Phenazin-5-ium bromide

Zhang, G.-X.; Li, P.; Dong, J.; Chen, H.-Y.

doi:10.1107/S1600536812027869

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2204

https://doi.org/10.1107/S1600536812027869

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Phenazin-5-ium bromide

Gong-Xiao Zhang,^a Ping Li,^a Jian Dong ^a and Hong-Yu Chen ^a ^*

^aFaculty of Chemistry and Chemical Engineering, TaiShan Medical University, Tai'an 271016, People's Republic of China
^*Correspondence e-mail: Binboll@126.com

(Received 10 June 2012; accepted 19 June 2012; online 23 June 2012)

In the title compound, C₁₂H₉N₂⁺·Br⁻, the protonated tricyclic ring system is slightly twisted, with a dihedral angle of 3.9 (1)° between the two outer benzene rings. In the crystal, N—H⋯Br and C—H⋯Br hydrogen bonds link two cations and two bromide anions into centrosymmetric assemblies, which are further packed into stacks along [010] via π–π interactions between the aromatic rings [centroid–centroid distance = 3.725 (4) Å].

Related literature

For applications of phenazines, see: Laursen & Nielsen (2004 ); Uchida & Kimura (1984 ). For related structures, see: Braga et al. (2010 ); Zhang et al. (2012 ).

Experimental

Crystal data

C₁₂H₉N₂⁺·Br⁻
M_r = 261.12
Triclinic, $[P \overline 1]$
a = 5.639 (5) Å
b = 7.958 (5) Å
c = 12.149 (5) Å
α = 73.284 (5)°
β = 86.896 (5)°
γ = 88.360 (5)°
V = 521.3 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.91 mm⁻¹
T = 293 K
0.18 × 0.16 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.541, T_max = 0.556
3029 measured reflections
2085 independent reflections
1840 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.105
S = 1.08
2085 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯Br1	0.86	2.31	3.155 (4)	167
C3—H3A⋯Br1ⁱ	0.93	2.82	3.750 (5)	176
Symmetry code: (i) -x-1, -y, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812027869/cv5312sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027869/cv5312Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027869/cv5312Isup3.cml

checkCIF report

Comment top

In the past decade, much interest has been focused on the phenazine as a template in crystal engineering. The electron rich aromatic system in phenazine enables it to be a good π-donor. Accordingly, phenazine has been employed in the design of charge-transfer complexes (Laursen et al., 2004; Uchida et al., 1984). In a continuation of our study of the compounds with phenazinium cation (Zhang et al., 2012), we present here the title compound, (I).

In (I) (Fig. 1), the bond lengths and angles are normal and correspond to those observed in the related phenazinium chloride (Braga et al., 2010). The asymmetric unit of (I) contains a phenazinium cation and a bromide anion. The phenazinium cations show planar configuration with the largest deviation from the least-square-plane of 0.053 (4) Å for C7. The protonated tricycle is twisted with a dihedral angle of 3.9 (1)° between the two utmost benzene rings.

The cations are packed along the b axis and the tilted angle between the phenazinium plane and b axis of 50.40 (5)°. In the crystal, N—H···Br and C—H···Br hydrogen bonds (Table 1) link two cations and two bromide anions into centrosymmetric clusters, which are further packed into stacks along [010] via π–π interactions between the aromatic rings [centroid-centroid distance = 3.725 (4) Å].

Related literature top

For applications of phenazines, see: Laursen & Nielsen (2004); Uchida & Kimura (1984). For related structures, see: Braga et al. (2010); Zhang et al. (2012).

Experimental top

Phenazine(10.0 g) and 2-bromopropane (4.2 mL) was placed in the teflon liner of an autoclave, which was sealed and heated to 433 K for 48 h, cooled at speed of 10 K/min, whereupon a few of black block of title crystal were obtained.

Structure description top

For applications of phenazines, see: Laursen & Nielsen (2004); Uchida & Kimura (1984). For related structures, see: Braga et al. (2010); Zhang et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic numbering and 50% probability displacement ellipsoids. Dashed line denotes hydrogen bond.

Phenazin-5-ium bromide top

Crystal data top

C₁₂H₉N₂⁺·Br⁻	Z = 2
M_r = 261.12	F(000) = 260
Triclinic, P1	D_x = 1.663 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 5.639 (5) Å	Cell parameters from 1973 reflections
b = 7.958 (5) Å	θ = 2.7–28.3°
c = 12.149 (5) Å	µ = 3.91 mm⁻¹
α = 73.284 (5)°	T = 293 K
β = 86.896 (5)°	Prism, black
γ = 88.360 (5)°	0.18 × 0.16 × 0.15 mm
V = 521.3 (6) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2085 independent reflections
Radiation source: fine-focus sealed tube	1840 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
phi and ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −4→7
T_min = 0.541, T_max = 0.556	k = −9→9
3029 measured reflections	l = −15→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.062P)² + 0.0297P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2085 reflections	Δρ_max = 0.81 e Å⁻³
137 parameters	Δρ_min = −0.65 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.028 (5)

Crystal data top

C₁₂H₉N₂⁺·Br⁻	γ = 88.360 (5)°
M_r = 261.12	V = 521.3 (6) Å³
Triclinic, P1	Z = 2
a = 5.639 (5) Å	Mo Kα radiation
b = 7.958 (5) Å	µ = 3.91 mm⁻¹
c = 12.149 (5) Å	T = 293 K
α = 73.284 (5)°	0.18 × 0.16 × 0.15 mm
β = 86.896 (5)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2085 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1840 reflections with I > 2σ(I)
T_min = 0.541, T_max = 0.556	R_int = 0.028
3029 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.08	Δρ_max = 0.81 e Å⁻³
2085 reflections	Δρ_min = −0.65 e Å⁻³
137 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
Br1	−0.54425 (5)	−0.08849 (4)	0.30612 (2)	0.04706 (19)
C1	0.2320 (6)	0.3452 (4)	−0.0468 (3)	0.0430 (7)
H1A	0.3740	0.4032	−0.0732	0.052*
C2	0.1020 (6)	0.2915 (5)	−0.1191 (3)	0.0494 (8)
H2A	0.1559	0.3123	−0.1955	0.059*
C3	−0.1152 (6)	0.2040 (5)	−0.0819 (3)	0.0492 (8)
H3A	−0.2033	0.1706	−0.1345	0.059*
C4	−0.1977 (6)	0.1679 (4)	0.0300 (3)	0.0435 (7)
H4A	−0.3401	0.1095	0.0543	0.052*
C5	−0.0634 (5)	0.2204 (4)	0.1074 (2)	0.0354 (6)
C6	0.1524 (5)	0.3133 (4)	0.0701 (2)	0.0353 (6)
C7	0.3209 (6)	0.4035 (5)	0.3284 (3)	0.0481 (8)
H7A	0.4564	0.4703	0.3029	0.058*
C8	0.2429 (7)	0.3683 (5)	0.4392 (3)	0.0544 (9)
H8A	0.3257	0.4105	0.4897	0.065*
C9	0.0368 (7)	0.2680 (5)	0.4799 (3)	0.0525 (9)
H9A	−0.0118	0.2442	0.5571	0.063*
C10	−0.0911 (5)	0.2059 (4)	0.4102 (3)	0.0433 (7)
H10A	−0.2270	0.1408	0.4382	0.052*
C11	−0.0137 (5)	0.2419 (4)	0.2938 (2)	0.0351 (6)
C12	0.1979 (5)	0.3395 (4)	0.2505 (2)	0.0363 (6)
N1	0.2781 (4)	0.3709 (3)	0.1416 (2)	0.0384 (6)
N2	−0.1337 (4)	0.1862 (3)	0.2191 (2)	0.0364 (5)
H2B	−0.2603	0.1264	0.2435	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0445 (3)	0.0526 (3)	0.0440 (2)	−0.01652 (15)	0.00696 (14)	−0.01376 (15)
C1	0.0355 (16)	0.0472 (18)	0.0418 (16)	0.0064 (13)	0.0064 (13)	−0.0076 (13)
C2	0.055 (2)	0.051 (2)	0.0394 (17)	0.0125 (16)	0.0031 (15)	−0.0116 (14)
C3	0.055 (2)	0.050 (2)	0.0484 (18)	0.0097 (16)	−0.0095 (15)	−0.0221 (15)
C4	0.0348 (16)	0.0428 (17)	0.0528 (18)	0.0010 (13)	−0.0036 (13)	−0.0136 (14)
C5	0.0311 (14)	0.0353 (15)	0.0385 (15)	0.0048 (12)	0.0017 (11)	−0.0096 (11)
C6	0.0279 (14)	0.0345 (15)	0.0401 (15)	0.0040 (12)	0.0015 (11)	−0.0062 (12)
C7	0.0362 (18)	0.0523 (19)	0.0532 (19)	−0.0104 (15)	0.0010 (14)	−0.0106 (15)
C8	0.058 (2)	0.062 (2)	0.0476 (19)	−0.0110 (18)	−0.0046 (15)	−0.0205 (16)
C9	0.057 (2)	0.060 (2)	0.0393 (17)	−0.0022 (17)	0.0052 (15)	−0.0127 (15)
C10	0.0381 (17)	0.0447 (18)	0.0437 (17)	−0.0050 (14)	0.0076 (13)	−0.0087 (13)
C11	0.0306 (14)	0.0340 (15)	0.0383 (15)	0.0006 (11)	0.0024 (11)	−0.0072 (11)
C12	0.0295 (15)	0.0368 (15)	0.0389 (15)	0.0003 (12)	0.0014 (11)	−0.0056 (12)
N1	0.0283 (12)	0.0398 (14)	0.0426 (13)	−0.0009 (10)	0.0043 (10)	−0.0056 (10)
N2	0.0263 (12)	0.0381 (13)	0.0430 (13)	−0.0042 (10)	0.0053 (10)	−0.0096 (10)

Geometric parameters (Å, º) top

C1—C2	1.339 (5)	C7—C12	1.417 (5)
C1—C6	1.418 (4)	C7—H7A	0.9300
C1—H1A	0.9300	C8—C9	1.413 (5)
C2—C3	1.413 (5)	C8—H8A	0.9300
C2—H2A	0.9300	C9—C10	1.344 (5)
C3—C4	1.364 (4)	C9—H9A	0.9300
C3—H3A	0.9300	C10—C11	1.407 (4)
C4—C5	1.397 (5)	C10—H10A	0.9300
C4—H4A	0.9300	C11—N2	1.339 (4)
C5—N2	1.345 (4)	C11—C12	1.433 (4)
C5—C6	1.426 (4)	C12—N1	1.329 (4)
C6—N1	1.336 (4)	N2—H2B	0.8600
C7—C8	1.345 (5)

C2—C1—C6	119.8 (3)	C12—C7—H7A	119.8
C2—C1—H1A	120.1	C7—C8—C9	120.8 (3)
C6—C1—H1A	120.1	C7—C8—H8A	119.6
C1—C2—C3	121.5 (3)	C9—C8—H8A	119.6
C1—C2—H2A	119.2	C10—C9—C8	122.0 (3)
C3—C2—H2A	119.2	C10—C9—H9A	119.0
C4—C3—C2	121.0 (3)	C8—C9—H9A	119.0
C4—C3—H3A	119.5	C9—C10—C11	118.2 (3)
C2—C3—H3A	119.5	C9—C10—H10A	120.9
C3—C4—C5	118.6 (3)	C11—C10—H10A	120.9
C3—C4—H4A	120.7	N2—C11—C10	121.6 (3)
C5—C4—H4A	120.7	N2—C11—C12	117.3 (3)
N2—C5—C4	121.3 (3)	C10—C11—C12	121.2 (3)
N2—C5—C6	117.8 (3)	N1—C12—C7	120.4 (3)
C4—C5—C6	120.9 (3)	N1—C12—C11	122.3 (3)
N1—C6—C1	120.0 (3)	C7—C12—C11	117.4 (3)
N1—C6—C5	121.8 (3)	C12—N1—C6	118.4 (2)
C1—C6—C5	118.2 (3)	C11—N2—C5	122.4 (2)
C8—C7—C12	120.4 (3)	C11—N2—H2B	118.8
C8—C7—H7A	119.8	C5—N2—H2B	118.8

C6—C1—C2—C3	0.4 (5)	C9—C10—C11—C12	1.1 (5)
C1—C2—C3—C4	−1.4 (5)	C8—C7—C12—N1	−178.4 (3)
C2—C3—C4—C5	0.5 (5)	C8—C7—C12—C11	1.9 (5)
C3—C4—C5—N2	−179.0 (3)	N2—C11—C12—N1	−1.7 (4)
C3—C4—C5—C6	1.4 (5)	C10—C11—C12—N1	178.0 (3)
C2—C1—C6—N1	−178.1 (3)	N2—C11—C12—C7	178.0 (3)
C2—C1—C6—C5	1.4 (5)	C10—C11—C12—C7	−2.3 (4)
N2—C5—C6—N1	−2.4 (4)	C7—C12—N1—C6	−177.8 (3)
C4—C5—C6—N1	177.2 (3)	C11—C12—N1—C6	1.9 (4)
N2—C5—C6—C1	178.1 (3)	C1—C6—N1—C12	179.7 (3)
C4—C5—C6—C1	−2.3 (4)	C5—C6—N1—C12	0.1 (4)
C12—C7—C8—C9	−0.4 (6)	C10—C11—N2—C5	179.5 (3)
C7—C8—C9—C10	−0.9 (6)	C12—C11—N2—C5	−0.7 (4)
C8—C9—C10—C11	0.5 (6)	C4—C5—N2—C11	−177.0 (3)
C9—C10—C11—N2	−179.2 (3)	C6—C5—N2—C11	2.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Br1	0.86	2.31	3.155 (4)	167
C3—H3A···Br1ⁱ	0.93	2.82	3.750 (5)	176

Symmetry code: (i) −x−1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₉N₂⁺·Br⁻
M_r	261.12
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.639 (5), 7.958 (5), 12.149 (5)
α, β, γ (°)	73.284 (5), 86.896 (5), 88.360 (5)
V (Å³)	521.3 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.91
Crystal size (mm)	0.18 × 0.16 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.541, 0.556
No. of measured, independent and observed [I > 2σ(I)] reflections	3029, 2085, 1840
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.105, 1.08
No. of reflections	2085
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.65

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Br1	0.86	2.3116	3.155 (4)	166.67
C3—H3A···Br1ⁱ	0.93	2.8212	3.750 (5)	176.02

Symmetry code: (i) −x−1, −y, −z.

Acknowledgements

This work was supported by the Shandong College research program (grant No. J11LB15) and the Young and Middle-aged Scientist Research Awards Foundation of Shandong Province (grant No. BS2010CL045).

References

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