Crystal structure of bis-(9H-6-amino-purin-1-ium) hexa-fluorido-silicate(IV) dihydrate.

The asymmetric unit of the title compound, 2C5H6N5 (+)·SiF6 (2-)·2H2O, contains one adeninium cation, half of a hexa-fluorido-silicate anion located on an inversion centre and one lattice water mol-ecule. The adeninium cations are connected through N-H⋯N hydrogen bonds involving one H atom of the -NH2 group and the H atom of the protonated N atom of the adenine ring system, forming centrosymmetric ring motifs of the type R 2 (2)(10) and R 2 (2)(8), respectively. The overall connection of the cation leads to the formation of planar ribbons parallel to (122). In the ribbons, slipped π-π stacking inter-actions, with a centroid-to-centroid distance of 3.6938 (9) Å, an inter-planar distance of 3.455 Å and a slippage of 1.306 Å is observed. The hexa-fluorido-silicate anion and the water mol-ecule are linked through O-H⋯F hydrogen bonds [ring motif R 4 (4)(12)] into chains parallel to [100]. The cationic ribbons and anionic chains are finally connected through additional N-H⋯O, N-H⋯F and O-H⋯F hydrogen bonds into a three-dimensional network in which layers of adeninium cations and fluorido-silicate anions alternate parallel to (001).

Related literature

The title compound was prepared as part of our ongoing studies of hydrogen-bonding inter­actions in the crystal structures of protonated amines (Bouacida et al., 2005a ▸,b ▸,c ▸; 2006 ▸; Belhouas et al., 2012 ▸). For π–π stacking inter­actions, see: Janiak (2000 ▸).

Experimental

Crystal data

2C5H6N5 +·SiF6 2−·2H2O

M = 450.42

Triclinic,

a = 5.7500 (7) Å

b = 7.8504 (3) Å

c = 10.0884 (6) Å

α = 79.141 (6)°

β = 84.534 (17)°

γ = 71.774 (9)°

V = 424.47 (6) Å3

Z = 1

Mo Kα radiation

μ = 0.24 mm−1

T = 295 K

0.55 × 0.12 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer

4025 measured reflections

1923 independent reflections

1757 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.082

S = 1.03

1923 reflections

133 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.22 e Å−3

Data collection: COLLECT (Otwinowski & Minor, 1997 ▸); cell refinement: DIRAX/LSQ (Duisenberg et al., 2003 ▸); data reduction: EVALCCD (Duisenberg et al., 2003 ▸); program(s) used to solve structure: SIR92 (Burla et al., 2005 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) SiAde, I. DOI: 10.1107/S2056989014027005/wm5099sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014027005/wm5099Isup2.hkl

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x y z . DOI: 10.1107/S2056989014027005/wm5099fig1.tif

The principal structural units in the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radius. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) −x, −y, 2 − z]

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x y z x y z x y z x y z . DOI: 10.1107/S2056989014027005/wm5099fig2.tif

Partial packing view of the title compound, showing the formation of (10) (A1) and (8) (A2) rings through N—H⋯N, N—H⋯O, N—H⋯F and O—H⋯F hydrogen bonds. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (i) −x, y − , −z + ; (ii) −x, y + , −z + ; (iii) x, y − 1, z; (iv) −x, −y, −z + 1.].

Click here for additional data file.

x y z . DOI: 10.1107/S2056989014027005/wm5099fig3.tif

Partial packing view showing chains formed between water mol­ecules and fluorido­silicate anions through O—H⋯F hydrogen bonds. For the sake of clarity, the cationic counterparts have been omitted. [Symmetry code: (i) x + 1, y, z]

Click here for additional data file.

. DOI: 10.1107/S2056989014027005/wm5099fig4.tif

Packing view in a projection aproximately along [100] showing the formation of layers parallel to (001). Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

CCDC reference: 1038389

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

2C5H6N5+·SiF62−·2H2O	Z = 1
Mr = 450.42	F(000) = 230
Triclinic, P1	Dx = 1.762 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7500 (7) Å	Cell parameters from 2981 reflections
b = 7.8504 (3) Å	θ = 5.2–27.5°
c = 10.0884 (6) Å	µ = 0.24 mm−1
α = 79.141 (6)°	T = 295 K
β = 84.534 (17)°	Lath, colourless
γ = 71.774 (9)°	0.55 × 0.12 × 0.07 mm
V = 424.47 (6) Å3

Nonius KappaCCD diffractometer	1757 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 5.2°
CCD rotation images, thick slices scans	h = −6→7
4025 measured reflections	k = −10→10
1923 independent reflections	l = −13→13

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0373P)2 + 0.1468P] where P = (Fo2 + 2Fc2)/3
1923 reflections	(Δ/σ)max = 0.001
133 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.22 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
Si1	0.0000	0.0000	1.0000	0.02519 (13)
F1	0.16598 (16)	−0.01595 (12)	1.13081 (8)	0.0417 (2)
F2	−0.25721 (16)	0.04669 (12)	1.09945 (9)	0.0432 (2)
F3	−0.03226 (17)	0.22671 (11)	0.95904 (9)	0.0410 (2)
O1W	0.36312 (19)	0.33709 (13)	0.99720 (11)	0.0411 (3)
H1W	0.4831	0.2480	1.0279	0.062*
H2W	0.2551	0.2970	0.9859	0.062*
N1	0.4082 (2)	0.56497 (15)	0.76571 (10)	0.0304 (2)
H1	0.4261	0.4920	0.8417	0.036*
N7	0.7063 (2)	0.69851 (15)	0.44077 (11)	0.0322 (3)
N9	0.3304 (2)	0.89656 (15)	0.41590 (11)	0.0339 (3)
H9	0.2111	0.9840	0.3789	0.041*
N6	0.8149 (2)	0.42421 (16)	0.70564 (12)	0.0384 (3)
H6A	0.8298	0.3513	0.7817	0.046*
H6B	0.9376	0.4154	0.6487	0.046*
N3	0.1313 (2)	0.80786 (16)	0.63114 (11)	0.0344 (3)
C6	0.6057 (2)	0.54850 (16)	0.67661 (12)	0.0277 (3)
C4	0.3254 (2)	0.79502 (17)	0.54071 (12)	0.0287 (3)
C5	0.5581 (2)	0.67381 (16)	0.55526 (12)	0.0268 (3)
C8	0.5605 (3)	0.83344 (18)	0.36060 (14)	0.0347 (3)
H8	0.6093	0.8810	0.2748	0.042*
C2	0.1861 (3)	0.68935 (19)	0.74132 (13)	0.0334 (3)
H2	0.0632	0.6901	0.8084	0.040*

	U11	U22	U33	U12	U13	U23
Si1	0.0258 (2)	0.0253 (2)	0.0204 (2)	−0.00695 (18)	−0.00429 (17)	0.00622 (16)
F1	0.0428 (5)	0.0461 (5)	0.0328 (4)	−0.0095 (4)	−0.0160 (4)	0.0021 (3)
F2	0.0341 (4)	0.0502 (5)	0.0354 (4)	−0.0076 (4)	0.0041 (3)	0.0054 (4)
F3	0.0494 (5)	0.0291 (4)	0.0412 (5)	−0.0126 (4)	−0.0109 (4)	0.0080 (3)
O1W	0.0376 (6)	0.0361 (5)	0.0458 (6)	−0.0123 (4)	−0.0092 (4)	0.0080 (4)
N1	0.0364 (6)	0.0310 (5)	0.0209 (5)	−0.0091 (4)	−0.0034 (4)	0.0016 (4)
N7	0.0338 (6)	0.0308 (5)	0.0266 (5)	−0.0067 (5)	−0.0001 (4)	0.0027 (4)
N9	0.0354 (6)	0.0298 (5)	0.0279 (6)	−0.0023 (5)	−0.0052 (4)	0.0050 (4)
N6	0.0354 (6)	0.0376 (6)	0.0297 (6)	−0.0022 (5)	−0.0020 (5)	0.0106 (5)
N3	0.0323 (6)	0.0355 (6)	0.0286 (6)	−0.0024 (5)	−0.0022 (4)	−0.0017 (4)
C6	0.0328 (6)	0.0260 (6)	0.0232 (6)	−0.0086 (5)	−0.0038 (5)	−0.0009 (4)
C4	0.0328 (7)	0.0265 (6)	0.0244 (6)	−0.0061 (5)	−0.0044 (5)	−0.0021 (4)
C5	0.0306 (6)	0.0247 (5)	0.0229 (6)	−0.0064 (5)	−0.0028 (5)	−0.0009 (4)
C8	0.0380 (7)	0.0332 (6)	0.0270 (6)	−0.0079 (5)	−0.0013 (5)	0.0049 (5)
C2	0.0348 (7)	0.0361 (7)	0.0271 (6)	−0.0081 (5)	0.0008 (5)	−0.0051 (5)

Si1—F1	1.6646 (8)	N9—C4	1.3605 (16)
Si1—F1i	1.6646 (8)	N9—C8	1.3637 (19)
Si1—F2	1.6867 (9)	N9—H9	0.8600
Si1—F2i	1.6867 (9)	N6—C6	1.3080 (17)
Si1—F3	1.7041 (8)	N6—H6A	0.8600
Si1—F3i	1.7041 (8)	N6—H6B	0.8600
O1W—H1W	0.8476	N3—C2	1.3015 (17)
O1W—H2W	0.8046	N3—C4	1.3632 (17)
N1—C2	1.3543 (18)	C6—C5	1.4081 (16)
N1—C6	1.3681 (17)	C4—C5	1.3803 (18)
N1—H1	0.8600	C8—H8	0.9300
N7—C8	1.3154 (17)	C2—H2	0.9300
N7—C5	1.3892 (16)
F1—Si1—F1i	180.000 (1)	C4—N9—H9	126.5
F1—Si1—F2	89.86 (5)	C8—N9—H9	126.5
F1i—Si1—F2	90.14 (5)	C6—N6—H6A	120.0
F1—Si1—F2i	90.14 (5)	C6—N6—H6B	120.0
F1i—Si1—F2i	89.86 (5)	H6A—N6—H6B	120.0
F2—Si1—F2i	180.0	C2—N3—C4	112.33 (12)
F1—Si1—F3	90.31 (4)	N6—C6—N1	120.97 (11)
F1i—Si1—F3	89.69 (4)	N6—C6—C5	125.23 (12)
F2—Si1—F3	89.68 (5)	N1—C6—C5	113.80 (11)
F2i—Si1—F3	90.32 (5)	N9—C4—N3	127.47 (12)
F1—Si1—F3i	89.69 (4)	N9—C4—C5	105.20 (11)
F1i—Si1—F3i	90.31 (4)	N3—C4—C5	127.32 (11)
F2—Si1—F3i	90.32 (5)	C4—C5—N7	111.11 (11)
F2i—Si1—F3i	89.68 (5)	C4—C5—C6	117.64 (12)
F3—Si1—F3i	180.000 (1)	N7—C5—C6	131.23 (12)
H1W—O1W—H2W	107.5	N7—C8—N9	113.25 (12)
C2—N1—C6	123.90 (11)	N7—C8—H8	123.4
C2—N1—H1	118.1	N9—C8—H8	123.4
C6—N1—H1	118.1	N3—C2—N1	125.00 (13)
C8—N7—C5	103.37 (11)	N3—C2—H2	117.5
C4—N9—C8	107.06 (11)	N1—C2—H2	117.5

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···F2ii	0.85	1.88	2.7307 (14)	178
O1W—H2W···F3	0.80	1.95	2.7553 (14)	174
N1—H1···O1W	0.86	1.88	2.7059 (15)	162
N9—H9···N3iii	0.86	2.13	2.9378 (17)	157
N9—H9···F1iv	0.86	2.54	3.0009 (14)	115
N6—H6A···F3ii	0.86	1.98	2.7917 (14)	157
N6—H6A···F1v	0.86	2.61	3.2906 (15)	137
N6—H6B···N7vi	0.86	2.15	2.9648 (18)	159

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1WH1WF2i	0.85	1.88	2.7307(14)	178
O1WH2WF3	0.80	1.95	2.7553(14)	174
N1H1O1W	0.86	1.88	2.7059(15)	162
N9H9N3ii	0.86	2.13	2.9378(17)	157
N9H9F1iii	0.86	2.54	3.0009(14)	115
N6H6AF3i	0.86	1.98	2.7917(14)	157
N6H6AF1iv	0.86	2.61	3.2906(15)	137
N6H6BN7v	0.86	2.15	2.9648(18)	159

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