7-(5-Methyl­sulfanyl-β-d-erythrofuran­osyl)-7H-pyrrolo­[2,3-d]pyrimidin-4-amine monohydrate (MT-tubercidin·H2O)

Gainsford, G.J.; Fröhlich, R.F.G.; Evans, G.B.

doi:10.1107/S1600536810020179

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages o1688-o1689

doi:10.1107/S1600536810020179

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7-(5-Methylsulfanyl-β-D-erythrofuranosyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amine monohydrate (MT-tubercidin·H₂O)

Graeme J. Gainsford,^a ^* Richard F. G. Fröhlich ^a and Gary B. Evans ^a

^aCarbohydrate Chemistry Group, Industrial Research Limited, PO Box 31-310, Lower Hutt 5040, New Zealand
^*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 21 April 2010; accepted 28 May 2010; online 18 June 2010)

The title compound, C₁₂H₁₆N₄O₃S·H₂O, which has potential as a possible antimalarial drug, was studied when small deviations in melting points, for two differently aged preparations, were observed. The unexpected existence of a water molecule of crystallization is considered to be the cause of this variation. The 7H-pyrrolo[2,3-d]pyrimidine unit is very slightly puckered with a total puckering amplitude of 0.035 (2) Å; its mean plane makes an angle of 88.40 (12)° with the mean plane through the ribofuranosyl unit. In the crystal, the molecules are bound by strong O—H⋯N and N—H⋯O hydrogen bonds, utilizing all available protons and linking mainly through the water of crystallization.

Related literature

For details of the synthesis of and for background to the title compound, see: Riegelhaupt et al. (2010 ). For related structures, see: Seela et al. (2007 ); Abola & Sundaralingam (1973 ). For ring conformations, see: Cremer & Pople (1975 ). For hydrogen-bond motifs, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₂H₁₆N₄O₃S·H₂O
M_r = 314.36
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.790 (1) Å
b = 16.610 (3) Å
c = 18.020 (4) Å
V = 1433.7 (5) Å³
Z = 4
Cu Kα radiation
μ = 2.22 mm⁻¹
T = 100 K
0.50 × 0.02 × 0.02 mm

Data collection

Rigaku Spider diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.712, T_max = 1.0
8013 measured reflections
2582 independent reflections
2422 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.091
S = 1.08
2582 reflections
209 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 986 Friedel pairs
Flack parameter: 0.02 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2′—H2′O⋯N3ⁱ	0.79 (3)	1.99 (3)	2.776 (3)	173 (3)
O1W—H1A⋯O3′	0.82 (3)	1.96 (3)	2.748 (3)	162 (3)
O1W—H1B⋯O2′ⁱⁱ	0.80 (3)	2.07 (3)	2.848 (3)	162 (3)
O3′—H3′O⋯N1ⁱⁱⁱ	0.84 (3)	1.94 (3)	2.766 (3)	166 (3)
N6—H6A⋯O1W^iv	0.90 (3)	2.12 (3)	2.998 (3)	166 (3)
N6—H6B⋯O1W^v	0.82 (3)	2.13 (3)	2.928 (3)	164 (3)
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z; (iii) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku Americas, 2005 ); cell refinement: FSProcess in PROCESS-AUTO (Rigaku, 1998 ); data reduction: FSProcess in PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP in WinGX (Farrugia, 1999 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020179/kp2257sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020179/kp2257Isup2.hkl

checkCIF report

Comment top

The title compound was prepared as part of a study of purine transport or purine salvage pathway inhibitors with potential as alternative anti-malarial drugs (Riegelhaupt et al., 2010). Its common name is 7-(5'Methylthio-β-D-erythrofuranosyl)-7H-pyrrolo[2,3-d]pyrimidin-2-amine monohydrate usually shortened to MT-tubercidin.H₂O while the conventional name is 2-(4-Amino-pyrrolo[2,3-d]pyrimidin-7-yl)-5-methylsulfanylmethyl -tetrahydrofuran-3,4-diol monohydrate. The structural solution showed that in both batches there was an unexpected water molecule of crystallization, a likely cause of the variation in melting points with differently aged samples. The results for the better crystals are presented here. The asymmetric unit contents are shown in Figure 1.

The absolute configuration is defined as C1'(R), C2'(R), C3'(S) and C4'(S) with the ribofuranosyl unit adopting an (C2'-)endo-envelope Δ conformation (Q(2) 0.434 (3) Å, ϕ(2) 76.3 (3)°, Cremer & Pople (1975)). The 7H-pyrrolo[2,3-d]pyrimidine unit is very slightly puckered with total puckering amplitude of 0.035 (2) Å: its mean plane makes an angle of 88.40 (12)° with the mean plane through the ribofuranosyl unit. The orientation of the C4'–C5' bond is slightly different (with O4'-C1'-N9—C4 torsion angle of -126.6 (2)°) to that found in the related compounds 2'-Deoxy-2-fluorotubercidin (-110.2 (3)°, Seela et al., 2007) and tubercidin (-112.8 (4)°, Abola & Sundaralingam, 1973). Other dimensions are normal.

The molecules are packed in three dimensions using 6 strong hydrogen bonds of the O–H···O and N–H···O types (Table 1). The graph set motifs (Etter et al., 1990; Bernstein et al., 1995) are extensive at the binary level: C²₂(7), C²₂(9), C²₂(11), C²₂(12), C²₂(17), D³₃(10), D³₃(13), D³₃(14), D³₃(15), D³₃(17) and D³₃(18) types are found being based mainly on linked chains through the included water molecule (the latter feature is shown in Figure 2). The C–H···π interaction involving the methyl hydrogen H6'A and the 5-membered pyrrolo ring (at 2.80 Å) is considered fortuitous but noted here for completeness.

Related literature top

For details of the synthesis of and for background to the title compound, see: Riegelhaupt et al. (2010). For related structures, see: Seela et al. (2007); Abola & Sundaralingam (1973). For ring conformations, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

The title compound was prepared as described in the supplementary data section (compound 10) by Riegelhaupt et al. (2010).

Computing details top

Data collection: CrystalClear (Rigaku Americas, 2005); cell refinement: FSProcess in PROCESS-AUTO (Rigaku, 1998); data reduction: FSProcess in PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP in WinGX (Farrugia, 1999) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. An ORTEP (Farrugia, 1999) view showing the asymmetric unit of (I) with 50% probabilility ellipsoids. The dotted lines represents an intermolecular hydrogen bond.
	Fig. 2. Mercury cell packing view (Macrae et al., 2006) emphasizing the links with the water of crystallization: conventional hydrogen bonds not running up the a axis are shown (dotted lines).For the complete hydrogen bonding set see Table 1. Contact atoms are shown in ball mode; H atoms are omitted for clarity. Symmetry operations: (i) 1 - x, y - 1/2, 3/2 - z (ii) 1/2 - x, 1 - y, 1/2 + z.

7-(5-Methylsulfanyl-β-D-erythrofuranosyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amine monohydrate top

Crystal data top

C₁₂H₁₆N₄O₃S·H₂O	F(000) = 664
M_r = 314.36	D_x = 1.456 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1322 reflections
a = 4.790 (1) Å	θ = 10.7–72.1°
b = 16.610 (3) Å	µ = 2.22 mm⁻¹
c = 18.020 (4) Å	T = 100 K
V = 1433.7 (5) Å³	Needle, colourless
Z = 4	0.50 × 0.02 × 0.02 mm

Data collection top

Rigaku Spider diffractometer	2582 independent reflections
Radiation source: Rigaku MM007 rotating anode	2422 reflections with I > 2σ(I)
Rigaku VariMax-HF Confocal Optical System monochromator	R_int = 0.045
Detector resolution: 10 pixels mm^-1	θ_max = 71.9°, θ_min = 7.3°
ω–scans	h = −5→2
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −20→20
T_min = 0.712, T_max = 1.0	l = −21→19
8013 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.031P)² + 0.7234P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2582 reflections	Δρ_max = 0.29 e Å⁻³
209 parameters	Δρ_min = −0.33 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 986 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (2)

Crystal data top

C₁₂H₁₆N₄O₃S·H₂O	V = 1433.7 (5) Å³
M_r = 314.36	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 4.790 (1) Å	µ = 2.22 mm⁻¹
b = 16.610 (3) Å	T = 100 K
c = 18.020 (4) Å	0.50 × 0.02 × 0.02 mm

Data collection top

Rigaku Spider diffractometer	2582 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2422 reflections with I > 2σ(I)
T_min = 0.712, T_max = 1.0	R_int = 0.045
8013 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.091	Δρ_max = 0.29 e Å⁻³
S = 1.08	Δρ_min = −0.33 e Å⁻³
2582 reflections	Absolute structure: Flack (1983), 986 Friedel pairs
209 parameters	Absolute structure parameter: 0.02 (2)
2 restraints

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
S1	0.97214 (14)	0.38389 (4)	0.36963 (3)	0.01889 (16)
O1W	0.2297 (5)	0.66101 (10)	0.58560 (11)	0.0210 (4)
H1A	0.363 (5)	0.6337 (16)	0.5723 (16)	0.032*
H1B	0.110 (6)	0.6336 (16)	0.6041 (16)	0.032*
O2'	0.8902 (4)	0.53482 (10)	0.64314 (9)	0.0155 (4)
H2'O	0.971 (7)	0.5148 (17)	0.6768 (15)	0.023*
O3'	0.6026 (4)	0.56178 (10)	0.51450 (10)	0.0171 (4)
H3'O	0.553 (7)	0.5708 (17)	0.4704 (16)	0.026*
O4'	0.4719 (4)	0.38417 (10)	0.55162 (8)	0.0166 (4)
N1	0.1518 (5)	0.40830 (11)	0.87950 (11)	0.0148 (5)
C2	0.0798 (6)	0.45356 (14)	0.82094 (13)	0.0152 (5)
H2	−0.0681	0.4906	0.8293	0.018*
N3	0.1866 (5)	0.45398 (11)	0.75258 (11)	0.0132 (4)
C4	0.3891 (6)	0.39748 (13)	0.74463 (13)	0.0126 (5)
C5	0.4795 (6)	0.34442 (13)	0.79930 (13)	0.0130 (5)
C6	0.3551 (5)	0.35230 (14)	0.87012 (13)	0.0144 (5)
N6	0.4318 (5)	0.30707 (13)	0.92757 (12)	0.0188 (5)
H6A	0.355 (7)	0.3126 (17)	0.9726 (16)	0.028*
H6B	0.552 (7)	0.2722 (17)	0.9214 (17)	0.028*
C7	0.6937 (6)	0.29487 (14)	0.76725 (14)	0.0155 (5)
H7	0.7949	0.2532	0.7913	0.019*
C8	0.7228 (6)	0.31939 (14)	0.69593 (14)	0.0141 (5)
H8	0.8501	0.2971	0.6611	0.017*
N9	0.5374 (4)	0.38247 (11)	0.68120 (10)	0.0128 (4)
C1'	0.5393 (6)	0.43227 (14)	0.61535 (12)	0.0139 (5)
H1'	0.3971	0.4760	0.6208	0.017*
C2'	0.8210 (6)	0.46963 (14)	0.59653 (13)	0.0133 (5)
H2'	0.9698	0.4276	0.5998	0.016*
C3'	0.7750 (6)	0.49214 (14)	0.51606 (14)	0.0138 (5)
H3'	0.9552	0.5009	0.4892	0.017*
C4'	0.6191 (6)	0.41680 (15)	0.48763 (13)	0.0139 (5)
H4'	0.4815	0.4328	0.4486	0.017*
C5'	0.8164 (6)	0.35258 (16)	0.45686 (13)	0.0188 (6)
H5'A	0.7116	0.3019	0.4492	0.023*
H5'B	0.9660	0.3419	0.4935	0.023*
C6'	0.7305 (6)	0.34328 (16)	0.30226 (15)	0.0219 (6)
H6'A	0.7358	0.2843	0.3041	0.033*
H6'B	0.7835	0.3615	0.2525	0.033*
H6'C	0.5412	0.3620	0.3137	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0145 (4)	0.0267 (3)	0.0155 (3)	−0.0023 (3)	0.0037 (3)	−0.0050 (3)
O1W	0.0206 (12)	0.0217 (9)	0.0208 (10)	−0.0034 (8)	0.0045 (8)	0.0000 (8)
O2'	0.0170 (10)	0.0174 (8)	0.0120 (9)	−0.0004 (7)	−0.0028 (8)	−0.0007 (7)
O3'	0.0200 (11)	0.0205 (9)	0.0108 (8)	0.0075 (8)	−0.0027 (8)	0.0023 (7)
O4'	0.0138 (10)	0.0262 (9)	0.0096 (8)	−0.0044 (9)	0.0006 (8)	−0.0020 (7)
N1	0.0160 (12)	0.0172 (10)	0.0113 (10)	0.0002 (8)	−0.0001 (9)	0.0006 (8)
C2	0.0135 (14)	0.0164 (11)	0.0157 (12)	0.0007 (10)	−0.0020 (11)	−0.0023 (10)
N3	0.0108 (11)	0.0172 (9)	0.0117 (11)	0.0010 (8)	−0.0005 (9)	−0.0015 (9)
C4	0.0102 (13)	0.0155 (11)	0.0121 (12)	−0.0032 (9)	−0.0034 (10)	−0.0014 (10)
C5	0.0113 (14)	0.0155 (10)	0.0123 (11)	−0.0002 (10)	0.0009 (11)	0.0012 (9)
C6	0.0153 (14)	0.0157 (11)	0.0121 (11)	−0.0018 (10)	−0.0028 (11)	−0.0004 (10)
N6	0.0235 (15)	0.0226 (10)	0.0104 (10)	0.0066 (10)	0.0018 (10)	0.0015 (9)
C7	0.0130 (14)	0.0162 (11)	0.0174 (12)	0.0012 (10)	−0.0002 (12)	0.0008 (10)
C8	0.0105 (14)	0.0158 (11)	0.0160 (13)	0.0017 (10)	0.0025 (11)	−0.0035 (10)
N9	0.0104 (11)	0.0170 (9)	0.0110 (10)	−0.0010 (9)	0.0025 (9)	0.0006 (8)
C1'	0.0133 (15)	0.0196 (11)	0.0089 (11)	0.0001 (10)	−0.0008 (10)	−0.0001 (9)
C2'	0.0077 (13)	0.0178 (11)	0.0142 (12)	−0.0002 (10)	−0.0020 (11)	0.0008 (10)
C3'	0.0110 (14)	0.0174 (11)	0.0131 (12)	0.0020 (10)	0.0011 (11)	0.0001 (10)
C4'	0.0098 (14)	0.0227 (12)	0.0091 (11)	0.0009 (10)	−0.0027 (10)	0.0029 (10)
C5'	0.0184 (15)	0.0227 (12)	0.0153 (12)	0.0002 (12)	−0.0011 (12)	−0.0042 (11)
C6'	0.0177 (16)	0.0283 (14)	0.0197 (14)	−0.0005 (12)	−0.0007 (12)	−0.0054 (12)

Geometric parameters (Å, º) top

S1—C6'	1.808 (3)	N6—H6A	0.90 (3)
S1—C5'	1.816 (3)	N6—H6B	0.82 (3)
O1W—H1A	0.820 (18)	C7—C8	1.355 (3)
O1W—H1B	0.805 (18)	C7—H7	0.9500
O2'—C2'	1.410 (3)	C8—N9	1.399 (3)
O2'—H2'O	0.79 (3)	C8—H8	0.9500
O3'—C3'	1.422 (3)	N9—C1'	1.446 (3)
O3'—H3'O	0.84 (3)	C1'—C2'	1.523 (4)
O4'—C1'	1.436 (3)	C1'—H1'	1.0000
O4'—C4'	1.456 (3)	C2'—C3'	1.514 (3)
N1—C2	1.341 (3)	C2'—H2'	1.0000
N1—C6	1.357 (3)	C3'—C4'	1.545 (3)
C2—N3	1.334 (3)	C3'—H3'	1.0000
C2—H2	0.9500	C4'—C5'	1.529 (3)
N3—C4	1.357 (3)	C4'—H4'	1.0000
C4—N9	1.369 (3)	C5'—H5'A	0.9900
C4—C5	1.391 (3)	C5'—H5'B	0.9900
C5—C6	1.415 (3)	C6'—H6'A	0.9800
C5—C7	1.436 (3)	C6'—H6'B	0.9800
C6—N6	1.331 (3)	C6'—H6'C	0.9800

C6'—S1—C5'	102.20 (14)	O4'—C1'—H1'	109.2
H1A—O1W—H1B	111 (3)	N9—C1'—H1'	109.2
C2'—O2'—H2'O	104 (2)	C2'—C1'—H1'	109.2
C3'—O3'—H3'O	109 (2)	O2'—C2'—C3'	114.53 (19)
C1'—O4'—C4'	108.50 (17)	O2'—C2'—C1'	112.9 (2)
C2—N1—C6	118.1 (2)	C3'—C2'—C1'	100.7 (2)
N3—C2—N1	129.2 (2)	O2'—C2'—H2'	109.5
N3—C2—H2	115.4	C3'—C2'—H2'	109.5
N1—C2—H2	115.4	C1'—C2'—H2'	109.5
C2—N3—C4	111.6 (2)	O3'—C3'—C2'	107.7 (2)
N3—C4—N9	125.8 (2)	O3'—C3'—C4'	111.8 (2)
N3—C4—C5	125.9 (2)	C2'—C3'—C4'	100.83 (19)
N9—C4—C5	108.3 (2)	O3'—C3'—H3'	112.0
C4—C5—C6	116.7 (2)	C2'—C3'—H3'	112.0
C4—C5—C7	107.5 (2)	C4'—C3'—H3'	112.0
C6—C5—C7	135.8 (2)	O4'—C4'—C5'	109.07 (19)
N6—C6—N1	119.2 (2)	O4'—C4'—C3'	105.84 (19)
N6—C6—C5	122.2 (2)	C5'—C4'—C3'	112.7 (2)
N1—C6—C5	118.6 (2)	O4'—C4'—H4'	109.7
C6—N6—H6A	122 (2)	C5'—C4'—H4'	109.7
C6—N6—H6B	119 (2)	C3'—C4'—H4'	109.7
H6A—N6—H6B	119 (3)	C4'—C5'—S1	111.59 (18)
C8—C7—C5	106.4 (2)	C4'—C5'—H5'A	109.3
C8—C7—H7	126.8	S1—C5'—H5'A	109.3
C5—C7—H7	126.8	C4'—C5'—H5'B	109.3
C7—C8—N9	109.9 (2)	S1—C5'—H5'B	109.3
C7—C8—H8	125.1	H5'A—C5'—H5'B	108.0
N9—C8—H8	125.1	S1—C6'—H6'A	109.5
C4—N9—C8	107.91 (19)	S1—C6'—H6'B	109.5
C4—N9—C1'	125.7 (2)	H6'A—C6'—H6'B	109.5
C8—N9—C1'	125.5 (2)	S1—C6'—H6'C	109.5
O4'—C1'—N9	109.66 (18)	H6'A—C6'—H6'C	109.5
O4'—C1'—C2'	104.34 (19)	H6'B—C6'—H6'C	109.5
N9—C1'—C2'	114.9 (2)

C6—N1—C2—N3	−2.3 (4)	C4'—O4'—C1'—N9	−148.2 (2)
N1—C2—N3—C4	2.3 (4)	C4'—O4'—C1'—C2'	−24.6 (2)
C2—N3—C4—N9	179.6 (2)	C4—N9—C1'—O4'	−126.6 (2)
C2—N3—C4—C5	0.3 (3)	C8—N9—C1'—O4'	65.6 (3)
N3—C4—C5—C6	−2.4 (4)	C4—N9—C1'—C2'	116.2 (3)
N9—C4—C5—C6	178.2 (2)	C8—N9—C1'—C2'	−51.6 (3)
N3—C4—C5—C7	179.5 (2)	O4'—C1'—C2'—O2'	164.56 (18)
N9—C4—C5—C7	0.1 (3)	N9—C1'—C2'—O2'	−75.3 (3)
C2—N1—C6—N6	179.5 (2)	O4'—C1'—C2'—C3'	42.0 (2)
C2—N1—C6—C5	−0.2 (3)	N9—C1'—C2'—C3'	162.11 (19)
C4—C5—C6—N6	−177.4 (2)	O2'—C2'—C3'—O3'	−45.9 (3)
C7—C5—C6—N6	0.1 (5)	C1'—C2'—C3'—O3'	75.5 (2)
C4—C5—C6—N1	2.2 (3)	O2'—C2'—C3'—C4'	−163.2 (2)
C7—C5—C6—N1	179.7 (3)	C1'—C2'—C3'—C4'	−41.8 (2)
C4—C5—C7—C8	−0.1 (3)	C1'—O4'—C4'—C5'	119.1 (2)
C6—C5—C7—C8	−177.8 (3)	C1'—O4'—C4'—C3'	−2.5 (2)
C5—C7—C8—N9	0.2 (3)	O3'—C3'—C4'—O4'	−85.9 (2)
N3—C4—N9—C8	−179.4 (2)	C2'—C3'—C4'—O4'	28.4 (2)
C5—C4—N9—C8	0.0 (3)	O3'—C3'—C4'—C5'	155.0 (2)
N3—C4—N9—C1'	11.0 (4)	C2'—C3'—C4'—C5'	−90.8 (2)
C5—C4—N9—C1'	−169.5 (2)	O4'—C4'—C5'—S1	172.20 (16)
C7—C8—N9—C4	−0.1 (3)	C3'—C4'—C5'—S1	−70.5 (2)
C7—C8—N9—C1'	169.5 (2)	C6'—S1—C5'—C4'	−91.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2′—H2′O···N3ⁱ	0.79 (3)	1.99 (3)	2.776 (3)	173 (3)
O1W—H1A···O3′	0.82 (3)	1.96 (3)	2.748 (3)	162 (3)
O1W—H1B···O2′ⁱⁱ	0.80 (3)	2.07 (3)	2.848 (3)	162 (3)
O3′—H3′O···N1ⁱⁱⁱ	0.84 (3)	1.94 (3)	2.766 (3)	166 (3)
N6—H6A···O1W^iv	0.90 (3)	2.12 (3)	2.998 (3)	166 (3)
N6—H6B···O1W^v	0.82 (3)	2.13 (3)	2.928 (3)	164 (3)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1/2, −y+1, z−1/2; (iv) −x+1/2, −y+1, z+1/2; (v) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₄O₃S·H₂O
M_r	314.36
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	4.790 (1), 16.610 (3), 18.020 (4)
V (Å³)	1433.7 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.22
Crystal size (mm)	0.50 × 0.02 × 0.02

Data collection
Diffractometer	Rigaku Spider diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.712, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	8013, 2582, 2422
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.091, 1.08
No. of reflections	2582
No. of parameters	209
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.33
Absolute structure	Flack (1983), 986 Friedel pairs
Absolute structure parameter	0.02 (2)

Computer programs: CrystalClear (Rigaku Americas, 2005), FSProcess in PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), ORTEP in WinGX (Farrugia, 1999) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2'—H2'O···N3ⁱ	0.79 (3)	1.99 (3)	2.776 (3)	173 (3)
O1W—H1A···O3'	0.82 (3)	1.96 (3)	2.748 (3)	162 (3)
O1W—H1B···O2'ⁱⁱ	0.80 (3)	2.07 (3)	2.848 (3)	162 (3)
O3'—H3'O···N1ⁱⁱⁱ	0.84 (3)	1.94 (3)	2.766 (3)	166 (3)
N6—H6A···O1W^iv	0.90 (3)	2.12 (3)	2.998 (3)	166 (3)
N6—H6B···O1W^v	0.82 (3)	2.13 (3)	2.928 (3)	164 (3)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1/2, −y+1, z−1/2; (iv) −x+1/2, −y+1, z+1/2; (v) −x+1, y−1/2, −z+3/2.

Acknowledgements

We thank the MacDiarmid Institute for Advanced Materials and Nanotechnology for funding of the diffractometer equipment.

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