2,8-Di­hydroxy-1,3,7,9-tetra­methyl-6,12-di­hydro­dipyrido­[1,2-a:1′,2′-d]pyrazine­diyl­ium dichloride dihydrate

The 2,8-di­hydroxy-1,3,7,9-tetra­methyl-6,12-di­hydro­di­pyrido[1,2-a:1′,2′-d]pyrazine­diyl­ium dication possesses 2/m symmetry and lies in the mirror plane together with a chloride anion and the water O atom. The dication also lies on an inversion centre, i.e. C₁₆H₂₀N₂O₂²⁺·2Cl⁻·2H₂O. Due to these symmetry constrictions the dication adopts an unexpected planar conformation. Molecules are linked by O—H...O and O—H...Cl hydrogen bonds to form chains, which are cross-connected by C—H...Cl attractive interactions forming a complex three-dimensional hydrogen-bond network.

Computing details

Data collection: STADI4 (Stoe & Cie, 1996a); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON2000 (Spek, 2000); software used to prepare material for publication: SHELXL97 and PARST96 (Nardelli, 1995).

6,12-Dihydro-2,8-dihydroxy-1,3,7,9-tetramethyl-dipyrido[1,2 - a:1',2'-d] pyrazinediylium dichloride dihydrate

Crystal data

C16H20N2O2^2+·2Cl^−·2H2O	F(000) = 400
Mr = 379.28	Dx = 1.407 Mg m^−3
Monoclinic, I2/m	Mo Kα radiation, λ = 0.71073 Å
a = 11.255 (15) Å	Cell parameters from 10 reflections
b = 6.8650 (13) Å	θ = 6.4–14.3°
c = 11.9530 (12) Å	µ = 0.39 mm^−1
β = 104.15 (2)°	T = 293 K
V = 895.5 (12) Å^3	Prism, colourless
Z = 2	0.50 × 0.45 × 0.40 mm

Data collection

Philips PW1100 upgraded by Stoe & Cie diffractometer	1146 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.021
Graphite monochromator	θmax = 30.0°, θmin = 3.0°
ω–scan	h = −15→15
Absorption correction: numerical X-RED (Stoe & Cie, 1996b)	k = −9→0
Tmin = 0.801, Tmax = 0.888	l = 0→16
2776 measured reflections	3 standard reflections every 60 min
1388 independent reflections	intensity decay: 1.0%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0895P)^2] where P = (Fo^2 + 2Fc^2)/3
1388 reflections	(Δ/σ)max < 0.001
78 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.70308 (5)	0.0000	0.11959 (5)	0.0599 (3)
O1W	0.43032 (18)	0.0000	0.13863 (17)	0.0822 (9)
H1W	0.4015 (12)	0.0000	0.070 (3)	0.090 (14)*
H2W	0.495 (3)	0.0000	0.1464 (3)	0.086 (13)*
N5	0.01901 (14)	0.0000	0.38809 (14)	0.0343 (4)
O2'	0.35773 (15)	0.0000	0.32597 (15)	0.0652 (6)
H2'	0.3673 (5)	0.0000	0.262 (3)	0.060 (9)*
C13	0.11818 (16)	0.0000	0.47604 (16)	0.0344 (4)
C6	−0.10741 (17)	0.0000	0.40238 (17)	0.0424 (5)
H6A	−0.1494	−0.1140	0.3639	0.051*	0.50
C1	0.23454 (18)	0.0000	0.45637 (18)	0.0429 (5)
C1'	0.34721 (19)	0.0000	0.5551 (2)	0.0578 (7)
H1'1	0.4191	0.0000	0.5253	0.087*
H1'2	0.3472	−0.1142	0.6015	0.087*	0.50
C2	0.24504 (19)	0.0000	0.34112 (19)	0.0488 (6)
C4	0.02755 (19)	0.0000	0.27661 (18)	0.0426 (5)
H4	−0.0436	0.0000	0.2174	0.051*
C3'	0.1451 (2)	0.0000	0.1251 (2)	0.0682 (9)
H3'1	0.2292	0.0000	0.1209	0.102*
H3'2	0.1049	0.1142	0.0875	0.102*	0.50
C3	0.1392 (2)	0.0000	0.25002 (18)	0.0481 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0415 (4)	0.0965 (6)	0.0401 (4)	0.000	0.0067 (2)	0.000
O1W	0.0398 (9)	0.174 (3)	0.0367 (9)	0.000	0.0161 (7)	0.000
N5	0.0242 (7)	0.0509 (9)	0.0276 (7)	0.000	0.0062 (5)	0.000
O2'	0.0291 (7)	0.1341 (18)	0.0354 (9)	0.000	0.0134 (6)	0.000
C13	0.0255 (8)	0.0505 (10)	0.0277 (8)	0.000	0.0072 (6)	0.000
C6	0.0230 (8)	0.0761 (14)	0.0277 (9)	0.000	0.0055 (7)	0.000
C1	0.0246 (8)	0.0752 (14)	0.0284 (9)	0.000	0.0052 (7)	0.000
C1'	0.0238 (8)	0.115 (2)	0.0329 (10)	0.000	0.0043 (7)	0.000
C2	0.0270 (9)	0.0885 (17)	0.0318 (10)	0.000	0.0091 (7)	0.000
C4	0.0299 (8)	0.0692 (14)	0.0279 (8)	0.000	0.0058 (7)	0.000
C3'	0.0393 (11)	0.136 (3)	0.0297 (10)	0.000	0.0099 (9)	0.000
C3	0.0314 (9)	0.0851 (16)	0.0280 (9)	0.000	0.0074 (7)	0.000

Geometric parameters (Å, º)

O1W—H1W	0.81 (3)	C1—C2	1.411 (3)
O1W—H2W	0.71 (3)	C1—C1'	1.506 (3)
N5—C13	1.333 (3)	C1'—H1'1	0.96
N5—C4	1.359 (3)	C1'—H1'2	0.96
N5—C6	1.474 (3)	C1'—H1'3	0.96
O2'—C2	1.324 (3)	C2—C3	1.403 (3)
O2'—H2'	0.80 (3)	C4—C3	1.370 (3)
C13—C1	1.386 (3)	C4—H4	0.93
C13—C6^i	1.488 (3)	C3'—C3	1.510 (3)
C6—C13^i	1.488 (3)	C3'—H3'1	0.96
C6—H6A	0.97	C3'—H3'2	0.96
C6—H6B	0.97	C3'—H3'3	0.96
H1W—O1W—H2W	106.3	H1'1—C1'—H1'2	109.5
C13—N5—C4	121.8 (2)	C1—C1'—H1'3	109.5
C13—N5—C6	123.7 (2)	H1'1—C1'—H1'3	109.5
C4—N5—C6	114.5 (2)	H1'2—C1'—H1'3	109.5
C2—O2'—H2'	119.3	O2'—C2—C3	123.6 (2)
N5—C13—C1	120.7 (2)	O2'—C2—C1	116.4 (2)
N5—C13—C6^i	121.2 (2)	C3—C2—C1	120.0 (2)
C1—C13—C6^i	118.2 (2)	N5—C4—C3	121.1 (2)
N5—C6—C13^i	115.1 (2)	N5—C4—H4	119.5
N5—C6—H6A	108.5	C3—C4—H4	119.5
C13^i—C6—H6A	108.5	C3—C3'—H3'1	109.5
N5—C6—H6B	108.5	C3—C3'—H3'2	109.5
C13^i—C6—H6B	108.5	H3'1—C3'—H3'2	109.5
H6A—C6—H6B	107.5	C3—C3'—H3'3	109.5
C13—C1—C2	118.3 (2)	H3'1—C3'—H3'3	109.5
C13—C1—C1'	121.1 (2)	H3'2—C3'—H3'3	109.5
C2—C1—C1'	120.6 (2)	C4—C3—C2	118.2 (2)
C1—C1'—H1'1	109.5	C4—C3—C3'	119.6 (2)
C1—C1'—H1'2	109.5	C2—C3—C3'	122.2 (2)
C4—N5—C13—C1	0.0	C1'—C1—C2—O2'	0.0
C6—N5—C13—C1	180.0	C13—C1—C2—C3	0.0
C4—N5—C13—C6^i	180.0	C1'—C1—C2—C3	180.0
C6—N5—C13—C6^i	0.0	C13—N5—C4—C3	0.0
C13—N5—C6—C13^i	0.0	C6—N5—C4—C3	180.0
C4—N5—C6—C13^i	180.0	N5—C4—C3—C2	0.0
N5—C13—C1—C2	0.0	N5—C4—C3—C3'	180.0
C6^i—C13—C1—C2	180.0	O2'—C2—C3—C4	180.0
N5—C13—C1—C1'	180.0	C1—C2—C3—C4	0.0
C6^i—C13—C1—C1'	0.0	O2'—C2—C3—C3'	0.0
C13—C1—C2—O2'	180.0	C1—C2—C3—C3'	180.0

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2′—H2′···O1W	0.80 (3)	1.79 (3)	2.564 (4)	165 (2)
O1W—H2W···Cl1	0.71 (3)	2.44 (3)	3.133 (5)	165 (4)
O1W—H1W···Cl1^ii	0.81 (3)	2.28 (3)	3.085 (5)	173 (2)
C4—H4···Cl1^iii	0.93	2.81	3.675 (5)	156
C6—H6A···Cl1^iv	0.97	2.74	3.588 (5)	147

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