Phenazine–naphthalene-1,5-diamine–water (1/1/2)

Czapik, A.; Gdaniec, M.

doi:10.1107/S1600536809049009

organic compounds

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Volume 65| Part 12| December 2009| Page o3177

doi:10.1107/S1600536809049009

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Phenazine–naphthalene-1,5-diamine–water (1/1/2)

Agnieszka Czapik ^a and Maria Gdaniec ^a ^*

^aFaculty of Chemistry, Adam Mickiewicz University, 60-780 Poznań, Poland
^*Correspondence e-mail: magdan@amu.edu.pl

(Received 6 November 2009; accepted 17 November 2009; online 21 November 2009)

The asymmetric unit of the title compound, C₁₂H₈N₂·C₁₀H₁₀N₂·2H₂O, contains one half-molecule of phenazine, one half-molecule of naphthalene-1,5-diamine and one water molecule. The phenazine and naphthalene-1,5-diamine molecules are located on inversion centers. The water molecules serve as bridges between the naphthalene-1,5-diamine molecules and also between the naphthalene-1,5-diamine and phenazine molecules. The naphthalene-1,5-diamine and water molecules are connected via N—H⋯O and O—H⋯N hydrogen bonds, forming a T4(2) motif. They are arranged into a two-dimensional polymeric structure parallel to (10 $[\overline{1}]$ ) in which the water molecule is a single donor and a double acceptor, whereas the amino group is a double donor and a single acceptor in the hydrogen bonding. These two-dimensional assemblies alternate with the layers of phenazine molecules arranged into a herringbone motif. Each phenazine molecule is hydrogen bonded to two water molecules and thus a three-dimensional framework of hydrogen-bonded molecules is generated.

Related literature

For the structures of co-crystals of aromatic diazaheterocycles with small aromatic molecules, see: Thalladi et al. (2000 ); Kadzewski & Gdaniec (2006 ); Czapik & Gdaniec (2008 ). For structures with similar T4(2) hydrogen-bond motifs, see: Anthony et al. (2007 ); Neely et al. (2007 ). For symbols of hydrogen-bond motifs, see: Infantes et al. (2003 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₂H₈N₂·C₁₀H₁₀N₂·2H₂O
M_r = 374.44
Monoclinic, P 2₁ /n
a = 13.0395 (10) Å
b = 4.9266 (2) Å
c = 15.7211 (12) Å
β = 112.508 (9)°
V = 933.00 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 130 K
0.25 × 0.25 × 0.25 mm

Data collection

Kuma KM-4-CCD κ-geometry diffractometer
Absorption correction: none
5251 measured reflections
1643 independent reflections
1357 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.140
S = 1.08
1643 reflections
143 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1N⋯O1W	0.91 (4)	2.10 (4)	2.999 (3)	169 (3)
N1A—H2N⋯O1Wⁱ	0.97 (3)	2.15 (3)	3.102 (3)	166 (2)
O1W—H1W⋯N1Aⁱⁱ	0.85 (5)	2.04 (5)	2.871 (3)	167 (4)
O1W—H2W⋯N1B	0.89 (3)	2.07 (3)	2.953 (3)	174 (3)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ); 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 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049009/rz2392sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049009/rz2392Isup2.hkl

checkCIF report

Comment top

The title compound has been obtained unintentionally during our attempts to co-crystallize phenazine with naphthalene-1,5-diamine. Heterocycles like phenazine and quinoxaline are known to form a robust host framework with one-dimensional channels filled with small aromatic guest molecules (Thalladi et al., 2000; Kadzewski & Gdaniec; 2006). Inclusion of water molecules have however a significant impact on arrangement of molecules in these co-crystals (Czapik & Gdaniec, 2008).

Crystal packing of the title compound is shown in Fig. 2. Phenazine and naphthalene-1,5-diamine molecules are situated around inversion centers and are arranged into stacks along [010] by π–π stacking interactions. The molecules of naphthalene-1,5-diamine and water are connected via N—H···O and O—H···N hydrogen bonds that form the T4(2) motif (Table 1, Fig. 3). These hydrogen bonds connect molecules into a two-dimensional polymeric structure parallel to (1 0 - 1) in which the water molecule is a single donor and a double acceptor whereas the amino group plays a role a double donor and a single acceptor (Fig. 3). The layers of naphthalene-1,5-diamine and water molecules alternate with the layers of phenazine in which these aromatic molecules show a herringbone arrangement (Fig. 4). The phenazine molecules are hydrogen bonded to two water molecules and thus a three-dimensional framework of hydrogen-bonded molecules is generated (Fig. 2).

The Cambridge Structural Database (Allen, 2002) was searched for the structures containing C—NH₂ groups and water molecules to look for the frequency of the T4(2) motif (Infantes et al., 2003) generated by primary amino groups and water molecules. The search was limited to organic compounds with polymeric and ionic structures excluded and gave only two structures with the CSD refcodes DISNEZ, (Anthony et al., 2007) and MIMWAH01 (Neely et al., 2007). In both cases the donor and acceptor functions of the amino group and water molecule were analogous to those in the title compound.

Related literature top

For the structures of co-crystals of aromatic diazaheterocycles with small aromatic molecules, see: Thalladi et al. (2000); Kadzewski & Gdaniec (2006); Czapik & Gdaniec (2008). For structures with similar T4(2) hydrogen-bond motifs, see: Anthony et al. (2007); Neely et al. (2007). For symbols of hydrogen-bond motifs, see: Infantes et al. (2003). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The title compound was obtained by dissolving phenazine (0.100 g, 0.55 mmol) and naphthalene-1,5-diamine (0.088 g, 0.55 mmol) in 5 ml of acetone. Slow evaporation of the solution yielded red cuboid crystals.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); 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) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. : The molecular structure of the title compound with displacement ellipsoids shown at the 50% probability level. Hydrogen bonds are shown as dashed lines and only atoms from the asymmetric unit are labelled.
	Fig. 2. : Crystal packing viewed down the y axis. Hydrogen bonds are shown with dashed lines.
	Fig. 3. Hydrogen-bonded water molecule and aromatic amine generating the T4(2) motif.
	Fig. 4. The herringbone arrangement of phenazine molecules parallel to (1 0 - 1)

Phenazine–naphthalene-1,5-diamine–water (1/1/2) top

Crystal data top

C₁₂H₈N₂·C₁₀H₁₀N₂·2H₂O	F(000) = 396
M_r = 374.44	D_x = 1.333 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3369 reflections
a = 13.0395 (10) Å	θ = 2.6–27.9°
b = 4.9266 (2) Å	µ = 0.09 mm⁻¹
c = 15.7211 (12) Å	T = 130 K
β = 112.508 (9)°	Cube, red
V = 933.00 (11) Å³	0.25 × 0.25 × 0.25 mm
Z = 2

Data collection top

Kuma KM-4-CCD κ-geometry diffractometer	1357 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 25.0°, θ_min = 4.4°
ω scans	h = −15→15
5251 measured reflections	k = −5→5
1643 independent reflections	l = −18→18

Refinement top

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0606P)² + 1.1003P] where P = (F_o² + 2F_c²)/3
1643 reflections	(Δ/σ)_max < 0.001
143 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₈N₂·C₁₀H₁₀N₂·2H₂O	V = 933.00 (11) Å³
M_r = 374.44	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.0395 (10) Å	µ = 0.09 mm⁻¹
b = 4.9266 (2) Å	T = 130 K
c = 15.7211 (12) Å	0.25 × 0.25 × 0.25 mm
β = 112.508 (9)°

Data collection top

Kuma KM-4-CCD κ-geometry diffractometer	1357 reflections with I > 2σ(I)
5251 measured reflections	R_int = 0.022
1643 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.22 e Å⁻³
1643 reflections	Δρ_min = −0.23 e Å⁻³
143 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1A	0.12558 (17)	0.2658 (5)	0.18906 (13)	0.0249 (5)
H1N	0.116 (3)	0.419 (8)	0.218 (2)	0.054 (10)*
H2N	0.198 (3)	0.258 (6)	0.1847 (19)	0.038 (8)*
C1A	0.03659 (18)	0.2272 (5)	0.10357 (15)	0.0220 (5)
C2A	−0.05954 (19)	0.3753 (5)	0.08078 (15)	0.0245 (5)
H2A	−0.0655	0.5056	0.1214	0.029*
C3A	−0.14918 (19)	0.3314 (5)	−0.00367 (16)	0.0248 (5)
H3A	−0.2135	0.4343	−0.0185	0.030*
C4A	0.14256 (19)	−0.1391 (5)	0.06406 (16)	0.0243 (5)
H4A	0.2021	−0.1134	0.1197	0.029*
C5A	0.04549 (18)	0.0218 (5)	0.04242 (15)	0.0223 (5)
N1B	0.05503 (15)	0.9466 (4)	0.43964 (12)	0.0220 (5)
C2B	0.08133 (18)	0.8115 (5)	0.51930 (15)	0.0211 (5)
C3B	0.16597 (18)	0.6111 (5)	0.54398 (16)	0.0252 (5)
H3B	0.2031	0.5753	0.5051	0.030*
C4B	0.19301 (19)	0.4712 (5)	0.62413 (17)	0.0279 (6)
H4B	0.2489	0.3411	0.6399	0.033*
C5B	−0.02539 (18)	1.1344 (5)	0.41932 (15)	0.0217 (5)
C6B	−0.0560 (2)	1.2869 (5)	0.33626 (15)	0.0258 (6)
H6B	−0.0206	1.2553	0.2959	0.031*
C7B	−0.1367 (2)	1.4781 (5)	0.31585 (16)	0.0290 (6)
H7B	−0.1555	1.5778	0.2617	0.035*
O1W	0.12857 (15)	0.7813 (4)	0.29145 (12)	0.0297 (5)
H1W	0.137 (3)	0.932 (10)	0.269 (3)	0.074 (13)*
H2W	0.107 (2)	0.819 (6)	0.337 (2)	0.035 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0267 (11)	0.0260 (12)	0.0211 (10)	−0.0033 (9)	0.0081 (8)	−0.0025 (9)
C1A	0.0246 (12)	0.0221 (12)	0.0212 (11)	−0.0043 (10)	0.0108 (9)	0.0018 (9)
C2A	0.0294 (12)	0.0227 (12)	0.0247 (12)	−0.0004 (10)	0.0138 (10)	0.0008 (10)
C3A	0.0222 (11)	0.0244 (13)	0.0292 (12)	0.0022 (10)	0.0114 (10)	0.0043 (10)
C4A	0.0223 (11)	0.0243 (13)	0.0261 (12)	−0.0029 (10)	0.0089 (9)	0.0011 (10)
C5A	0.0261 (11)	0.0201 (12)	0.0240 (11)	−0.0036 (9)	0.0132 (10)	0.0020 (9)
N1B	0.0252 (10)	0.0201 (10)	0.0230 (10)	−0.0026 (8)	0.0119 (8)	−0.0032 (8)
C2B	0.0226 (11)	0.0181 (12)	0.0247 (11)	−0.0044 (9)	0.0114 (9)	−0.0038 (9)
C3B	0.0245 (12)	0.0240 (12)	0.0302 (12)	−0.0001 (10)	0.0139 (10)	−0.0017 (10)
C4B	0.0250 (12)	0.0216 (13)	0.0346 (13)	0.0027 (10)	0.0085 (10)	−0.0008 (10)
C5B	0.0228 (11)	0.0196 (12)	0.0246 (12)	−0.0039 (9)	0.0111 (9)	−0.0040 (9)
C6B	0.0312 (12)	0.0262 (13)	0.0220 (12)	−0.0006 (11)	0.0124 (10)	−0.0005 (10)
C7B	0.0355 (13)	0.0237 (13)	0.0257 (12)	−0.0014 (11)	0.0094 (10)	0.0021 (10)
O1W	0.0405 (10)	0.0279 (11)	0.0257 (9)	0.0042 (8)	0.0182 (8)	−0.0001 (8)

Geometric parameters (Å, º) top

N1A—C1A	1.412 (3)	N1B—C5B	1.342 (3)
N1A—H1N	0.91 (4)	C2B—C3B	1.420 (3)
N1A—H2N	0.97 (3)	C2B—C5Bⁱⁱ	1.440 (3)
C1A—C2A	1.374 (3)	C3B—C4B	1.359 (3)
C1A—C5A	1.431 (3)	C3B—H3B	0.9300
C2A—C3A	1.410 (3)	C4B—C7Bⁱⁱ	1.422 (4)
C2A—H2A	0.9300	C4B—H4B	0.9300
C3A—C4Aⁱ	1.367 (3)	C5B—C6B	1.425 (3)
C3A—H3A	0.9300	C6B—C7B	1.356 (3)
C4A—C3Aⁱ	1.367 (3)	C6B—H6B	0.9300
C4A—C5A	1.420 (3)	C7B—H7B	0.9300
C4A—H4A	0.9300	O1W—H1W	0.85 (5)
C5A—C5Aⁱ	1.422 (4)	O1W—H2W	0.89 (3)
N1B—C2B	1.341 (3)

C1A—N1A—H1N	111 (2)	N1B—C2B—C3B	119.61 (19)
C1A—N1A—H2N	113.2 (16)	N1B—C2B—C5Bⁱⁱ	121.3 (2)
H1N—N1A—H2N	113 (3)	C3B—C2B—C5Bⁱⁱ	119.1 (2)
C2A—C1A—N1A	120.8 (2)	C4B—C3B—C2B	120.3 (2)
C2A—C1A—C5A	120.1 (2)	C4B—C3B—H3B	119.8
N1A—C1A—C5A	119.1 (2)	C2B—C3B—H3B	119.8
C1A—C2A—C3A	120.6 (2)	C3B—C4B—C7Bⁱⁱ	120.7 (2)
C1A—C2A—H2A	119.7	C3B—C4B—H4B	119.7
C3A—C2A—H2A	119.7	C7Bⁱⁱ—C4B—H4B	119.7
C4Aⁱ—C3A—C2A	120.7 (2)	N1B—C5B—C6B	120.1 (2)
C4Aⁱ—C3A—H3A	119.7	N1B—C5B—C2Bⁱⁱ	121.2 (2)
C2A—C3A—H3A	119.7	C6B—C5B—C2Bⁱⁱ	118.7 (2)
C3Aⁱ—C4A—C5A	120.5 (2)	C7B—C6B—C5B	120.2 (2)
C3Aⁱ—C4A—H4A	119.7	C7B—C6B—H6B	119.9
C5A—C4A—H4A	119.7	C5B—C6B—H6B	119.9
C4A—C5A—C5Aⁱ	119.2 (3)	C6B—C7B—C4Bⁱⁱ	121.0 (2)
C4A—C5A—C1A	121.9 (2)	C6B—C7B—H7B	119.5
C5Aⁱ—C5A—C1A	118.9 (3)	C4Bⁱⁱ—C7B—H7B	119.5
C2B—N1B—C5B	117.47 (18)	H1W—O1W—H2W	107 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1N···O1W	0.91 (4)	2.10 (4)	2.999 (3)	169 (3)
N1A—H2N···O1Wⁱⁱⁱ	0.97 (3)	2.15 (3)	3.102 (3)	166 (2)
O1W—H1W···N1A^iv	0.85 (5)	2.04 (5)	2.871 (3)	167 (4)
O1W—H2W···N1B	0.89 (3)	2.07 (3)	2.953 (3)	174 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₈N₂·C₁₀H₁₀N₂·2H₂O
M_r	374.44
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	130
a, b, c (Å)	13.0395 (10), 4.9266 (2), 15.7211 (12)
β (°)	112.508 (9)
V (Å³)	933.00 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.25 × 0.25

Data collection
Diffractometer	Kuma KM-4-CCD κ-geometry diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5251, 1643, 1357
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.140, 1.08
No. of reflections	1643
No. of parameters	143
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.23

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1N···O1W	0.91 (4)	2.10 (4)	2.999 (3)	169 (3)
N1A—H2N···O1Wⁱ	0.97 (3)	2.15 (3)	3.102 (3)	166 (2)
O1W—H1W···N1Aⁱⁱ	0.85 (5)	2.04 (5)	2.871 (3)	167 (4)
O1W—H2W···N1B	0.89 (3)	2.07 (3)	2.953 (3)	174 (3)

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

References

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doi:10.1107/S1600536809049009

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