1—C1—C2—C8	−0.26 (17)	C4—C3—C8—C2	179.62 (15)
N1—C1—C2—S1	−174.86 (11)	N1—C7—C8—C3	178.96 (13)
C9—S1—C2—C1	−95.95 (14)	C6—C7—C8—C3	−1.2 (2)
C9—S1—C2—C8	90.45 (13)	N1—C7—C8—C2	−0.71 (15)
C8—C3—C4—C5	1.3 (2)	C6—C7—C8—C2	179.17 (13)
C3—C4—C5—C6	−1.7 (2)	C1—C2—C8—C3	−179.01 (16)
C4—C5—C6—C7	0.6 (2)	S1—C2—C8—C3	−4.5 (2)
C1—N1—C7—C6	−179.29 (15)	C1—C2—C8—C7	0.60 (16)
C1—N1—C7—C8	0.58 (16)	S1—C2—C8—C7	175.14 (11)
C5—C6—C7—N1	−179.32 (14)	C2—S1—C9—N2	4.19 (14)
C5—C6—C7—C8	0.8 (2)	C2—S1—C9—N3	−176.06 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.880 (18)	2.036 (19)	2.8290 (16)	149.4 (16)
N2—H2N···O1	0.87 (2)	2.00 (2)	2.8679 (17)	174.2 (16)
N2—H3N···O2ii	0.90 (2)	2.108 (19)	2.9013 (16)	147.0 (16)
N3—H4N···O2	0.90 (2)	2.00 (2)	2.8966 (19)	172.5 (19)
N3—H5N···O3iii	0.89 (2)	2.10 (2)	2.8817 (17)	145.0 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.880 (18)	2.036 (19)	2.8290 (16)	149.4 (16)
N2—H2N⋯O1	0.87 (2)	2.00 (2)	2.8679 (17)	174.2 (16)
N2—H3N⋯O2ii	0.90 (2)	2.108 (19)	2.9013 (16)	147.0 (16)
N3—H4N⋯O2	0.90 (2)	2.00 (2)	2.8966 (19)	172.5 (19)
N3—H5N⋯O3iii	0.89 (2)	2.10 (2)	2.8817 (17)	145.0 (18)

Symmetry codes: (i) ; (ii) ; (iii) .