Bis(2,4,6-triamino-1,3,5-triazin-1-ium) pyrazine-2,3-dicarboxyl-ate tetra-hydrate: a synchrotron radiation study.

The title compound, 2C(3)H(7)N(6) (+)·C(6)H(2)N(2)O(4) (2-)·4H(2)O or (tataH)(2)(pzdc)·4H(2)O, was synthesised by a reaction between pyrazine-2,3-dicarboxylic acid (H(2)pzdc) as a proton donor and 2,4,6-triamino-1,3,5-triazin (tata) as a proton acceptor. In the crystal structure, an extensive series of O-H⋯O, O-H⋯N, N-H⋯O and N-H⋯N hydrogen bonds generates a three-dimensional framework with the hydrogen bonding involving most donor and acceptor centers. π-π stacking inter-actions are also observed between adjacent triazine rings, with centroid-centroid distances of 3.4994 (8) and 3.5922 (7) Å.

Related literature

For related structures, see Xu et al. (1999 ▶); Wang et al. (2008 ▶); Liu et al. (2008 ▶); Moghimi et al. (2007 ▶); Smith et al. (2006a ▶,b ▶); Zafar et al. (2000 ▶).

Experimental

Crystal data

2C3H7N6 +·C6H2N2O4 2−·4H2O

M = 492.45

Triclinic,

a = 7.0200 (14) Å

b = 9.763 (2) Å

c = 15.397 (3) Å

α = 101.06 (3)°

β = 99.82 (3)°

γ = 96.98 (3)°

V = 1007.4 (4) Å3

Z = 2

Synchrotron radiation

λ = 0.73800 Å

μ = 0.14 mm−1

T = 100 K

0.15 × 0.04 × 0.03 mm

Data collection

Huber single-axis diffractometer

34176 measured reflections

4609 independent reflections

4314 reflections with I > 2σ(I)

R int = 0.086

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.117

S = 1.07

4609 reflections

339 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.39 e Å−3

Data collection: MXCUBE (Gabadinho & McSweeney, 2010 ▶); cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ▶); data reduction: HKL-2000; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810017290/sj2786sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017290/sj2786Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2C3H7N6+·C6H2N2O42−·4H2O	Z = 2
Mr = 492.45	F(000) = 516
Triclinic, P1	Dx = 1.623 Mg m−3
Hall symbol: -P 1	Synchrotron radiation, λ = 0.73800 Å
a = 7.0200 (14) Å	Cell parameters from 130 reflections
b = 9.763 (2) Å	θ = 2.4–26.4°
c = 15.397 (3) Å	µ = 0.14 mm−1
α = 101.06 (3)°	T = 100 K
β = 99.82 (3)°	Needle, colourless
γ = 96.98 (3)°	0.15 × 0.04 × 0.03 mm
V = 1007.4 (4) Å3

Huber single-axis diffractometer	4314 reflections with I > 2σ(I)
Radiation source: synchrotron, ESRF-CRG BM16	Rint = 0.086
Si 111	θmax = 29.1°, θmin = 3.5°
Detector resolution: 9.6 pixels mm-1	h = −9→9
CCD rotation images, thick slices scans	k = −12→12
34176 measured reflections	l = −20→20
4609 independent 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0613P)2 + 0.6264P] where P = (Fo2 + 2Fc2)/3
4609 reflections	(Δ/σ)max = 0.007
339 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

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.

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
C1	0.08476 (18)	0.61767 (13)	0.86568 (7)	0.0064 (2)
C2	0.16442 (17)	0.76548 (13)	0.92207 (8)	0.0062 (2)
C3	0.32806 (19)	0.89895 (14)	1.05809 (8)	0.0108 (2)
H3	0.3999	0.9071	1.1160	0.013*
C4	0.28663 (19)	1.02060 (14)	1.02974 (8)	0.0104 (2)
H4	0.3310	1.1079	1.0693	0.012*
C5	0.12373 (17)	0.88757 (13)	0.89268 (8)	0.0071 (2)
C6	0.00697 (19)	0.87874 (14)	0.79864 (8)	0.0090 (2)
C7	0.14712 (17)	0.41260 (13)	0.60348 (8)	0.0060 (2)
C8	0.26659 (17)	0.22077 (13)	0.65562 (8)	0.0062 (2)
C9	0.16042 (17)	0.20889 (13)	0.50575 (8)	0.0062 (2)
C10	−0.21253 (17)	0.27644 (13)	0.69392 (8)	0.0062 (2)
C11	−0.32874 (17)	0.22388 (13)	0.54233 (8)	0.0065 (2)
C12	−0.35228 (17)	0.44240 (13)	0.62008 (8)	0.0058 (2)
N1	0.26800 (16)	0.77076 (12)	1.00488 (7)	0.0090 (2)
N2	0.18487 (16)	1.01601 (11)	0.94733 (7)	0.0090 (2)
N3	0.22544 (15)	0.35575 (11)	0.67361 (6)	0.0062 (2)
H3A	0.2485	0.4042	0.7282	0.007*
N4	0.23486 (15)	0.14484 (11)	0.57220 (7)	0.0065 (2)
N5	0.11417 (15)	0.34110 (11)	0.51846 (7)	0.0066 (2)
N6	0.10542 (16)	0.54193 (11)	0.62315 (7)	0.0083 (2)
H6A	0.0564	0.5807	0.5806	0.010*
H6B	0.1273	0.5874	0.6785	0.010*
N7	0.34237 (16)	0.17081 (12)	0.72576 (7)	0.0097 (2)
H7A	0.3722	0.0870	0.7176	0.012*
H7B	0.3617	0.2222	0.7795	0.012*
N8	0.13301 (16)	0.13572 (11)	0.42175 (7)	0.0093 (2)
H8A	0.1619	0.0518	0.4112	0.011*
H8B	0.0863	0.1720	0.3776	0.011*
N9	−0.24368 (15)	0.18109 (11)	0.61670 (7)	0.0071 (2)
N10	−0.38609 (15)	0.35169 (11)	0.54089 (7)	0.0065 (2)
N11	−0.26557 (15)	0.40727 (11)	0.69764 (7)	0.0068 (2)
H11	−0.2446	0.4672	0.7484	0.008*
N12	−0.12818 (16)	0.24938 (11)	0.77090 (7)	0.0090 (2)
H12A	−0.0920	0.1685	0.7718	0.011*
H12B	−0.1094	0.3126	0.8201	0.011*
N13	−0.35804 (16)	0.13295 (11)	0.46429 (7)	0.0098 (2)
H13A	−0.3238	0.0509	0.4620	0.012*
H13B	−0.4114	0.1557	0.4156	0.012*
N14	−0.40337 (16)	0.56927 (11)	0.62636 (7)	0.0082 (2)
H14A	−0.4592	0.5939	0.5788	0.010*
H14B	−0.3808	0.6272	0.6780	0.010*
O1	−0.08939 (13)	0.57080 (10)	0.86815 (6)	0.0115 (2)
O2	0.19694 (13)	0.55284 (10)	0.82467 (6)	0.00925 (19)
O3	0.00778 (18)	0.77035 (11)	0.74052 (6)	0.0206 (3)
O4	−0.08449 (14)	0.97813 (10)	0.78707 (6)	0.0132 (2)
O1W	0.56057 (15)	0.67742 (10)	0.81619 (6)	0.0126 (2)
O2W	−0.48261 (15)	0.90431 (11)	0.72480 (6)	0.0137 (2)
O3W	0.15750 (16)	1.31613 (11)	0.94758 (7)	0.0163 (2)
O4W	0.49780 (15)	0.38403 (11)	0.88426 (6)	0.0142 (2)
H1WA	0.454 (4)	0.635 (3)	0.8298 (16)	0.033 (6)*
H1WB	0.665 (4)	0.644 (3)	0.8469 (18)	0.047 (7)*
H2WA	−0.503 (4)	0.845 (3)	0.7578 (19)	0.051 (8)*
H2WB	−0.348 (4)	0.933 (3)	0.7402 (19)	0.054 (8)*
H3WA	0.151 (4)	1.213 (3)	0.9435 (17)	0.042 (6)*
H3WB	0.144 (3)	1.353 (3)	1.0051 (17)	0.037 (6)*
H4WA	0.390 (4)	0.379 (3)	0.9119 (18)	0.046 (7)*
H4WB	0.589 (4)	0.362 (3)	0.9250 (18)	0.043 (7)*

	U11	U22	U33	U12	U13	U23
C1	0.0111 (5)	0.0052 (5)	0.0026 (5)	0.0015 (4)	−0.0003 (4)	0.0015 (4)
C2	0.0071 (5)	0.0074 (6)	0.0038 (5)	0.0015 (4)	0.0012 (4)	0.0002 (4)
C3	0.0126 (6)	0.0121 (6)	0.0051 (5)	0.0011 (5)	−0.0011 (4)	−0.0011 (4)
C4	0.0122 (5)	0.0086 (6)	0.0070 (5)	−0.0006 (5)	0.0002 (4)	−0.0036 (4)
C5	0.0086 (5)	0.0073 (6)	0.0051 (5)	0.0017 (4)	0.0016 (4)	−0.0001 (4)
C6	0.0142 (6)	0.0076 (6)	0.0055 (5)	0.0032 (5)	0.0008 (4)	0.0018 (4)
C7	0.0058 (5)	0.0065 (6)	0.0055 (5)	0.0009 (4)	0.0013 (4)	0.0012 (4)
C8	0.0062 (5)	0.0064 (6)	0.0063 (5)	0.0004 (4)	0.0018 (4)	0.0014 (4)
C9	0.0067 (5)	0.0057 (6)	0.0061 (5)	0.0007 (4)	0.0016 (4)	0.0014 (4)
C10	0.0061 (5)	0.0053 (6)	0.0073 (5)	−0.0001 (4)	0.0017 (4)	0.0022 (4)
C11	0.0065 (5)	0.0060 (6)	0.0067 (5)	0.0007 (4)	0.0009 (4)	0.0012 (4)
C12	0.0058 (5)	0.0053 (6)	0.0060 (5)	−0.0005 (4)	0.0012 (4)	0.0014 (4)
N1	0.0113 (5)	0.0098 (5)	0.0046 (4)	0.0020 (4)	−0.0007 (4)	0.0004 (4)
N2	0.0118 (5)	0.0066 (5)	0.0077 (5)	0.0009 (4)	0.0020 (4)	−0.0007 (4)
N3	0.0106 (5)	0.0044 (5)	0.0027 (4)	0.0013 (4)	0.0004 (3)	−0.0009 (3)
N4	0.0102 (5)	0.0047 (5)	0.0047 (4)	0.0015 (4)	0.0009 (4)	0.0012 (4)
N5	0.0102 (5)	0.0054 (5)	0.0043 (4)	0.0026 (4)	0.0013 (3)	0.0007 (4)
N6	0.0148 (5)	0.0060 (5)	0.0042 (4)	0.0048 (4)	0.0012 (4)	0.0001 (4)
N7	0.0171 (5)	0.0074 (5)	0.0045 (4)	0.0045 (4)	0.0000 (4)	0.0011 (4)
N8	0.0165 (5)	0.0070 (5)	0.0042 (5)	0.0052 (4)	−0.0001 (4)	0.0002 (4)
N9	0.0097 (5)	0.0060 (5)	0.0050 (5)	0.0021 (4)	−0.0001 (4)	0.0004 (4)
N10	0.0095 (5)	0.0047 (5)	0.0047 (4)	0.0015 (4)	0.0000 (3)	0.0008 (4)
N11	0.0112 (5)	0.0046 (5)	0.0034 (4)	0.0014 (4)	−0.0002 (4)	−0.0007 (3)
N12	0.0141 (5)	0.0067 (5)	0.0050 (5)	0.0025 (4)	−0.0011 (4)	0.0009 (4)
N13	0.0169 (5)	0.0068 (5)	0.0049 (5)	0.0055 (4)	−0.0013 (4)	−0.0003 (4)
N14	0.0139 (5)	0.0050 (5)	0.0050 (4)	0.0030 (4)	0.0001 (4)	−0.0001 (4)
O1	0.0109 (4)	0.0108 (5)	0.0097 (4)	−0.0016 (3)	0.0017 (3)	−0.0026 (3)
O2	0.0132 (4)	0.0073 (4)	0.0069 (4)	0.0035 (3)	0.0018 (3)	−0.0003 (3)
O3	0.0402 (6)	0.0143 (5)	0.0055 (4)	0.0160 (5)	−0.0039 (4)	−0.0020 (4)
O4	0.0189 (5)	0.0086 (5)	0.0116 (4)	0.0065 (4)	−0.0011 (4)	0.0023 (3)
O1W	0.0148 (5)	0.0107 (5)	0.0116 (4)	0.0004 (4)	0.0025 (3)	0.0020 (3)
O2W	0.0181 (5)	0.0127 (5)	0.0093 (4)	0.0024 (4)	−0.0007 (4)	0.0034 (4)
O3W	0.0225 (5)	0.0155 (5)	0.0119 (5)	0.0038 (4)	0.0052 (4)	0.0040 (4)
O4W	0.0160 (5)	0.0172 (5)	0.0102 (4)	0.0060 (4)	0.0013 (4)	0.0038 (4)

C1—O2	1.2477 (15)	C11—N9	1.3613 (15)
C1—O1	1.2618 (16)	C11—N10	1.3599 (15)
C1—C2	1.5187 (17)	C12—N14	1.3214 (16)
C2—N1	1.3441 (15)	C12—N10	1.3278 (15)
C2—C5	1.3975 (17)	C12—N11	1.3691 (15)
C3—N1	1.3325 (17)	N3—H3A	0.8600
C3—C4	1.3876 (19)	N6—H6A	0.8600
C3—H3	0.9300	N6—H6B	0.8600
C4—N2	1.3354 (16)	N7—H7A	0.8600
C4—H4	0.9300	N7—H7B	0.8600
C5—N2	1.3438 (16)	N8—H8A	0.8600
C5—C6	1.5186 (17)	N8—H8B	0.8600
C6—O3	1.2491 (16)	N11—H11	0.8600
C6—O4	1.2507 (16)	N12—H12A	0.8600
C7—N6	1.3210 (16)	N12—H12B	0.8600
C7—N5	1.3271 (15)	N13—H13A	0.8600
C7—N3	1.3703 (15)	N13—H13B	0.8600
C8—N7	1.3253 (16)	N14—H14A	0.8600
C8—N4	1.3213 (16)	N14—H14B	0.8600
C8—N3	1.3699 (16)	O1W—H1WA	0.89 (3)
C9—N8	1.3217 (16)	O1W—H1WB	0.93 (3)
C9—N4	1.3615 (15)	O2W—H2WA	0.85 (3)
C9—N5	1.3551 (16)	O2W—H2WB	0.93 (3)
C10—N12	1.3205 (16)	O3W—H3WA	0.99 (3)
C10—N9	1.3286 (16)	O3W—H3WB	0.92 (3)
C10—N11	1.3669 (15)	O4W—H4WA	0.93 (3)
C11—N13	1.3176 (16)	O4W—H4WB	0.89 (3)
O2—C1—O1	126.43 (11)	N10—C12—N11	121.27 (11)
O2—C1—C2	118.10 (11)	C3—N1—C2	116.34 (11)
O1—C1—C2	115.41 (11)	C4—N2—C5	116.88 (11)
N1—C2—C5	122.02 (11)	C7—N3—C8	119.18 (10)
N1—C2—C1	115.11 (11)	C7—N3—H3A	120.4
C5—C2—C1	122.77 (10)	C8—N3—H3A	120.4
N1—C3—C4	122.00 (11)	C8—N4—C9	116.13 (11)
N1—C3—H3	119.0	C7—N5—C9	115.98 (11)
C4—C3—H3	119.0	C7—N6—H6A	120.0
N2—C4—C3	121.90 (12)	C7—N6—H6B	120.0
N2—C4—H4	119.0	H6A—N6—H6B	120.0
C3—C4—H4	119.0	C8—N7—H7A	120.0
N2—C5—C2	120.86 (11)	C8—N7—H7B	120.0
N2—C5—C6	118.16 (11)	H7A—N7—H7B	120.0
C2—C5—C6	120.98 (11)	C9—N8—H8A	120.0
O3—C6—O4	126.16 (12)	C9—N8—H8B	120.0
O3—C6—C5	116.43 (11)	H8A—N8—H8B	120.0
O4—C6—C5	117.39 (11)	C10—N9—C11	115.33 (11)
N6—C7—N5	120.70 (11)	C12—N10—C11	115.81 (10)
N6—C7—N3	117.75 (11)	C12—N11—C10	119.65 (10)
N5—C7—N3	121.55 (11)	C12—N11—H11	120.2
N7—C8—N4	121.63 (11)	C10—N11—H11	120.2
N7—C8—N3	116.81 (11)	C10—N12—H12A	120.0
N4—C8—N3	121.55 (11)	C10—N12—H12B	120.0
N8—C9—N4	116.83 (11)	H12A—N12—H12B	120.0
N8—C9—N5	117.57 (11)	C11—N13—H13A	120.0
N4—C9—N5	125.60 (11)	C11—N13—H13B	120.0
N12—C10—N9	121.52 (11)	H13A—N13—H13B	120.0
N12—C10—N11	116.74 (11)	C12—N14—H14A	120.0
N9—C10—N11	121.74 (11)	C12—N14—H14B	120.0
N13—C11—N9	116.94 (11)	H14A—N14—H14B	120.0
N13—C11—N10	116.87 (11)	H1WA—O1W—H1WB	105 (2)
N9—C11—N10	126.20 (11)	H2WA—O2W—H2WB	103 (2)
N14—C12—N10	120.75 (11)	H3WA—O3W—H3WB	105 (2)
N14—C12—N11	117.99 (11)	H4WA—O4W—H4WB	101 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2	0.86	1.98	2.7726 (16)	153
N6—H6A···N5i	0.86	2.10	2.9449 (17)	169
N6—H6B···O3	0.86	2.19	2.8206 (17)	130
N6—H6B···O2	0.86	2.32	3.0378 (15)	141
N7—H7A···O2Wii	0.86	2.17	3.0080 (16)	164
N7—H7B···O4W	0.86	2.04	2.8407 (19)	156
N8—H8A···N9iii	0.86	2.39	3.2495 (17)	180
N8—H8B···O3i	0.86	2.03	2.8842 (16)	170
N11—H11···O1	0.86	1.98	2.7883 (17)	155
N12—H12A···O4iv	0.86	1.92	2.7557 (15)	162
N12—H12B···O3Wiv	0.86	2.46	2.9981 (18)	121
N12—H12B···O1	0.86	2.47	3.1643 (17)	139
N13—H13A···N4iii	0.86	2.08	2.9275 (16)	167
N13—H13B···O2Wv	0.86	2.10	2.8713 (16)	148
N14—H14B···O1Wvi	0.86	2.21	2.9756 (16)	148
O1W—H1WA···O2	0.89 (3)	1.87 (2)	2.7263 (16)	163 (2)
O1W—H1WB···O1vii	0.93 (3)	1.95 (3)	2.8342 (16)	159 (2)
O2W—H2WA···O1Wvi	0.85 (3)	2.07 (3)	2.8623 (16)	154 (3)
O2W—H2WB···O4	0.93 (3)	1.83 (3)	2.7533 (17)	171 (3)
O3W—H3WA···N2	0.99 (3)	1.97 (3)	2.9589 (16)	170 (2)
O3W—H3WB···O1viii	0.92 (3)	2.07 (3)	2.9810 (15)	176 (2)
O4W—H4WA···O3Wiv	0.93 (3)	1.88 (3)	2.7846 (17)	164 (2)
O4W—H4WB···N1ix	0.89 (3)	2.08 (3)	2.9219 (17)	156 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2	0.86	1.98	2.7726 (16)	153
N6—H6A⋯N5i	0.86	2.10	2.9449 (17)	169
N6—H6B⋯O3	0.86	2.19	2.8206 (17)	130
N6—H6B⋯O2	0.86	2.32	3.0378 (15)	141
N7—H7A⋯O2Wii	0.86	2.17	3.0080 (16)	164
N7—H7B⋯O4W	0.86	2.04	2.8407 (19)	156
N8—H8A⋯N9iii	0.86	2.39	3.2495 (17)	180
N8—H8B⋯O3i	0.86	2.03	2.8842 (16)	170
N11—H11⋯O1	0.86	1.98	2.7883 (17)	155
N12—H12A⋯O4iv	0.86	1.92	2.7557 (15)	162
N12—H12B⋯O3Wiv	0.86	2.46	2.9981 (18)	121
N12—H12B⋯O1	0.86	2.47	3.1643 (17)	139
N13—H13A⋯N4iii	0.86	2.08	2.9275 (16)	167
N13—H13B⋯O2Wv	0.86	2.10	2.8713 (16)	148
N14—H14B⋯O1Wvi	0.86	2.21	2.9756 (16)	148
O1W—H1WA⋯O2	0.89 (3)	1.87 (2)	2.7263 (16)	163 (2)
O1W—H1WB⋯O1vii	0.93 (3)	1.95 (3)	2.8342 (16)	159 (2)
O2W—H2WA⋯O1Wvi	0.85 (3)	2.07 (3)	2.8623 (16)	154 (3)
O2W—H2WB⋯O4	0.93 (3)	1.83 (3)	2.7533 (17)	171 (3)
O3W—H3WA⋯N2	0.99 (3)	1.97 (3)	2.9589 (16)	170 (2)
O3W—H3WB⋯O1viii	0.92 (3)	2.07 (3)	2.9810 (15)	176 (2)
O4W—H4WA⋯O3Wiv	0.93 (3)	1.88 (3)	2.7846 (17)	164 (2)
O4W—H4WB⋯N1ix	0.89 (3)	2.08 (3)	2.9219 (17)	156 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .