4,5,6-Triamino-2-(methyl­sulfanyl)­pyrimidine: π-stacked hydrogen-bonded sheets of R22(8), R22(10) and R66(32) rings

Cobo, J.; Sánchez Rodrigo, A.; Nogueras Montiel, M.; Low, J.N.; Glidewell, C.

doi:10.1107/S0108270106003805

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 3| March 2006| Pages o142-o144

doi:10.1107/S0108270106003805

4,5,6-Triamino-2-(methylsulfanyl)pyrimidine: π-stacked hydrogen-bonded sheets of R₂²(8), R₂²(10) and R₆⁶(32) rings

Justo Cobo,^a Adolfo Sánchez Rodrigo,^a Manuel Nogueras Montiel,^a John N. Low ^b and Christopher Glidewell ^c ^*

^aDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 30 January 2006; accepted 31 January 2006; online 28 February 2006)

In the title compound, C₅H₉N₅S, the three independent C—NH₂ units are all somewhat pyramidal. The molecules are linked by a combination of one N—H⋯S and two N—H⋯N hydrogen bonds into sheets containing three types of ring motif, viz. R₂²(8), R₂²(10) and R₆⁶(32), all of them centrosymmetric. Adjacent sheets are linked by a single π–π stacking interaction.

Comment

The title compound, (I), was prepared following a published procedure (Baddiley et al., 1943 ) for use as an intermediate in the synthesis of fused pyrimidine derivatives of potential biological interest.

Within the heterocyclic ring in the molecule of (I), the bond distances (Table 1) provide evidence for aromatic delocalization. The internal bond angles at atoms N1, N3 and C5 are all significantly less than the idealized value of 120°; those at N1 and N3 reflect the stereochemical influence of the lone pairs of electrons on these atoms, while that at C5 is influenced by the behaviour of the exocyclic amino group.

Each of the three independent C—NH₂ units is, to a greater or lesser extent, pyramidal, and this is least marked for atom N6 and most marked for atom N5. The sums of the interbond angles at atoms N4, N5 and N6 deviate by 12, 26 and 3°, respectively, from 360°. Closely associated with the degree of pyramidalization at the amino N atoms is the variation in the exocyclic C—N bond distances (Table 1), with C5—N5 the longest of these and C6—N6 the shortest. The very long C5—N5 bond is also doubtless influenced by the rotation of the lone pair at N5 to be almost coplanar with the pyrimidine ring (Table 1 and Fig. 1). The mean values (Allen et al., 1987 ) for C—S bonds of the types found in (I) are 1.773 and 1.789 Å, so that the difference between the S2—C2 and S2—C21 distances is larger than expected.

Amino atoms N4 and N5 are, therefore, potential acceptors of hydrogen bonds, in addition to ring atoms N1 and N3 and sulfanyl atom S2, while each amino group is potentially a double donor of hydrogen bonds. In practice, there is one intramolecular N—H⋯N hydrogen bond (Table 2), with the highly pyramidal N5 atom as the acceptor, and each amino group acts as a single donor in intermolecular hydrogen bonds, with one ring N atom, one amino N atom and the S atom as the three acceptors (Table 2). Hence, two of the N—H bonds do not participate in any hydrogen-bond formation.

The three intermolecular hydrogen bonds generate a sheet containing three distinct types of ring, all centrosymmetric, but the formation of this rather complex sheet is readily analysed in terms of two straightforward one-dimensional substructures, one built from two independent N—H⋯N hydrogen bonds and the other built using only N—H⋯S hydrogen bonds.

Amino atom N5 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyramidal amino N4 atom in the molecule at (−x, −y, 1 − z), so forming a centrosymmetric R₂²(10) (Bernstein et al., 1995 ) ring centred at (0, 0, $[{1 \over 2}]$ ). Similarly, amino atom N6 at (x, y, z) acts as hydrogen-bond donor to ring atom N1 in the molecule at (1 − x, 1 − y, 1 − z), so forming a second ring motif, this time of R₂²(8) type, centred at ( $[{1 \over 2}]$ , $[{1 \over 2}]$ , $[{1 \over 2}]$ ). Propagation by inversion of these two hydrogen bonds then generates a chain of centrosymmetric rings running parallel to the [110] direction, with R₂²(8) rings centred at (n + $[{1 \over 2}]$ , n + $[{1 \over 2}]$ , $[{1 \over 2}]$ ) (n = zero or integer) and R₂²(10) rings centred at (n, n, $[{1 \over 2}]$ ) (n = zero or integer) (Fig. 2).

In the second one-dimensional substructure, amino atom N4 in the molecule at (x, y, z) acts as hydrogen-bond donor to the S atom in the molecule at (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z), thereby forming a C(6) chain running parallel to the [101] direction and generated by the n-glide plane at y = $[{1 \over 4}]$ (Fig. 3).

The combination of the [110] and [101] chains generates a ( $[\overline{1}]$ 11) sheet built from R₂²(8), R₂²(10) and R₆⁶(32) rings, all of them centrosymmetric (Fig. 4), and these sheets are linked by a centrosymmetric π–π stacking interaction. The pyrimidine rings of the molecules at (x, y, z) and (−x, 1 − y, 1 − z) are strictly parallel, with an interplanar spacing of 3.337 (2) Å. The ring-centroid separation is 3.649 (2) Å, corresponding to a near-ideal ring offset of 1.476 (2) Å. The combination of this interaction with the R₂²(8) rings generates a chain running parallel to the [100] direction, while the combination of the π-stacking interaction with the R₂²(10) rings generates a chain parallel to the [010] direction. In this manner, the ( $[\overline{1}]$ 11) sheets are linked into a single three-dimensional structure.

Figure 1
The molecule of compound (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of (I)

, showing a chain of alternating R₂²(8) and R₂²(10) rings along [110]. For the sake of clarity, the H atoms of the methyl group have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (1 − x, 1 − y, 1 − z), (−x, −y, 1 − z), (1 + x, 1 + y, z) and (−1 + x, −1 + y, z), respectively.

Figure 3
Part of the crystal structure of (I)

, showing a C(6) chain along [101]. For the sake of clarity, H atoms bonded to C or N atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z), ( $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) and (1 + x, y, 1 + z), respectively.

Figure 4
A stereoview of part of the crystal structure of compound (I)

, showing the formation of a ( $[\overline{1}]$ 11) sheet of R₂²(8), R₂²(10) and R₆⁶(32) rings. For the sake of clarity, the H atoms of the methyl group have been omitted.

Experimental

Crystals of the title compound, (I), were prepared according to the procedure of Baddiley et al. (1943).

Crystal data

C₅H₉N₅S
M_r = 171.23
Monoclinic, P 2₁ /n
a = 7.7824 (2) Å
b = 8.9623 (3) Å
c = 10.5078 (4) Å
β = 95.261 (2)°
V = 729.81 (4) Å³
Z = 4
D_x = 1.558 Mg m⁻³
Mo Kα radiation
Cell parameters from 1659 reflections
θ = 3.9–27.5°
μ = 0.38 mm⁻¹
T = 120 (2) K
Rod, yellow
0.40 × 0.20 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.863, T_max = 0.963
9338 measured reflections
1659 independent reflections
1533 reflections with I > 2σ(I)
R_int = 0.024
θ_max = 27.5°
h = −9 → 10
k = −11 → 11
l = −13 → 13

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.073
S = 1.11
1659 reflections
101 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0279P)² + 0.4621P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

N1—C2	1.3337 (16)
C2—N3	1.3242 (16)
N3—C4	1.3573 (17)
C4—C5	1.3888 (18)
C5—C6	1.4104 (17)
C6—N1	1.3557 (16)
C4—N4	1.3759 (16)
C5—N5	1.4292 (16)
C6—N6	1.3518 (16)
C2—S2	1.7694 (13)
S2—C21	1.7997 (13)

C6—N1—C2	115.40 (11)
N1—C2—N3	129.07 (11)
C2—N3—C4	114.55 (11)
N3—C4—C5	123.14 (11)
C4—C5—C6	116.22 (11)
C5—C6—N1	121.60 (11)
N3—C4—N4	114.95 (11)
C5—C4—N4	121.88 (12)
C4—C5—N5	124.73 (11)
C6—C5—N5	119.04 (11)
C5—C6—N6	121.56 (11)
N1—C6—N6	116.82 (11)
N1—C2—S2	112.03 (9)
N3—C2—S2	118.90 (9)
C2—S2—C21	101.71 (6)
C4—N4—H4A	114.9
C4—N4—H4B	111.4
H4A—N4—H4B	118.1
C5—N5—H5A	112.1
C5—N5—H5B	113.7
H5A—N5—H5B	108.0
C6—N6—H6A	117.9
C6—N6—H6B	119.2
H6A—N6—H6B	119.7

N3—C4—N4—H4A	163
C4—C5—N5—H5A	−69
C5—C6—N6—H6A	170
N3—C4—N4—H4B	26
C4—C5—N5—H5B	54
C5—C6—N6—H6B	10

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯S2ⁱ	0.88	2.75	3.5902 (12)	159
N5—H5A⋯N4ⁱⁱ	0.88	2.48	3.3379 (16)	166
N6—H6A⋯N1ⁱⁱⁱ	0.88	2.23	3.1049 (15)	176
N6—H6B⋯N5	0.88	2.48	2.8134 (16)	103
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y, -z+1; (iii) -x+1, -y+1, -z+1.

The space group P2₁/n was uniquely assigned from the systematic absences. All H atoms were located from difference maps and then treated as riding atoms. The H atoms of the methyl group were assigned C—H distances of 0.98 Å, with U_iso(H) = 1.5U_eq(C). The amino H atoms were allowed to ride at the locations deduced from the difference maps, with N—H = 0.88 Å and U_iso(H) = 1.2U_eq(N).

Data collection: COLLECT (Nonius, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270106003805/sk1899sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106003805/sk1899Isup2.hkl

Comment top

The title compound, (I), was prepared following a published procedure (Baddiley et al., 1943) for use as an intermediate in the synthesis of fused pyrimidine derivatives of potential biological interest.

Each of the three independent C—NH₂ units is, to a greater or lesser extent, pyramidal, and this is least marked for atom N6 and most marked for atom N5. The sums of the interbond angles at atoms N4, N5 and N6 deviate by 12, 26 and 3°, respectively, from 360°. Closely associated with the degree of pyramidalization at the amino N atoms is the variation in the exocyclic C—N bond distances (Table 1), with C5—N5 the longest of these and C6—N6 the shortest. The very long C5—N5 bond is also doubtless influenced by the rotation of the lone pair at N5 to be almost coplanar with the pyrimidine ring (Table 1, Fig. 1). The mean values (Allen et al., 1987) for C—S bonds of the types found in (I) are 1.773 and 1.789 Å, so that the difference between the C2—C2 and S2—C21 distances is larger than expected.

Both amino atoms N4 an N5 are, therefore, potential acceptors of hydrogen bonds, in addition to the ring atoms N1 and N3 and the sulfanyl atom S2, while each amino group is potentially a double donor of hydrogen bonds. In practice, there is one intramolecular N—H···N hydrogen bond (Table 2), with the highly pyramidal atom N5 as the acceptor, and each amino group acts as a single donor in intermolecular hydrogen bonds, with one ring N atom, one amino N atom and the S atom as the three acceptors (Table 2). Hence, two of the N—H bonds do not participate in any hydrogen-bond formation.

The three intermolecular hydrogen bonds generate a sheet containing three distinct types of ring, all centrosymmetric, but the formation of this rather complex sheet is readily analysed in terms of two straightforward one-dimensional substructures, one of then built from two independent N—H···N hydrogen bonds and the other built using only N—H···S hydrogen bonds.

Amino atom N5 in the molecule at (x, y, z) acts as hydrogen-bond donor to the pyramidal amino atom N4 in the molecule at (−x, −y, 1 − z), so forming a centrosymmetric R₂²(10) (Bernstein et al., 1995) ring centred at (0,0,1/2). Similarly, amino atom N6 at (x, y, z) acts as hydrogen-bond donor to ring atom N1 in the molecule at (1 − x, 1 − y, 1 − z), so forming a second ring motif, this time of R₂²(8) type, centred at (1/2, 1/2, 1/2). Propagation by inversion of these two hydrogen bonds then generates a chain of centrosymmetric rings running parallel to the [110] direction, with R₂²(8) rings centred at (n + 1/2, n + 1/2, 1/2) (n = zero or integer) and R₂²(10) rings centred at (n, n, 1/2) (n = zero or integer) (Fig. 2).

In the second one-dimensional substructure, amino atom N4 in the molecule at (x, y, z) acts as hydrogen-bond donor to the S atom in the molecule at (−1/2 + x, 1/2 − y, −1/2 + z), thereby forming a C(6) chain running parallel to the [101] direction and generated by the n-glide plane at y = 1/4 (Fig. 3).

The combination of the [110] and [101] chains generates a (111) sheet built from R₂²(8), R₂²(10) and R₆⁶(32) rings, all of them centrosymmetric (Fig. 4), and these sheets are linked by a centrosymmetric π–π stacking interaction. The pyrimidine rings of the molecules at (x, y, z) and (−x, 1 − y, 1 − z) are strictly parallel, with an interplanar spacing of 3.337 (2) Å. The ring-centroid separation is 3.649 (2) Å, corresponding to a near-ideal ring offset of 1.476 (2) Å. The combination of this interaction with the R₂²(8) rings generates a chain running parallel to the [100] direction, while the combination of the π-stacking interaction with the R₂²(10) rings generates a chain parallel to the [010] direction. In this manner, the (111) sheets are linked into a single three-dimensional structure.

Experimental top

Crystals of the title compound, (I), were prepared according to the published procedure of Baddiley et al. (1943).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing a chain of alternating R₂²(8) and R₂²(10) rings along [110]. For the sake of clarity, the H atoms of the methyl group have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (1 − x, 1 − y, 1 − z), (−x, −y, 1 − z), (1 + x, 1 + y, z) and (−1 + x, −1 + y, z), respectively.
	Fig. 3. Part of the crystal structure of (I), showing a C(6) chain along [101]. For the sake of clarity, the H atoms bonded to C or N atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (), a hash (#) or an ampersand (&) are at the symmetry positions (−1/2 + x, 1/2 − y, −1/2 + z), (1/2 + x, 1/2 − y, 1/2 + z) and ? [Please complete]*, respectively.
	Fig. 4. A stereoview of part of the crystal structure of compound (I), showing the formation of a (111) sheet of R₂²(8), R₂²(10) and R₆⁶(32) rings. For the sake of clarity, the H atoms of the methyl group have been omitted.

4,5,6-Triamino-2-(methylsulfanyl)pyrimidine top

Crystal data top

C₅H₉N₅S	F(000) = 360
M_r = 171.23	D_x = 1.558 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1659 reflections
a = 7.7824 (2) Å	θ = 3.9–27.5°
b = 8.9623 (3) Å	µ = 0.38 mm⁻¹
c = 10.5078 (4) Å	T = 120 K
β = 95.261 (2)°	Rod, yellow
V = 729.81 (4) Å³	0.40 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	1659 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1533 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.9°
ϕ and ω scans	h = −9→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
T_min = 0.863, T_max = 0.963	l = −13→13
9338 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0279P)² + 0.4621P] where P = (F_o² + 2F_c²)/3
1659 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₅H₉N₅S	V = 729.81 (4) Å³
M_r = 171.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.7824 (2) Å	µ = 0.38 mm⁻¹
b = 8.9623 (3) Å	T = 120 K
c = 10.5078 (4) Å	0.40 × 0.20 × 0.10 mm
β = 95.261 (2)°

Data collection top

Bruker Nonius KappaCCD area-detector diffractometer	1659 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1533 reflections with I > 2σ(I)
T_min = 0.863, T_max = 0.963	R_int = 0.024
9338 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.11	Δρ_max = 0.32 e Å⁻³
1659 reflections	Δρ_min = −0.25 e Å⁻³
101 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S2	0.20359 (4)	0.56815 (4)	0.76430 (3)	0.01392 (11)
N1	0.29835 (13)	0.43416 (12)	0.56444 (10)	0.0127 (2)
N3	0.02044 (13)	0.36293 (12)	0.62592 (10)	0.0123 (2)
N4	−0.14454 (14)	0.18287 (13)	0.51618 (11)	0.0160 (2)
N5	0.11872 (15)	0.14725 (13)	0.33624 (11)	0.0181 (2)
N6	0.41062 (14)	0.32976 (13)	0.38935 (11)	0.0166 (2)
C2	0.16664 (15)	0.43941 (13)	0.63708 (12)	0.0114 (2)
C4	0.00458 (16)	0.26619 (14)	0.52615 (12)	0.0122 (3)
C5	0.13097 (16)	0.24760 (13)	0.44239 (12)	0.0121 (3)
C6	0.27909 (15)	0.33792 (14)	0.46462 (12)	0.0121 (3)
C21	0.00427 (17)	0.55706 (15)	0.83815 (13)	0.0167 (3)
H4A	−0.1695	0.1400	0.4415	0.019*
H4B	−0.2280	0.2287	0.5516	0.019*
H5A	0.1231	0.0533	0.3608	0.022*
H5B	0.0248	0.1595	0.2839	0.022*
H6A	0.4913	0.3987	0.3987	0.020*
H6B	0.3970	0.2779	0.3180	0.020*
H21A	−0.0930	0.5695	0.7729	0.025*
H21B	0.0012	0.6361	0.9024	0.025*
H21C	−0.0039	0.4596	0.8794	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.01338 (18)	0.01476 (18)	0.01352 (18)	−0.00151 (11)	0.00070 (12)	−0.00268 (11)
N1	0.0116 (5)	0.0127 (5)	0.0136 (5)	−0.0009 (4)	0.0007 (4)	−0.0007 (4)
N3	0.0122 (5)	0.0121 (5)	0.0123 (5)	−0.0003 (4)	0.0004 (4)	0.0012 (4)
N4	0.0142 (5)	0.0172 (6)	0.0169 (6)	−0.0054 (4)	0.0026 (4)	−0.0017 (4)
N5	0.0189 (6)	0.0155 (6)	0.0196 (6)	−0.0011 (4)	0.0009 (4)	−0.0030 (4)
N6	0.0150 (5)	0.0175 (6)	0.0180 (6)	−0.0040 (4)	0.0056 (4)	−0.0048 (4)
C2	0.0117 (6)	0.0108 (6)	0.0113 (6)	0.0009 (4)	−0.0009 (4)	0.0019 (4)
C4	0.0122 (6)	0.0109 (6)	0.0132 (6)	−0.0004 (4)	−0.0010 (5)	0.0036 (5)
C5	0.0136 (6)	0.0101 (6)	0.0123 (6)	0.0002 (4)	−0.0003 (5)	0.0012 (5)
C6	0.0124 (6)	0.0111 (6)	0.0128 (6)	0.0016 (4)	0.0006 (4)	0.0027 (5)
C21	0.0191 (7)	0.0176 (6)	0.0142 (6)	−0.0021 (5)	0.0050 (5)	−0.0017 (5)

Geometric parameters (Å, º) top

N1—C2	1.3337 (16)	S2—C21	1.7997 (13)
C2—N3	1.3242 (16)	C21—H21A	0.98
N3—C4	1.3573 (17)	C21—H21B	0.98
C4—C5	1.3888 (18)	C21—H21C	0.98
C5—C6	1.4104 (17)	N4—H4A	0.88
C6—N1	1.3557 (16)	N4—H4B	0.88
C4—N4	1.3759 (16)	N5—H5A	0.88
C5—N5	1.4292 (16)	N5—H5B	0.88
C6—N6	1.3518 (16)	N6—H6A	0.88
C2—S2	1.7694 (13)	N6—H6B	0.88

C6—N1—C2	115.40 (11)	C4—N4—H4A	114.9
N1—C2—N3	129.07 (11)	C4—N4—H4B	111.4
C2—N3—C4	114.55 (11)	H4A—N4—H4B	118.1
N3—C4—C5	123.14 (11)	C5—N5—H5A	112.1
C4—C5—C6	116.22 (11)	C5—N5—H5B	113.7
C5—C6—N1	121.60 (11)	H5A—N5—H5B	108.0
N3—C4—N4	114.95 (11)	C6—N6—H6A	117.9
C5—C4—N4	121.88 (12)	C6—N6—H6B	119.2
C4—C5—N5	124.73 (11)	H6A—N6—H6B	119.7
C6—C5—N5	119.04 (11)	S2—C21—H21A	109.5
C5—C6—N6	121.56 (11)	S2—C21—H21B	109.5
N1—C6—N6	116.82 (11)	H21A—C21—H21B	109.5
N1—C2—S2	112.03 (9)	S2—C21—H21C	109.5
N3—C2—S2	118.90 (9)	H21A—C21—H21C	109.5
C2—S2—C21	101.71 (6)	H21B—C21—H21C	109.5

C6—N1—C2—N3	0.61 (19)	C2—N1—C6—N6	−179.84 (11)
C6—N1—C2—S2	−179.87 (8)	C2—N1—C6—C5	−1.53 (17)
N3—C2—S2—C21	−3.12 (11)	C4—C5—C6—N6	−179.96 (11)
N1—C2—S2—C21	177.30 (9)	N5—C5—C6—N6	−1.20 (18)
N1—C2—N3—C4	0.02 (19)	C4—C5—C6—N1	1.81 (18)
S2—C2—N3—C4	−179.47 (9)	N5—C5—C6—N1	−179.43 (11)
C2—N3—C4—N4	178.05 (11)	N3—C4—N4—H4A	163
C2—N3—C4—C5	0.28 (18)	C4—C5—N5—H5A	−69
N3—C4—C5—C6	−1.16 (18)	C5—C6—N6—H6A	170
N4—C4—C5—C6	−178.78 (11)	N3—C4—N4—H4B	26
N3—C4—C5—N5	−179.84 (11)	C4—C5—N5—H5B	54
N4—C4—C5—N5	2.5 (2)	C5—C6—N6—H6B	10

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···S2ⁱ	0.88	2.75	3.5902 (12)	159
N5—H5A···N4ⁱⁱ	0.88	2.48	3.3379 (16)	166
N6—H6A···N1ⁱⁱⁱ	0.88	2.23	3.1049 (15)	176
N6—H6B···N5	0.88	2.48	2.8134 (16)	103

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₅H₉N₅S
M_r	171.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	7.7824 (2), 8.9623 (3), 10.5078 (4)
β (°)	95.261 (2)
V (Å³)	729.81 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Bruker Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.863, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	9338, 1659, 1533
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.11
No. of reflections	1659
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.25

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top

N1—C2	1.3337 (16)	C4—N4	1.3759 (16)
C2—N3	1.3242 (16)	C5—N5	1.4292 (16)
N3—C4	1.3573 (17)	C6—N6	1.3518 (16)
C4—C5	1.3888 (18)	C2—S2	1.7694 (13)
C5—C6	1.4104 (17)	S2—C21	1.7997 (13)
C6—N1	1.3557 (16)

C6—N1—C2	115.40 (11)	N1—C2—S2	112.03 (9)
N1—C2—N3	129.07 (11)	N3—C2—S2	118.90 (9)
C2—N3—C4	114.55 (11)	C2—S2—C21	101.71 (6)
N3—C4—C5	123.14 (11)	C4—N4—H4A	114.9
C4—C5—C6	116.22 (11)	C4—N4—H4B	111.4
C5—C6—N1	121.60 (11)	H4A—N4—H4B	118.1
N3—C4—N4	114.95 (11)	C5—N5—H5A	112.1
C5—C4—N4	121.88 (12)	C5—N5—H5B	113.7
C4—C5—N5	124.73 (11)	H5A—N5—H5B	108.0
C6—C5—N5	119.04 (11)	C6—N6—H6A	117.9
C5—C6—N6	121.56 (11)	C6—N6—H6B	119.2
N1—C6—N6	116.82 (11)	H6A—N6—H6B	119.7

N3—C4—N4—H4A	163	N3—C4—N4—H4B	26
C4—C5—N5—H5A	−69	C4—C5—N5—H5B	54
C5—C6—N6—H6A	170	C5—C6—N6—H6B	10

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···S2ⁱ	0.88	2.75	3.5902 (12)	159
N5—H5A···N4ⁱⁱ	0.88	2.48	3.3379 (16)	166
N6—H6A···N1ⁱⁱⁱ	0.88	2.23	3.1049 (15)	176
N6—H6B···N5	0.88	2.48	2.8134 (16)	103

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1.

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England. JC, ASR and MNM thank the Consejería de Innovación, Ciencia y Empresa (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Baddiley, J., Lythgoe, B., McNeil, D. & Todd, A. R. (1943). J. Chem. Soc. pp. 383–386. CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 62| Part 3| March 2006| Pages o142-o144

doi:10.1107/S0108270106003805

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