Crystal structure of 2,4-di-amino-7-(hydroxy-meth-yl)pteridin-1-ium nitrate.

In the crystal of the title mol-ecular salt, C7H9N6O(+)·NO3 (-), the cations and anions are linked via N-H⋯O and O-H⋯O hydrogen bonds, forming sheets parallel to (100). Within the sheets there are numerous hydrogen-bonding ring motifs.

Related literature

For background to and the biological activity of pteridine derivatives, see: Benkovic Annu (1980 ▸); Blakeley (1969 ▸); Van Beelen et al. (1984 ▸); Dolphin (1980 ▸); Pfleiderer (1982 ▸); Blakely & Cocco (1985 ▸); Pfleiderer & Taylor (1964 ▸); Müller et al. (1991 ▸); Weinstock et al. (1968 ▸). For related structures, see: Kuyper (1990 ▸); Schwalbe & Williams (1986 ▸); Robertson et al. (1998 ▸). For hydrogen-bond motifs, see: Etter (1990 ▸); Bernstein et al. (1995 ▸); Allen et al. (1998 ▸).

Experimental

Crystal data

C7H9N6O+·NO3 −

M = 255.21

Orthorhombic,

a = 6.4060 (17) Å

b = 14.960 (6) Å

c = 10.867 (3) Å

V = 1041.4 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 294 K

0.27 × 0.10 × 0.07 mm

Data collection

Bruker SMART APEXII Duo CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.964, T max = 0.991

2866 measured reflections

862 independent reflections

720 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.074

S = 1.03

862 reflections

127 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.09 e Å−3

Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015008397/su5127sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008397/su5127Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015008397/su5127Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015008397/su5127fig1.tif

The mol­ecular structure of the title salt, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The N-H⋯O hydrogen bonds are shown as dashed lines (see Table 1 for details).

Click here for additional data file.

a . DOI: 10.1107/S2056989015008397/su5127fig2.tif

A view along the a axis of the crystal packing of the title mol­ecular salt. The N-H⋯O hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1062258

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

C7H9N6O+·NO3−	F(000) = 528
Mr = 255.21	Dx = 1.628 Mg m−3
Orthorhombic, Cmc21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 1083 reflections
a = 6.4060 (17) Å	θ = 2.7–24.6°
b = 14.960 (6) Å	µ = 0.14 mm−1
c = 10.867 (3) Å	T = 294 K
V = 1041.4 (6) Å3	Block, bronze
Z = 4	0.27 × 0.10 × 0.07 mm

Bruker SMART APEXII Duo CCD area-detector diffractometer	862 independent reflections
Radiation source: fine-focus sealed tube	720 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→7
Tmin = 0.964, Tmax = 0.991	k = −17→17
2866 measured reflections	l = −8→12

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) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0382P)2 + 0.1935P] where P = (Fo2 + 2Fc2)/3
862 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.09 e Å−3
1 restraint	Δρmin = −0.16 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	Occ. (<1)
O1	0.5000	0.63088 (17)	0.8666 (3)	0.0557 (8)
O2	0.5000	0.2129 (2)	0.5161 (3)	0.0585 (9)
O3	0.5000	0.12875 (19)	0.3553 (3)	0.0584 (9)
O4	0.5000	0.06903 (19)	0.5342 (3)	0.0608 (9)
N1	0.5000	0.4061 (2)	0.9909 (3)	0.0415 (9)
N2	0.5000	0.1632 (3)	0.9791 (4)	0.0451 (9)
N3	0.5000	0.2207 (2)	0.7764 (3)	0.0447 (9)
N4	0.5000	0.3731 (2)	0.7360 (4)	0.0499 (10)
N5	0.5000	0.2581 (3)	1.1464 (4)	0.0524 (10)
H1N5	0.5000	0.210 (3)	1.199 (4)	0.042 (13)*
H2N5	0.5000	0.312 (3)	1.185 (5)	0.062 (14)*
N6	0.5000	0.0703 (3)	0.8120 (4)	0.0546 (11)
H1N6	0.5000	0.028 (3)	0.854 (5)	0.056 (15)*
H2N6	0.5000	0.060 (2)	0.723 (3)	0.020 (9)*
N7	0.5000	0.1359 (2)	0.4687 (4)	0.0448 (9)
C1	0.5000	0.5648 (3)	0.9606 (5)	0.0467 (11)
H1A	0.3776	0.5726	1.0120	0.056*	0.50
H1B	0.6224	0.5726	1.0120	0.056*	0.50
C2	0.5000	0.4726 (2)	0.9092 (4)	0.0390 (10)
C3	0.5000	0.3228 (3)	0.9449 (4)	0.0384 (11)
C4	0.5000	0.2451 (2)	1.0250 (4)	0.0401 (10)
C5	0.5000	0.1519 (2)	0.8573 (5)	0.0408 (11)
C6	0.5000	0.3074 (2)	0.8204 (5)	0.0391 (10)
C7	0.5000	0.4546 (3)	0.7834 (4)	0.0498 (13)
H7A	0.5000	0.5028	0.7293	0.060*
H1O1	0.5000	0.689 (4)	0.901 (6)	0.072 (14)*
H1N3	0.5000	0.208 (3)	0.683 (5)	0.046 (11)*

	U11	U22	U33	U12	U13	U23
O1	0.0954 (19)	0.0284 (13)	0.0435 (17)	0.000	0.000	0.0045 (16)
O2	0.090 (2)	0.0310 (14)	0.054 (2)	0.000	0.000	−0.0078 (16)
O3	0.096 (2)	0.0401 (17)	0.039 (2)	0.000	0.000	−0.0029 (17)
O4	0.093 (2)	0.0323 (15)	0.057 (2)	0.000	0.000	0.0045 (15)
N1	0.0534 (19)	0.0299 (17)	0.041 (2)	0.000	0.000	0.0027 (15)
N2	0.062 (2)	0.0276 (17)	0.046 (2)	0.000	0.000	0.0055 (15)
N3	0.068 (2)	0.0304 (18)	0.035 (2)	0.000	0.000	0.0005 (14)
N4	0.082 (3)	0.0300 (15)	0.038 (2)	0.000	0.000	0.0011 (17)
N5	0.086 (2)	0.035 (2)	0.036 (2)	0.000	0.000	0.0041 (18)
N6	0.082 (3)	0.0308 (18)	0.051 (3)	0.000	0.000	−0.001 (2)
N7	0.058 (2)	0.036 (2)	0.040 (2)	0.000	0.000	−0.0012 (17)
C1	0.069 (3)	0.034 (2)	0.037 (2)	0.000	0.000	0.0015 (19)
C2	0.056 (2)	0.032 (2)	0.029 (2)	0.000	0.000	0.0006 (18)
C3	0.046 (2)	0.027 (2)	0.041 (3)	0.000	0.000	0.0013 (15)
C4	0.049 (2)	0.032 (2)	0.040 (3)	0.000	0.000	0.007 (2)
C5	0.049 (2)	0.029 (2)	0.044 (3)	0.000	0.000	0.006 (2)
C6	0.050 (2)	0.0322 (19)	0.035 (2)	0.000	0.000	−0.0005 (18)
C7	0.075 (3)	0.036 (2)	0.038 (3)	0.000	0.000	0.003 (2)

O1—C1	1.422 (6)	N5—C4	1.333 (7)
O1—H1O1	0.94 (6)	N5—H1N5	0.92 (5)
O2—N7	1.262 (5)	N5—H2N5	0.91 (5)
O3—N7	1.237 (5)	N6—C5	1.317 (5)
O4—N7	1.228 (5)	N6—H1N6	0.78 (5)
N1—C2	1.334 (5)	N6—H2N6	0.98 (4)
N1—C3	1.342 (5)	C1—C2	1.487 (6)
N2—C4	1.322 (5)	C1—H1A	0.9700
N2—C5	1.334 (7)	C1—H1B	0.9700
N3—C5	1.353 (6)	C2—C7	1.394 (5)
N3—C6	1.383 (5)	C3—C6	1.372 (6)
N3—H1N3	1.03 (5)	C3—C4	1.454 (5)
N4—C7	1.323 (5)	C7—H7A	0.9300
N4—C6	1.344 (6)
C1—O1—H1O1	111 (4)	C2—C1—H1B	109.2
C2—N1—C3	116.4 (4)	H1A—C1—H1B	107.9
C4—N2—C5	119.5 (4)	N1—C2—C7	120.6 (3)
C5—N3—C6	119.3 (4)	N1—C2—C1	116.2 (4)
C5—N3—H1N3	120 (2)	C7—C2—C1	123.3 (3)
C6—N3—H1N3	121 (2)	N1—C3—C6	121.6 (4)
C7—N4—C6	114.1 (5)	N1—C3—C4	121.3 (4)
C4—N5—H1N5	120 (3)	C6—C3—C4	117.2 (4)
C4—N5—H2N5	126 (3)	N2—C4—N5	120.6 (3)
H1N5—N5—H2N5	114 (4)	N2—C4—C3	121.0 (5)
C5—N6—H1N6	122 (4)	N5—C4—C3	118.4 (4)
C5—N6—H2N6	121 (2)	N6—C5—N2	119.3 (4)
H1N6—N6—H2N6	117 (4)	N6—C5—N3	117.5 (5)
O4—N7—O3	120.5 (4)	N2—C5—N3	123.2 (4)
O4—N7—O2	120.4 (4)	N4—C6—C3	123.4 (4)
O3—N7—O2	119.0 (4)	N4—C6—N3	116.8 (4)
O1—C1—C2	112.0 (4)	C3—C6—N3	119.9 (4)
O1—C1—H1A	109.2	N4—C7—C2	124.1 (4)
C2—C1—H1A	109.2	N4—C7—H7A	118.0
O1—C1—H1B	109.2	C2—C7—H7A	118.0
C3—N1—C2—C7	0.000 (2)	C6—N3—C5—N6	180.000 (1)
C3—N1—C2—C1	180.000 (2)	C6—N3—C5—N2	0.000 (2)
O1—C1—C2—N1	180.000 (2)	C7—N4—C6—C3	0.000 (2)
O1—C1—C2—C7	0.000 (2)	C7—N4—C6—N3	180.000 (1)
C2—N1—C3—C6	0.000 (2)	N1—C3—C6—N4	0.000 (2)
C2—N1—C3—C4	180.000 (2)	C4—C3—C6—N4	180.000 (2)
C5—N2—C4—N5	180.000 (2)	N1—C3—C6—N3	180.000 (2)
C5—N2—C4—C3	0.000 (2)	C4—C3—C6—N3	0.000 (2)
N1—C3—C4—N2	180.000 (2)	C5—N3—C6—N4	180.000 (1)
C6—C3—C4—N2	0.000 (2)	C5—N3—C6—C3	0.000 (2)
N1—C3—C4—N5	0.000 (2)	C6—N4—C7—C2	0.000 (2)
C6—C3—C4—N5	180.000 (2)	N1—C2—C7—N4	0.000 (2)
C4—N2—C5—N6	180.000 (2)	C1—C2—C7—N4	180.000 (2)
C4—N2—C5—N3	0.000 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···O2	1.03 (5)	1.82 (5)	2.831 (5)	167 (4)
N6—H2N6···O4	0.98 (3)	2.06 (3)	3.019 (6)	167 (3)
O1—H1O1···O2i	0.95 (6)	1.93 (6)	2.846 (4)	163 (6)
N5—H1N5···O3ii	0.92 (4)	2.09 (4)	2.983 (6)	164 (4)
N5—H2N5···O1i	0.91 (5)	2.15 (5)	2.913 (5)	141 (4)
N6—H1N6···O3iii	0.78 (5)	2.35 (4)	3.015 (5)	145 (5)
N6—H1N6···O4iii	0.78 (5)	2.44 (5)	3.190 (6)	162 (5)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H1N3O2	1.03(5)	1.82(5)	2.831(5)	167(4)
N6H2N6O4	0.98(3)	2.06(3)	3.019(6)	167(3)
O1H1O1O2i	0.95(6)	1.93(6)	2.846(4)	163(6)
N5H1N5O3ii	0.92(4)	2.09(4)	2.983(6)	164(4)
N5H2N5O1i	0.91(5)	2.15(5)	2.913(5)	141(4)
N6H1N6O3iii	0.78(5)	2.35(4)	3.015(5)	145(5)
N6H1N6O4iii	0.78(5)	2.44(5)	3.190(6)	162(5)

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