Adenin-1-ium hydrogen isophthalate di-methyl-formamide monosolvate.

In the title proton-transfer organic salt, C5H6.3N5 (+)·C8H4.7O4 (-)·C3H7NO, the adeninium moiety is protonated at the N atom in the 1-position of the 6-amino-7H-purin-1-ium (adeninium) cation. In the solid state, the second acidic proton of isophthalic acid is partially transferred to the imidazole N atom of the adeninium cation [refined O-H versus N-H ratio = 0.70 (11):0.30 (11)]. Through the partially transferred proton, the adeninium cation is strongly hydrogen bonded (N-H⋯O/O-H⋯N) to the isophthalate anion. This strong inter-action is assisted by another N-H⋯O hydrogen bond originating from the adeninium NH2 group towards the isophthalate keto O atom, with an R (2) 2(8) graph-set motif. This arrangement is linked via N-H⋯O hydrogen bonds to the O atoms of the carboxyl-ate group of an isophthalate anion. Together, these hydrogen bonds lead to the formation criss-cross zigzag isophthalate⋯adeninium chains lying parallel to (501) and (50-1). The adeninium cations and the isophthalate anions are arranged in infinite π stacks that extend along the c-axis direction [inter-planar distance = 3.305 (3) Å]. Mol-ecules are inclined with respect to this direction and within the stacks they are offset by ca. half a mol-ecule each. Combination of the N-H⋯O and O-H⋯N hydrogen bonds with the π-π inter-actions forms infinitely stacked isophthalate⋯adeninium chains, thus leading to a two-dimensional supra-molecular structure with parallel inter-digitating layers formed by the π stacked isophthalate⋯adeninium chains. The DMF mol-ecules of crystallization are bonded to the adeninium cations through strong N-H⋯O hydrogen bonds and project into the lattice space in between the anions and cations. There are also C-H⋯O hydrogen bonds present which, combined with the other inter-actions, form a three-dimensional network. The crystal under investigation was found to be split and was handled as if non-merohedrally twinned.

Related literature

For supra­molecular structures comprising 3-carb­oxy­benzo­ates, see, for example: Siddiqui et al. (2012 ▶). For adenine as a linker and biomolecular building block, see: An et al. (2010 ▶). For n class="Chemical">hydrogen bonding, see: Gilli & Gilli (2009 ▶). For graph-set analysis, see: Etter (1990 ▶); Bernstein et al. (1995 ▶)·The crystal under investigation was found to be split and was handled as if non-merohedrally twinned. The orientation matrices for the two components were identified using the program CELL NOW (Sheldrick, 2004 ▶).

Experimental

Crystal data

C5H6.30N5 +·n class="Chemical">C8H4.70O4 −·C3H7NO

M = 374.36

Orthorhombic,

a = 38.307 (18) Å

b = 46.05 (2) Å

c = 3.7832 (18) Å

V = 6674 (5) Å3

Z = 16

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.55 × 0.15 × 0.04 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (TWINABS; Bruker, 2009 ▶) T min = 0.730, T max = 1.000

3888 measured reflections

3888 independent reflections

2703 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.088

wR(F 2) = 0.233

S = 1.05

3888 reflections

251 parameters

2 restraints

H atoms treated my a mixture of independent and constrained refinement

Δρmax = 0.58 e Å−3

Δρmin = −0.50 e Å−3

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2011 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶) and SHELXLE (Hübschle et al., 2011 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL2013 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813034971/su2677sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813034971/su2677Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813034971/su2677Isup3.cml

CCDC reference:

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

C5H6.30N5+·C8H4.70O4−·C3H7NO	Dx = 1.490 Mg m−3
Mr = 374.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 290 reflections
a = 38.307 (18) Å	θ = 4.3–30.4°
b = 46.05 (2) Å	µ = 0.11 mm−1
c = 3.7832 (18) Å	T = 100 K
V = 6674 (5) Å3	Plate, colourless
Z = 16	0.55 × 0.15 × 0.04 mm
F(000) = 3136

Bruker SMART APEX CCD diffractometer	3888 independent reflections
Radiation source: fine-focus sealed tube	2703 reflections with I > 2σ(I)
Graphite monochromator	θmax = 30.6°, θmin = 1.4°
ω scans	h = 0→54
Absorption correction: multi-scan (TWINABS; Bruker, 2009)	k = 0→66
Tmin = 0.730, Tmax = 1.000	l = 0→5
3888 measured reflections

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)] = 0.088	Hydrogen site location: mixed
wR(F2) = 0.233	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0928P)2 + 48.0632P] where P = (Fo2 + 2Fc2)/3
3888 reflections	(Δ/σ)max < 0.001
251 parameters	Δρmax = 0.58 e Å−3
2 restraints	Δρmin = −0.50 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. Refined as a 2-component twin.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.05925 (14)	0.13091 (12)	0.512 (2)	0.0190 (13)
C2	0.04322 (13)	0.15984 (12)	0.4520 (16)	0.0123 (11)
C3	0.06001 (14)	0.18481 (13)	0.566 (2)	0.0194 (13)
H3	0.0822	0.1834	0.6767	0.023*
C4	0.04487 (14)	0.21170 (12)	0.5214 (17)	0.0156 (11)
H4	0.0564	0.2287	0.6040	0.019*
C5	0.01246 (13)	0.21387 (12)	0.3538 (18)	0.0161 (12)
H5	0.0019	0.2323	0.3205	0.019*
C6	−0.00425 (13)	0.18877 (12)	0.2360 (18)	0.0144 (11)
C7	0.01070 (13)	0.16197 (12)	0.2957 (19)	0.0157 (12)
H7	−0.0014	0.1448	0.2289	0.019*
C8	−0.03904 (14)	0.19030 (12)	0.0547 (19)	0.0171 (12)
C9	0.12077 (13)	0.05012 (13)	0.7880 (19)	0.0175 (12)
C10	0.13647 (13)	0.00114 (14)	0.7890 (18)	0.0181 (12)
H10	0.1535	−0.0127	0.8607	0.022*
C11	0.08680 (14)	0.01200 (13)	0.5326 (19)	0.0183 (12)
C12	0.04224 (15)	0.03628 (13)	0.335 (2)	0.0230 (14)
H12	0.0206	0.0404	0.2233	0.028*
C13	0.09038 (13)	0.04118 (13)	0.604 (2)	0.0185 (13)
C14	0.18697 (14)	0.19317 (13)	0.289 (2)	0.0216 (14)
H14	0.1657	0.2008	0.3782	0.026*
C15	0.21815 (16)	0.15444 (15)	0.010 (2)	0.0275 (15)
H15A	0.2141	0.1338	−0.0415	0.041*
H15B	0.2368	0.1563	0.1853	0.041*
H15C	0.2250	0.1645	−0.2079	0.041*
C16	0.15440 (17)	0.15073 (17)	0.128 (3)	0.0343 (17)
H16A	0.1355	0.1615	0.2439	0.051*
H16B	0.1577	0.1321	0.2481	0.051*
H16C	0.1483	0.1473	−0.1198	0.051*
N1	0.14293 (12)	0.02850 (11)	0.8754 (17)	0.0188 (11)
H1	0.1621	0.0327	0.9926	0.023*
N2	0.10912 (11)	−0.00944 (11)	0.6145 (17)	0.0194 (11)
N3	0.05564 (12)	0.00939 (11)	0.3618 (16)	0.0184 (11)
H3A	0.0461	−0.0068	0.2839	0.022*
N4	0.06190 (12)	0.05623 (11)	0.4781 (17)	0.0210 (12)
H4A	0.0579	0.0750	0.4911	0.025*	0.30 (11)
N5	0.12746 (11)	0.07718 (11)	0.8667 (17)	0.0195 (11)
H5A	0.1468	0.0817	0.9795	0.023*
H5B	0.1126	0.0909	0.8070	0.023*
N6	0.18633 (12)	0.16733 (11)	0.1475 (19)	0.0219 (12)
O1	0.08756 (10)	0.12818 (9)	0.6562 (15)	0.0227 (10)
O2	0.04090 (10)	0.10943 (9)	0.3921 (16)	0.0239 (11)
H2	0.047 (3)	0.0918 (8)	0.40 (4)	0.036*	0.70 (11)
O3	−0.05527 (10)	0.16840 (9)	−0.0170 (16)	0.0247 (11)
O4	−0.04896 (10)	0.21663 (9)	−0.0238 (14)	0.0219 (10)
O5	0.21343 (10)	0.20846 (9)	0.3152 (15)	0.0233 (10)

	U11	U22	U33	U12	U13	U23
C1	0.011 (2)	0.022 (2)	0.024 (4)	0.0015 (19)	0.005 (3)	0.002 (3)
C2	0.009 (2)	0.022 (2)	0.006 (3)	0.0007 (19)	0.002 (2)	0.000 (2)
C3	0.011 (2)	0.029 (3)	0.019 (3)	−0.002 (2)	−0.006 (3)	0.000 (3)
C4	0.014 (2)	0.025 (3)	0.008 (3)	−0.006 (2)	0.001 (2)	−0.001 (3)
C5	0.011 (2)	0.023 (3)	0.014 (3)	0.002 (2)	0.000 (2)	−0.002 (3)
C6	0.008 (2)	0.025 (3)	0.011 (3)	0.0014 (19)	−0.002 (2)	0.003 (3)
C7	0.010 (2)	0.022 (2)	0.016 (3)	−0.0029 (19)	0.001 (2)	0.002 (3)
C8	0.010 (2)	0.025 (3)	0.016 (3)	0.001 (2)	0.003 (2)	0.001 (3)
C9	0.011 (2)	0.028 (3)	0.013 (3)	−0.001 (2)	0.002 (2)	0.001 (3)
C10	0.009 (2)	0.036 (3)	0.009 (3)	0.002 (2)	0.006 (2)	0.003 (3)
C11	0.013 (2)	0.028 (3)	0.014 (3)	0.000 (2)	0.005 (2)	0.001 (3)
C12	0.015 (2)	0.031 (3)	0.023 (4)	−0.003 (2)	0.002 (3)	0.003 (3)
C13	0.007 (2)	0.028 (3)	0.020 (3)	0.001 (2)	0.001 (2)	−0.002 (3)
C14	0.012 (2)	0.028 (3)	0.025 (4)	0.005 (2)	0.000 (3)	0.003 (3)
C15	0.024 (3)	0.032 (3)	0.026 (4)	0.010 (2)	−0.002 (3)	−0.006 (3)
C16	0.023 (3)	0.050 (4)	0.030 (4)	−0.009 (3)	−0.001 (3)	−0.008 (4)
N1	0.0079 (18)	0.031 (2)	0.018 (3)	−0.0006 (18)	−0.003 (2)	−0.001 (3)
N2	0.010 (2)	0.029 (2)	0.019 (3)	−0.0032 (18)	−0.001 (2)	−0.002 (3)
N3	0.013 (2)	0.028 (2)	0.015 (3)	−0.0002 (18)	−0.001 (2)	0.000 (2)
N4	0.012 (2)	0.025 (2)	0.026 (3)	0.0035 (18)	0.002 (2)	0.002 (3)
N5	0.0090 (19)	0.026 (2)	0.023 (3)	0.0006 (18)	0.000 (2)	−0.001 (3)
N6	0.015 (2)	0.027 (2)	0.024 (3)	0.0008 (18)	−0.001 (2)	−0.001 (3)
O1	0.0114 (18)	0.030 (2)	0.027 (3)	0.0020 (16)	−0.0071 (19)	0.000 (2)
O2	0.0124 (17)	0.0213 (19)	0.038 (3)	−0.0002 (15)	−0.008 (2)	0.000 (2)
O3	0.0128 (17)	0.025 (2)	0.037 (3)	−0.0015 (15)	−0.006 (2)	0.000 (2)
O4	0.0119 (17)	0.026 (2)	0.028 (3)	0.0003 (16)	−0.002 (2)	0.000 (2)
O5	0.0141 (18)	0.030 (2)	0.025 (3)	0.0009 (16)	−0.002 (2)	−0.003 (2)

C1—O1	1.220 (7)	C11—N3	1.363 (8)
C1—O2	1.296 (7)	C11—C13	1.378 (8)
C1—C2	1.485 (7)	C12—N4	1.305 (8)
C2—C7	1.382 (8)	C12—N3	1.345 (8)
C2—C3	1.386 (8)	C12—H12	0.9500
C3—C4	1.378 (8)	C13—N4	1.378 (7)
C3—H3	0.9500	C14—O5	1.238 (7)
C4—C5	1.398 (8)	C14—N6	1.305 (8)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.394 (8)	C15—N6	1.453 (8)
C5—H5	0.9500	C15—H15A	0.9800
C6—C7	1.380 (7)	C15—H15B	0.9800
C6—C8	1.501 (8)	C15—H15C	0.9800
C7—H7	0.9500	C16—N6	1.444 (8)
C8—O3	1.215 (7)	C16—H16A	0.9800
C8—O4	1.305 (7)	C16—H16B	0.9800
C9—N5	1.307 (7)	C16—H16C	0.9800
C9—N1	1.349 (7)	N1—H1	0.8800
C9—C13	1.417 (8)	N3—H3A	0.8800
C10—N1	1.325 (8)	N4—H4A	0.8800
C10—N2	1.331 (8)	N5—H5A	0.8800
C10—H10	0.9500	N5—H5B	0.8800
C11—N2	1.342 (7)	O2—H2	0.84 (2)
O1—C1—O2	124.1 (5)	N4—C13—C11	110.1 (5)
O1—C1—C2	121.9 (5)	N4—C13—C9	132.4 (5)
O2—C1—C2	114.0 (5)	C11—C13—C9	117.5 (5)
C7—C2—C3	119.5 (5)	O5—C14—N6	124.5 (6)
C7—C2—C1	120.1 (5)	O5—C14—H14	117.7
C3—C2—C1	120.3 (5)	N6—C14—H14	117.7
C4—C3—C2	120.8 (5)	N6—C15—H15A	109.5
C4—C3—H3	119.6	N6—C15—H15B	109.5
C2—C3—H3	119.6	H15A—C15—H15B	109.5
C3—C4—C5	119.6 (5)	N6—C15—H15C	109.5
C3—C4—H4	120.2	H15A—C15—H15C	109.5
C5—C4—H4	120.2	H15B—C15—H15C	109.5
C6—C5—C4	119.6 (5)	N6—C16—H16A	109.5
C6—C5—H5	120.2	N6—C16—H16B	109.5
C4—C5—H5	120.2	H16A—C16—H16B	109.5
C7—C6—C5	119.9 (5)	N6—C16—H16C	109.5
C7—C6—C8	119.1 (5)	H16A—C16—H16C	109.5
C5—C6—C8	121.0 (5)	H16B—C16—H16C	109.5
C6—C7—C2	120.5 (5)	C10—N1—C9	121.6 (5)
C6—C7—H7	119.8	C10—N1—H1	119.2
C2—C7—H7	119.8	C9—N1—H1	119.2
O3—C8—O4	124.9 (6)	C10—N2—C11	110.3 (5)
O3—C8—C6	121.1 (5)	C12—N3—C11	106.8 (5)
O4—C8—C6	114.0 (5)	C12—N3—H3A	126.6
N5—C9—N1	121.6 (5)	C11—N3—H3A	126.6
N5—C9—C13	123.4 (5)	C12—N4—C13	104.3 (5)
N1—C9—C13	115.0 (5)	C12—N4—H4A	127.9
N1—C10—N2	128.1 (6)	C13—N4—H4A	127.9
N1—C10—H10	115.9	C9—N5—H5A	120.0
N2—C10—H10	115.9	C9—N5—H5B	120.0
N2—C11—N3	127.0 (6)	H5A—N5—H5B	120.0
N2—C11—C13	127.5 (6)	C14—N6—C16	121.3 (6)
N3—C11—C13	105.5 (5)	C14—N6—C15	120.3 (5)
N4—C12—N3	113.4 (6)	C16—N6—C15	118.4 (6)
N4—C12—H12	123.3	C1—O2—H2	126 (8)
N3—C12—H12	123.3
O1—C1—C2—C7	−178.4 (7)	N2—C11—C13—C9	−0.6 (11)
O2—C1—C2—C7	3.1 (9)	N3—C11—C13—C9	179.1 (6)
O1—C1—C2—C3	−1.4 (10)	N5—C9—C13—N4	−1.9 (12)
O2—C1—C2—C3	−179.9 (6)	N1—C9—C13—N4	178.6 (7)
C7—C2—C3—C4	−0.9 (10)	N5—C9—C13—C11	178.9 (6)
C1—C2—C3—C4	−178.0 (6)	N1—C9—C13—C11	−0.5 (9)
C2—C3—C4—C5	−1.0 (10)	N2—C10—N1—C9	−0.1 (11)
C3—C4—C5—C6	0.4 (9)	N5—C9—N1—C10	−178.6 (6)
C4—C5—C6—C7	2.2 (9)	C13—C9—N1—C10	0.9 (9)
C4—C5—C6—C8	−179.9 (6)	N1—C10—N2—C11	−0.9 (10)
C5—C6—C7—C2	−4.1 (9)	N3—C11—N2—C10	−178.4 (7)
C8—C6—C7—C2	177.9 (6)	C13—C11—N2—C10	1.2 (10)
C3—C2—C7—C6	3.5 (9)	N4—C12—N3—C11	−0.7 (8)
C1—C2—C7—C6	−179.5 (6)	N2—C11—N3—C12	−179.7 (7)
C7—C6—C8—O3	5.3 (10)	C13—C11—N3—C12	0.5 (7)
C5—C6—C8—O3	−172.6 (7)	N3—C12—N4—C13	0.6 (8)
C7—C6—C8—O4	−172.8 (6)	C11—C13—N4—C12	−0.2 (8)
C5—C6—C8—O4	9.3 (9)	C9—C13—N4—C12	−179.4 (8)
N2—C11—C13—N4	−179.9 (6)	O5—C14—N6—C16	179.7 (7)
N3—C11—C13—N4	−0.2 (7)	O5—C14—N6—C15	0.6 (11)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N4	0.84 (2)	1.77 (4)	2.599 (6)	170 (16)
N4—H4A···O2	0.88	1.75	2.599 (6)	160
N5—H5B···O1	0.88	2.05	2.913 (7)	168
N1—H1···O4i	0.88	1.73	2.601 (6)	168
N5—H5A···O3i	0.88	2.07	2.933 (7)	166
N3—H3A···O5ii	0.88	1.84	2.700 (7)	166
C12—H12···O5iii	0.95	2.27	3.196 (7)	165
C16—H16C···O1iv	0.98	2.63	3.290 (8)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N4	0.84 (2)	1.77 (4)	2.599 (6)	170 (16)
N4—H4A⋯O2	0.88	1.75	2.599 (6)	160
N5—H5B⋯O1	0.88	2.05	2.913 (7)	168
N1—H1⋯O4i	0.88	1.73	2.601 (6)	168
N5—H5A⋯O3i	0.88	2.07	2.933 (7)	166
N3—H3A⋯O5ii	0.88	1.84	2.700 (7)	166
C12—H12⋯O5iii	0.95	2.27	3.196 (7)	165
C16—H16C⋯O1iv	0.98	2.63	3.290 (8)	125

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