Phenazin-5-ium bromide.

In the title compound, C(12)H(9)N(2) (+)·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 inter-actions 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 = 261.12

Triclinic,

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[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.105

S = 1.08

2085 reflections

137 parameters

H-atom parameters constrained

Δρmax = 0.81 e Å−3

Δρmin = −0.65 e Å−3

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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812027869/cv5312sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027869/cv5312Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812027869/cv5312Isup3.cml

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

C12H9N2+·Br−	Z = 2
Mr = 261.12	F(000) = 260
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.062P)2 + 0.0297P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
2085 reflections	Δρmax = 0.81 e Å−3
137 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .