Synthesis and crystal structure of a silver(I) 6-methyl­mercaptopurine riboside com­plex

Silver nitrate reacts with 6-methyl­mercaptopurine riboside (6-MMPR) in aqueous solution containing methanol and dimethyl sulfoxide at room tem­per­ature to give a colourless crystalline com­plex, namely, bis­(6-methyl­mercaptopurine riboside-κN⁷)(nitrato-κ²O,O′)silver(I) 2.32-hydrate, [Ag(NO₃)(C₁₁H₁₄N₄O₄S)₂]·2.32H₂O. The crystal structure, determined from synchrotron diffraction data, shows a central Ag^I ion on a crystallographic twofold rotation axis, coordinated in an almost linear fashion by two 6-MMPR ligands via atom N7 (purine numbering), with the nitrate counter-ion loosely coordinated as a bidentate ligand, forming a discrete mol­ecular com­plex as an approximate dihydrate. The com­plex and water mol­ecules are connected in a three-dimensional network by hydrogen bonding.

Computing details

Bis(6-methylmercaptopurine riboside-κN⁷)(nitrato-κ²O,O')silver(I) 2.32-hydrate

Crystal data

[Ag(NO3)(C11H14N4O4S)2]·2.32H2O	Dx = 1.766 Mg m^−3
Mr = 808.23	Synchrotron radiation, λ = 0.6889 Å
Orthorhombic, C2221	Cell parameters from 9898 reflections
a = 4.8791 (10) Å	θ = 2.3–27.4°
b = 22.049 (5) Å	µ = 0.82 mm^−1
c = 28.256 (6) Å	T = 100 K
V = 3039.8 (11) Å^3	Needle, colourless
Z = 4	0.06 × 0.02 × 0.01 mm
F(000) = 1653

Data collection

Rigaku Saturn 724+ CCD on kappa diffractometer	3410 reflections with I > 2σ(I)
Radiation source: Diamond Light Source beamline I19	Rint = 0.045
wide–frame ω scans	θmax = 27.4°, θmin = 1.9°
Absorption correction: multi-scan (SADABS2016; Krause et al., 2015)	h = −6→4
Tmin = 0.734, Tmax = 0.976	k = −29→29
14892 measured reflections	l = −37→37
3672 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0364P)^2 + 0.133P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
3672 reflections	Δρmax = 0.62 e Å^−3
245 parameters	Δρmin = −0.53 e Å^−3
6 restraints	Absolute structure: Flack x determined using 1339 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.034 (13)

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ag1	0.500000	0.48262 (2)	0.250000	0.01830 (11)
N1	0.4555 (7)	0.62576 (11)	0.39219 (9)	0.0137 (7)
C2	0.6321 (8)	0.61247 (15)	0.42763 (11)	0.0141 (7)
H2	0.625192	0.638377	0.454471	0.017*
N3	0.8149 (7)	0.56747 (12)	0.42956 (9)	0.0138 (6)
C4	0.8081 (8)	0.53252 (13)	0.39020 (10)	0.0114 (7)
C5	0.6400 (7)	0.54124 (13)	0.35099 (11)	0.0112 (7)
C6	0.4602 (9)	0.59102 (13)	0.35238 (10)	0.0128 (7)
N7	0.6944 (7)	0.49620 (11)	0.31771 (9)	0.0132 (6)
C8	0.8843 (8)	0.46154 (14)	0.33674 (11)	0.0154 (8)
H8	0.958394	0.426672	0.321696	0.019*
N9	0.9641 (7)	0.48148 (10)	0.38105 (8)	0.0111 (6)
S10	0.2470 (2)	0.60662 (4)	0.30433 (3)	0.0168 (2)
C11	0.0746 (8)	0.67522 (15)	0.32338 (12)	0.0208 (9)
H11A	−0.052445	0.688637	0.298633	0.031*
H11B	0.210604	0.707039	0.329266	0.031*
H11C	−0.027732	0.667085	0.352547	0.031*
C12	1.1592 (8)	0.45314 (14)	0.41483 (11)	0.0127 (7)
H12	1.290651	0.484284	0.426943	0.015*
O13	1.3034 (6)	0.40653 (10)	0.39125 (8)	0.0143 (5)
C14	1.2234 (8)	0.34702 (13)	0.41085 (11)	0.0132 (7)
H14	1.362906	0.333958	0.434694	0.016*
C15	0.9533 (9)	0.35998 (12)	0.43597 (10)	0.0128 (8)
H15	0.800478	0.361558	0.412424	0.015*
C16	1.0051 (10)	0.42359 (12)	0.45650 (9)	0.0118 (5)
H16	0.831291	0.445351	0.464463	0.014*
C17	1.2120 (9)	0.30047 (15)	0.37094 (12)	0.0195 (8)
H17A	1.387327	0.301301	0.353315	0.023*
H17B	1.190334	0.259462	0.384707	0.023*
O18	0.9923 (9)	0.31172 (10)	0.33897 (8)	0.0271 (6)
H18	1.062 (5)	0.324 (3)	0.3133 (8)	0.07 (2)*
O19	0.8890 (6)	0.31806 (10)	0.47253 (9)	0.0179 (6)
H19	0.833 (10)	0.2851 (13)	0.4618 (17)	0.040 (14)*
O20	1.1903 (6)	0.42100 (11)	0.49545 (8)	0.0146 (5)
H20	1.108 (10)	0.425 (2)	0.5211 (11)	0.056 (18)*
N21	0.500000	0.34498 (18)	0.250000	0.0337 (11)
O22	0.500000	0.28878 (17)	0.250000	0.0609 (15)
O23	0.2961 (8)	0.37404 (13)	0.26563 (12)	0.0436 (9)
O24	0.6331 (6)	0.21756 (11)	0.44335 (9)	0.0216 (6)
H24A	0.581 (9)	0.1987 (18)	0.4672 (10)	0.031 (13)*
H24B	0.732 (9)	0.1935 (17)	0.4280 (15)	0.038 (14)*
O25	1.037 (7)	0.2439 (7)	0.2636 (6)	0.036 (8)	0.157 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.0257 (2)	0.01947 (16)	0.00969 (14)	0.000	−0.00389 (19)	0.000
N1	0.015 (2)	0.0129 (10)	0.0133 (10)	0.0015 (12)	0.0001 (12)	−0.0016 (9)
C2	0.016 (2)	0.0154 (14)	0.0107 (13)	−0.0020 (13)	0.0014 (13)	−0.0019 (11)
N3	0.0176 (19)	0.0148 (12)	0.0090 (11)	−0.0019 (12)	−0.0012 (11)	−0.0013 (9)
C4	0.012 (2)	0.0121 (13)	0.0097 (12)	−0.0008 (12)	0.0007 (13)	0.0002 (10)
C5	0.011 (2)	0.0126 (13)	0.0102 (13)	−0.0020 (12)	0.0005 (12)	0.0022 (11)
C6	0.014 (2)	0.0139 (12)	0.0106 (11)	−0.0027 (13)	0.0009 (14)	0.0017 (9)
N7	0.0166 (18)	0.0135 (12)	0.0093 (11)	0.0003 (11)	−0.0021 (11)	0.0014 (9)
C8	0.024 (2)	0.0112 (13)	0.0110 (13)	0.0022 (13)	−0.0006 (13)	−0.0011 (11)
N9	0.0140 (18)	0.0106 (10)	0.0088 (9)	0.0017 (14)	−0.0016 (11)	0.0007 (8)
S10	0.0210 (6)	0.0186 (4)	0.0109 (3)	0.0053 (3)	−0.0029 (3)	0.0005 (3)
C11	0.025 (3)	0.0178 (15)	0.0201 (15)	0.0101 (14)	−0.0021 (14)	0.0024 (12)
C12	0.011 (2)	0.0145 (14)	0.0121 (13)	0.0007 (13)	−0.0014 (13)	0.0012 (11)
O13	0.0152 (15)	0.0129 (10)	0.0147 (10)	0.0010 (9)	0.0048 (10)	0.0033 (8)
C14	0.013 (2)	0.0127 (13)	0.0139 (13)	0.0015 (13)	0.0007 (14)	0.0018 (11)
C15	0.015 (3)	0.0129 (12)	0.0109 (12)	−0.0016 (13)	0.0010 (14)	0.0020 (9)
C16	0.0104 (17)	0.0154 (11)	0.0095 (10)	0.0032 (17)	−0.0017 (18)	0.0004 (9)
C17	0.024 (2)	0.0161 (14)	0.0181 (15)	0.0030 (14)	0.0033 (16)	−0.0015 (12)
O18	0.0317 (17)	0.0296 (11)	0.0199 (10)	−0.0023 (17)	−0.0077 (17)	−0.0008 (9)
O19	0.0259 (16)	0.0130 (11)	0.0148 (10)	−0.0049 (9)	0.0024 (10)	0.0051 (9)
O20	0.0145 (15)	0.0198 (11)	0.0096 (10)	0.0005 (10)	−0.0025 (10)	0.0000 (8)
N21	0.053 (4)	0.0209 (18)	0.028 (2)	0.000	0.000 (4)	0.000
O22	0.095 (4)	0.0182 (17)	0.070 (3)	0.000	−0.028 (5)	0.000
O23	0.051 (3)	0.0278 (14)	0.052 (2)	−0.0067 (15)	0.0118 (17)	−0.0023 (13)
O24	0.0278 (18)	0.0165 (11)	0.0205 (12)	0.0033 (11)	0.0021 (12)	−0.0015 (10)
O25	0.05 (2)	0.024 (8)	0.039 (11)	0.002 (10)	0.006 (13)	−0.007 (6)

Geometric parameters (Å, º)

Ag1—N7	2.156 (3)	C12—O13	1.412 (4)
Ag1—N7^i	2.156 (3)	C12—C16	1.541 (4)
Ag1—O23	2.630 (3)	O13—C14	1.477 (4)
Ag1—O23^i	2.630 (3)	C14—H14	1.000
N1—C2	1.353 (4)	C14—C15	1.524 (5)
N1—C6	1.361 (4)	C14—C17	1.526 (4)
C2—H2	0.950	C15—H15	1.000
C2—N3	1.335 (5)	C15—C16	1.539 (4)
N3—C4	1.353 (4)	C15—O19	1.421 (3)
C4—C5	1.392 (5)	C16—H16	1.000
C4—N9	1.383 (4)	C16—O20	1.425 (4)
C5—C6	1.406 (5)	C17—H17A	0.990
C5—N7	1.393 (4)	C17—H17B	0.990
C6—S10	1.745 (4)	C17—O18	1.424 (5)
N7—C8	1.316 (4)	O18—H18	0.846 (14)
C8—H8	0.950	O19—H19	0.834 (14)
C8—N9	1.383 (4)	O20—H20	0.835 (14)
N9—C12	1.486 (4)	N21—O22	1.239 (5)
S10—C11	1.813 (3)	N21—O23	1.263 (4)
C11—H11A	0.980	N21—O23^i	1.263 (4)
C11—H11B	0.980	O24—H24A	0.832 (13)
C11—H11C	0.980	O24—H24B	0.839 (14)
C12—H12	1.000
N7—Ag1—N7^i	164.03 (13)	N9—C12—C16	110.9 (3)
N7—Ag1—O23	98.27 (10)	H12—C12—O13	110.0
N7^i—Ag1—O23	96.26 (10)	H12—C12—C16	110.0
N7—Ag1—O23^i	96.26 (10)	O13—C12—C16	107.2 (2)
N7^i—Ag1—O23^i	98.27 (10)	C12—O13—C14	109.8 (2)
O23—Ag1—O23^i	48.91 (16)	O13—C14—H14	109.2
C2—N1—C6	118.6 (3)	O13—C14—C15	103.7 (2)
N1—C2—H2	116.0	O13—C14—C17	109.3 (2)
N1—C2—N3	128.1 (3)	H14—C14—C15	109.2
H2—C2—N3	116.0	H14—C14—C17	109.2
C2—N3—C4	111.9 (3)	C15—C14—C17	116.0 (3)
N3—C4—C5	126.1 (3)	C14—C15—H15	110.0
N3—C4—N9	127.1 (3)	C14—C15—C16	101.8 (3)
C5—C4—N9	106.7 (3)	C14—C15—O19	114.0 (3)
C4—C5—C6	117.0 (3)	H15—C15—C16	110.0
C4—C5—N7	109.1 (3)	H15—C15—O19	110.0
C6—C5—N7	134.0 (3)	C16—C15—O19	110.8 (2)
N1—C6—C5	118.2 (3)	C12—C16—C15	100.2 (2)
N1—C6—S10	121.5 (3)	C12—C16—H16	112.5
C5—C6—S10	120.3 (2)	C12—C16—O20	107.3 (3)
Ag1—N7—C5	127.9 (2)	C15—C16—H16	112.5
Ag1—N7—C8	126.3 (2)	C15—C16—O20	111.0 (2)
C5—N7—C8	105.8 (3)	H16—C16—O20	112.5
N7—C8—H8	123.7	C14—C17—H17A	109.1
N7—C8—N9	112.6 (3)	C14—C17—H17B	109.1
H8—C8—N9	123.7	C14—C17—O18	112.3 (3)
C4—N9—C8	105.8 (3)	H17A—C17—H17B	107.9
C4—N9—C12	125.1 (2)	H17A—C17—O18	109.1
C8—N9—C12	128.9 (3)	H17B—C17—O18	109.1
C6—S10—C11	102.13 (16)	C17—O18—H18	107.2 (16)
S10—C11—H11A	109.5	C15—O19—H19	112 (4)
S10—C11—H11B	109.5	C16—O20—H20	111 (4)
S10—C11—H11C	109.5	O22—N21—O23	120.5 (2)
H11A—C11—H11B	109.5	O22—N21—O23^i	120.5 (2)
H11A—C11—H11C	109.5	O23—N21—O23^i	119.0 (4)
H11B—C11—H11C	109.5	Ag1—O23—N21	96.0 (2)
N9—C12—H12	110.0	H24A—O24—H24B	106 (4)
N9—C12—O13	108.8 (2)
C6—N1—C2—N3	−1.4 (5)	N1—C6—S10—C11	3.1 (3)
N1—C2—N3—C4	−0.8 (5)	C5—C6—S10—C11	−177.8 (3)
C2—N3—C4—C5	1.5 (5)	C4—N9—C12—O13	−173.2 (3)
C2—N3—C4—N9	−178.3 (3)	C4—N9—C12—C16	69.2 (4)
N3—C4—C5—C6	0.0 (5)	C8—N9—C12—O13	12.0 (5)
N3—C4—C5—N7	179.6 (3)	C8—N9—C12—C16	−105.7 (4)
N9—C4—C5—C6	179.8 (3)	N9—C12—O13—C14	−112.2 (3)
N9—C4—C5—N7	−0.6 (4)	C16—C12—O13—C14	7.7 (4)
C2—N1—C6—C5	2.9 (5)	C12—O13—C14—C15	18.6 (3)
C2—N1—C6—S10	−177.9 (3)	C12—O13—C14—C17	142.9 (3)
C4—C5—C6—N1	−2.3 (5)	O13—C14—C15—C16	−36.9 (3)
C4—C5—C6—S10	178.6 (3)	O13—C14—C15—O19	−156.3 (3)
N7—C5—C6—N1	178.3 (3)	C17—C14—C15—C16	−156.7 (3)
N7—C5—C6—S10	−0.9 (6)	C17—C14—C15—O19	83.9 (3)
C4—C5—N7—Ag1	178.6 (2)	C14—C15—C16—C12	40.3 (3)
C4—C5—N7—C8	0.9 (4)	C14—C15—C16—O20	−72.9 (3)
C6—C5—N7—Ag1	−1.8 (6)	O19—C15—C16—C12	161.9 (3)
C6—C5—N7—C8	−179.6 (4)	O19—C15—C16—O20	48.8 (5)
Ag1—N7—C8—N9	−178.7 (2)	N9—C12—C16—C15	88.3 (3)
C5—N7—C8—N9	−0.9 (4)	N9—C12—C16—O20	−155.7 (2)
N7—C8—N9—C4	0.5 (4)	O13—C12—C16—C15	−30.3 (4)
N7—C8—N9—C12	176.1 (3)	O13—C12—C16—O20	85.7 (3)
N3—C4—N9—C8	179.9 (3)	O13—C14—C17—O18	−68.6 (4)
N3—C4—N9—C12	4.1 (5)	C15—C14—C17—O18	48.2 (4)
C5—C4—N9—C8	0.1 (3)	O22—N21—O23—Ag1	180.000 (1)
C5—C4—N9—C12	−175.7 (3)	O23^i—N21—O23—Ag1	0.000 (1)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O18—H18···O23^ii	0.85 (1)	2.08 (2)	2.895 (4)	161 (5)
O19—H19···O24	0.83 (1)	1.86 (2)	2.674 (4)	167 (5)
O20—H20···N3^iii	0.84 (1)	2.00 (2)	2.812 (4)	163 (5)
O24—H24A···O19^iv	0.83 (1)	1.98 (2)	2.772 (4)	159 (4)
O24—H24B···N1^v	0.84 (1)	2.11 (2)	2.943 (4)	174 (5)

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