9-Benzyl-6-benzyl-sulfanyl-9H-purin-2-amine.

In the title compound, C19H17N5S, the dihedral angles between the purine ring system (r.m.s. deviation = 0.009 Å) and the S-bound and methyl-ene-bound phenyl rings are 74.67 (8) and 71.28 (7)°, respectively. In the crystal, inversion dimers linked by pairs of N-H⋯N hydrogen bonds generate R 2 (2)(8) loops. C-H⋯N inter-actions link the dimers into (100) sheets.

Related literature

For background to the biological activity of thio­purine derivatives, see: Hadda et al. (2009 ▶); Nguyen et al. (2009 ▶). For further synthetic details, see: Banh et al. (2011 ▶); Salvatore et al. (2002 ▶, 2005 ▶).

Experimental

Crystal data

C19H17N5S

M = 347.44

Monoclinic,

a = 16.7346 (7) Å

b = 5.5511 (3) Å

c = 20.4817 (10) Å

β = 121.325 (3)°

V = 1625.31 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 100 K

0.69 × 0.19 × 0.14 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T min = 0.868, T max = 0.972

16728 measured reflections

4956 independent reflections

3416 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.137

S = 1.06

4956 reflections

234 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.58 e Å−3

Data collection: APEX2 (Bruker, 2009) ▶; cell refinement: SAINT (Bruker, 2009) ▶; data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814001986/hb7176sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001986/hb7176Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814001986/hb7176Isup3.cml

CCDC reference:

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

C19H17N5S	F(000) = 728
Mr = 347.44	Dx = 1.420 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3425 reflections
a = 16.7346 (7) Å	θ = 2.3–30.0°
b = 5.5511 (3) Å	µ = 0.21 mm−1
c = 20.4817 (10) Å	T = 100 K
β = 121.325 (3)°	Block, colourless
V = 1625.31 (14) Å3	0.69 × 0.19 × 0.14 mm
Z = 4

Bruker SMART APEXII CCD diffractometer	4956 independent reflections
Radiation source: fine-focus sealed tube	3416 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
φ and ω scans	θmax = 30.6°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −23→23
Tmin = 0.868, Tmax = 0.972	k = −7→7
16728 measured reflections	l = −25→29

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0602P)2 + 0.4349P] where P = (Fo2 + 2Fc2)/3
4956 reflections	(Δ/σ)max < 0.001
234 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.58 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
S1	0.24764 (3)	0.72454 (8)	0.12637 (3)	0.01824 (13)
N1	0.52964 (10)	1.0733 (3)	0.14394 (8)	0.0147 (3)
N2	0.42255 (10)	1.0996 (3)	0.17932 (8)	0.0169 (3)
N3	0.47003 (10)	0.7208 (3)	0.06126 (8)	0.0148 (3)
N4	0.32973 (10)	0.5624 (3)	0.05291 (8)	0.0151 (3)
N5	0.39014 (11)	0.3896 (3)	−0.01293 (9)	0.0183 (3)
C1	0.70179 (12)	0.7950 (3)	0.20967 (10)	0.0170 (4)
H1A	0.6619	0.7724	0.2293	0.020*
C2	0.77591 (13)	0.6376 (3)	0.23027 (10)	0.0200 (4)
H2A	0.7865	0.5080	0.2642	0.024*
C3	0.83454 (13)	0.6682 (4)	0.20170 (10)	0.0211 (4)
H3A	0.8838	0.5570	0.2147	0.025*
C4	0.82082 (13)	0.8621 (3)	0.15408 (10)	0.0210 (4)
H4A	0.8617	0.8863	0.1355	0.025*
C5	0.74731 (12)	1.0206 (3)	0.13374 (10)	0.0190 (4)
H5A	0.7385	1.1538	0.1016	0.023*
C6	0.68604 (12)	0.9858 (3)	0.16023 (9)	0.0154 (3)
C7	0.60378 (12)	1.1554 (3)	0.13203 (10)	0.0176 (4)
H7A	0.6271	1.3124	0.1581	0.021*
H7B	0.5767	1.1826	0.0767	0.021*
C8	0.49754 (13)	1.1938 (3)	0.18504 (10)	0.0165 (4)
H8A	0.5274	1.3330	0.2149	0.020*
C9	0.46824 (11)	0.8869 (3)	0.10795 (9)	0.0133 (3)
C10	0.39805 (12)	0.5647 (3)	0.03571 (9)	0.0144 (3)
C11	0.33280 (12)	0.7292 (3)	0.10083 (9)	0.0138 (3)
C12	0.40253 (12)	0.9046 (3)	0.13023 (9)	0.0141 (3)
C13	0.19169 (13)	0.4383 (3)	0.08654 (10)	0.0186 (4)
H13A	0.2409	0.3215	0.0950	0.022*
H13B	0.1636	0.3806	0.1160	0.022*
C14	0.11669 (12)	0.4322 (3)	0.00268 (10)	0.0166 (4)
C15	0.10259 (13)	0.6128 (3)	−0.04927 (10)	0.0198 (4)
H15A	0.1421	0.7504	−0.0327	0.024*
C16	0.03108 (13)	0.5934 (3)	−0.12532 (11)	0.0221 (4)
H16A	0.0219	0.7190	−0.1601	0.027*
C17	−0.02712 (13)	0.3932 (3)	−0.15127 (11)	0.0217 (4)
H17A	−0.0761	0.3812	−0.2033	0.026*
C18	−0.01235 (13)	0.2113 (3)	−0.09980 (11)	0.0217 (4)
H18A	−0.0512	0.0726	−0.1168	0.026*
C19	0.05850 (13)	0.2296 (3)	−0.02383 (11)	0.0196 (4)
H19A	0.0677	0.1032	0.0107	0.023*
H1N5	0.4310 (15)	0.370 (4)	−0.0289 (12)	0.030 (6)*
H2N5	0.3390 (15)	0.304 (4)	−0.0358 (12)	0.024 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.0183 (2)	0.0203 (2)	0.0209 (2)	−0.00120 (18)	0.0136 (2)	−0.00239 (18)
N1	0.0136 (7)	0.0158 (7)	0.0139 (7)	−0.0025 (6)	0.0066 (6)	−0.0020 (6)
N2	0.0205 (8)	0.0153 (7)	0.0157 (7)	0.0009 (6)	0.0100 (6)	−0.0001 (6)
N3	0.0160 (7)	0.0152 (7)	0.0150 (7)	−0.0017 (6)	0.0095 (6)	−0.0013 (6)
N4	0.0148 (7)	0.0163 (7)	0.0158 (7)	0.0013 (6)	0.0090 (6)	−0.0001 (6)
N5	0.0161 (8)	0.0203 (8)	0.0209 (8)	−0.0053 (7)	0.0113 (7)	−0.0083 (6)
C1	0.0161 (9)	0.0189 (9)	0.0148 (8)	−0.0039 (7)	0.0072 (7)	−0.0020 (7)
C2	0.0188 (9)	0.0186 (9)	0.0177 (9)	−0.0028 (7)	0.0061 (7)	−0.0005 (7)
C3	0.0174 (9)	0.0218 (9)	0.0200 (9)	0.0004 (7)	0.0067 (8)	−0.0035 (7)
C4	0.0183 (9)	0.0238 (10)	0.0231 (9)	−0.0039 (8)	0.0121 (8)	−0.0046 (8)
C5	0.0203 (9)	0.0188 (9)	0.0176 (8)	−0.0052 (7)	0.0097 (8)	−0.0025 (7)
C6	0.0151 (9)	0.0153 (8)	0.0140 (8)	−0.0039 (7)	0.0062 (7)	−0.0047 (6)
C7	0.0180 (9)	0.0156 (8)	0.0214 (9)	−0.0016 (7)	0.0117 (8)	0.0005 (7)
C8	0.0214 (9)	0.0140 (8)	0.0140 (8)	−0.0004 (7)	0.0092 (7)	−0.0013 (6)
C9	0.0140 (8)	0.0134 (8)	0.0107 (7)	0.0003 (6)	0.0051 (6)	0.0004 (6)
C10	0.0148 (8)	0.0141 (8)	0.0142 (8)	0.0004 (7)	0.0074 (7)	0.0006 (6)
C11	0.0134 (8)	0.0149 (8)	0.0129 (8)	0.0017 (6)	0.0066 (7)	0.0026 (6)
C12	0.0165 (8)	0.0131 (8)	0.0139 (8)	0.0007 (7)	0.0088 (7)	0.0002 (6)
C13	0.0196 (9)	0.0171 (9)	0.0222 (9)	−0.0022 (7)	0.0129 (8)	0.0012 (7)
C14	0.0133 (8)	0.0187 (9)	0.0196 (8)	−0.0001 (7)	0.0099 (7)	−0.0001 (7)
C15	0.0189 (9)	0.0178 (9)	0.0241 (9)	0.0003 (7)	0.0122 (8)	0.0008 (7)
C16	0.0227 (10)	0.0212 (9)	0.0225 (9)	0.0048 (8)	0.0118 (8)	0.0056 (8)
C17	0.0168 (9)	0.0252 (10)	0.0194 (9)	0.0033 (8)	0.0068 (7)	0.0007 (8)
C18	0.0180 (9)	0.0203 (9)	0.0268 (10)	−0.0015 (7)	0.0117 (8)	−0.0013 (8)
C19	0.0184 (9)	0.0187 (9)	0.0235 (9)	0.0003 (7)	0.0122 (8)	0.0017 (7)

S1—C11	1.7551 (17)	C5—C6	1.400 (2)
S1—C13	1.8091 (18)	C5—H5A	0.9500
N1—C9	1.372 (2)	C6—C7	1.513 (2)
N1—C8	1.384 (2)	C7—H7A	0.9900
N1—C7	1.456 (2)	C7—H7B	0.9900
N2—C8	1.307 (2)	C8—H8A	0.9500
N2—C12	1.395 (2)	C9—C12	1.396 (2)
N3—C9	1.340 (2)	C11—C12	1.393 (2)
N3—C10	1.349 (2)	C13—C14	1.512 (2)
N4—C11	1.331 (2)	C13—H13A	0.9900
N4—C10	1.360 (2)	C13—H13B	0.9900
N5—C10	1.348 (2)	C14—C15	1.390 (2)
N5—H1N5	0.90 (2)	C14—C19	1.399 (2)
N5—H2N5	0.87 (2)	C15—C16	1.390 (3)
C1—C2	1.392 (2)	C15—H15A	0.9500
C1—C6	1.392 (2)	C16—C17	1.388 (3)
C1—H1A	0.9500	C16—H16A	0.9500
C2—C3	1.390 (3)	C17—C18	1.386 (3)
C2—H2A	0.9500	C17—H17A	0.9500
C3—C4	1.389 (3)	C18—C19	1.385 (3)
C3—H3A	0.9500	C18—H18A	0.9500
C4—C5	1.388 (3)	C19—H19A	0.9500
C4—H4A	0.9500
C11—S1—C13	100.87 (8)	N3—C9—N1	127.88 (15)
C9—N1—C8	105.78 (14)	N3—C9—C12	126.53 (15)
C9—N1—C7	127.68 (14)	N1—C9—C12	105.59 (14)
C8—N1—C7	125.79 (14)	N5—C10—N3	118.33 (15)
C8—N2—C12	103.57 (14)	N5—C10—N4	114.32 (15)
C9—N3—C10	111.85 (14)	N3—C10—N4	127.34 (15)
C11—N4—C10	117.98 (14)	N4—C11—C12	120.50 (15)
C10—N5—H1N5	123.6 (14)	N4—C11—S1	118.92 (13)
C10—N5—H2N5	118.7 (14)	C12—C11—S1	120.58 (13)
H1N5—N5—H2N5	117.1 (19)	C11—C12—N2	133.42 (15)
C2—C1—C6	120.00 (16)	C11—C12—C9	115.76 (15)
C2—C1—H1A	120.0	N2—C12—C9	110.81 (15)
C6—C1—H1A	120.0	C14—C13—S1	117.49 (13)
C3—C2—C1	120.58 (17)	C14—C13—H13A	107.9
C3—C2—H2A	119.7	S1—C13—H13A	107.9
C1—C2—H2A	119.7	C14—C13—H13B	107.9
C4—C3—C2	119.68 (18)	S1—C13—H13B	107.9
C4—C3—H3A	120.2	H13A—C13—H13B	107.2
C2—C3—H3A	120.2	C15—C14—C19	118.40 (17)
C5—C4—C3	119.92 (17)	C15—C14—C13	124.32 (16)
C5—C4—H4A	120.0	C19—C14—C13	117.28 (16)
C3—C4—H4A	120.0	C16—C15—C14	120.45 (17)
C4—C5—C6	120.63 (17)	C16—C15—H15A	119.8
C4—C5—H5A	119.7	C14—C15—H15A	119.8
C6—C5—H5A	119.7	C17—C16—C15	120.97 (17)
C1—C6—C5	119.13 (16)	C17—C16—H16A	119.5
C1—C6—C7	122.79 (15)	C15—C16—H16A	119.5
C5—C6—C7	118.07 (15)	C18—C17—C16	118.67 (17)
N1—C7—C6	115.28 (14)	C18—C17—H17A	120.7
N1—C7—H7A	108.5	C16—C17—H17A	120.7
C6—C7—H7A	108.5	C19—C18—C17	120.73 (18)
N1—C7—H7B	108.5	C19—C18—H18A	119.6
C6—C7—H7B	108.5	C17—C18—H18A	119.6
H7A—C7—H7B	107.5	C18—C19—C14	120.75 (17)
N2—C8—N1	114.24 (15)	C18—C19—H19A	119.6
N2—C8—H8A	122.9	C14—C19—H19A	119.6
N1—C8—H8A	122.9
C6—C1—C2—C3	−0.2 (3)	C10—N4—C11—C12	2.0 (2)
C1—C2—C3—C4	2.1 (3)	C10—N4—C11—S1	−178.00 (12)
C2—C3—C4—C5	−1.6 (3)	C13—S1—C11—N4	9.65 (15)
C3—C4—C5—C6	−0.6 (3)	C13—S1—C11—C12	−170.34 (14)
C2—C1—C6—C5	−2.0 (2)	N4—C11—C12—N2	178.87 (17)
C2—C1—C6—C7	176.53 (16)	S1—C11—C12—N2	−1.1 (3)
C4—C5—C6—C1	2.4 (2)	N4—C11—C12—C9	−1.9 (2)
C4—C5—C6—C7	−176.18 (16)	S1—C11—C12—C9	178.12 (12)
C9—N1—C7—C6	−69.9 (2)	C8—N2—C12—C11	179.67 (19)
C8—N1—C7—C6	121.46 (18)	C8—N2—C12—C9	0.37 (18)
C1—C6—C7—N1	−14.7 (2)	N3—C9—C12—C11	0.5 (3)
C5—C6—C7—N1	163.78 (15)	N1—C9—C12—C11	−179.30 (14)
C12—N2—C8—N1	−0.76 (19)	N3—C9—C12—N2	179.94 (15)
C9—N1—C8—N2	0.87 (19)	N1—C9—C12—N2	0.13 (18)
C7—N1—C8—N2	171.58 (15)	C11—S1—C13—C14	−83.26 (14)
C10—N3—C9—N1	−179.61 (16)	S1—C13—C14—C15	15.4 (2)
C10—N3—C9—C12	0.6 (2)	S1—C13—C14—C19	−165.09 (13)
C8—N1—C9—N3	179.63 (17)	C19—C14—C15—C16	1.2 (3)
C7—N1—C9—N3	9.2 (3)	C13—C14—C15—C16	−179.25 (16)
C8—N1—C9—C12	−0.55 (17)	C14—C15—C16—C17	−0.6 (3)
C7—N1—C9—C12	−171.03 (16)	C15—C16—C17—C18	−0.3 (3)
C9—N3—C10—N5	178.94 (15)	C16—C17—C18—C19	0.6 (3)
C9—N3—C10—N4	−0.5 (2)	C17—C18—C19—C14	0.0 (3)
C11—N4—C10—N5	179.75 (15)	C15—C14—C19—C18	−0.9 (3)
C11—N4—C10—N3	−0.8 (3)	C13—C14—C19—C18	179.50 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H1N5···N3i	0.91 (3)	2.14 (3)	3.040 (3)	173 (2)
C7—H7B···N3ii	0.99	2.57	3.548 (2)	172
C8—H8A···N2iii	0.95	2.39	3.274 (2)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H1N5⋯N3i	0.91 (3)	2.14 (3)	3.040 (3)	173 (2)
C7—H7B⋯N3ii	0.99	2.57	3.548 (2)	172
C8—H8A⋯N2iii	0.95	2.39	3.274 (2)	155

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