Phenazinium methyl sulfate.

The title salt, C(12)H(9)N(2) (+)·CH(3)O(4)S(-), contains an almost planar phenazinium cation [largest deviation from the least-squares plane = 0.040 (3) Å] and a methyl sulfate anion. The sulfate moiety of the latter is disordered over two sets of sites in a 0.853 (5):0.147 (5) ratio. In the crystal, the cations and anions are arranged alternately in layers parallel to (010). The cations pack along [100] with a tilt angle of 28.96 (4)° between this axis and the mean plane and are linked through inter-planar π-π inter-actions [shortest inter-planar distance = 3.421 (4) Å]. N-H⋯O hydrogen-bonding between the cations and anions is also observed.

Related literature

For background to the use of phenazine in crystal engineering, see: Laursen & Nielsen (2004 ▶). For a related structure, see: Meszko et al. (2002 ▶).

Experimental

Crystal data

C12H9N2 +·CH3O4S−

M = 292.31

Triclinic,

a = 5.818 (5) Å

b = 9.667 (5) Å

c = 11.460 (5) Å

α = 95.241 (5)°

β = 90.336 (5)°

γ = 93.691 (5)°

V = 640.5 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.27 mm−1

T = 293 K

0.18 × 0.15 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.951, T max = 0.965

3642 measured reflections

2572 independent reflections

2266 reflections with I > 2σ(I)

R int = 0.127

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.185

S = 1.07

2572 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.54 e Å−3

Δρmin = −0.72 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: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812026025/wm2637sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026025/wm2637Isup2.hkl

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

C12H9N2+·CH3O4S−	Z = 2
Mr = 292.31	F(000) = 304
Triclinic, P1	Dx = 1.516 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 5.818 (5) Å	Cell parameters from 4012 reflections
b = 9.667 (5) Å	θ = 0.4–14.1°
c = 11.460 (5) Å	µ = 0.27 mm−1
α = 95.241 (5)°	T = 293 K
β = 90.336 (5)°	Block, yellow
γ = 93.691 (5)°	0.18 × 0.15 × 0.12 mm
V = 640.5 (7) Å3

Bruker APEXII CCD diffractometer	2572 independent reflections
Radiation source: fine-focus sealed tube	2266 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.127
φ– and ω– scans	θmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→6
Tmin = 0.951, Tmax = 0.965	k = −12→11
3642 measured reflections	l = −14→12

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.185	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.1118P)2 + 0.2488P] where P = (Fo2 + 2Fc2)/3
2572 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.72 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 > 2sigma(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	Occ. (<1)
N1	0.3313 (3)	0.1672 (2)	0.84021 (18)	0.0391 (5)
H101	0.2116	0.2132	0.8318	0.047*
N2	0.7148 (3)	0.0191 (2)	0.86741 (19)	0.0432 (5)
C1	0.4340 (4)	0.3195 (3)	1.0121 (2)	0.0447 (6)
H100	0.3031	0.3686	1.0053	0.054*
C2	0.5880 (5)	0.3558 (3)	1.1006 (2)	0.0512 (6)
H2	0.5613	0.4302	1.1550	0.061*
C3	0.7895 (5)	0.2821 (3)	1.1116 (2)	0.0508 (6)
H3	0.8952	0.3112	1.1714	0.061*
C4	0.8303 (4)	0.1705 (3)	1.0367 (2)	0.0461 (6)
H4	0.9602	0.1214	1.0468	0.055*
C5	0.6737 (4)	0.1283 (2)	0.9423 (2)	0.0380 (5)
C6	0.4758 (4)	0.2065 (2)	0.9312 (2)	0.0372 (5)
C7	0.3673 (4)	0.0595 (3)	0.7627 (2)	0.0406 (5)
C8	0.2129 (5)	0.0209 (3)	0.6681 (2)	0.0538 (7)
H8	0.0821	0.0694	0.6588	0.065*
C9	0.2593 (6)	−0.0875 (3)	0.5918 (3)	0.0640 (8)
H9	0.1585	−0.1136	0.5292	0.077*
C10	0.4572 (6)	−0.1629 (3)	0.6041 (3)	0.0636 (8)
H10	0.4855	−0.2361	0.5487	0.076*
C11	0.6058 (5)	−0.1301 (3)	0.6951 (3)	0.0557 (7)
H11	0.7332	−0.1820	0.7032	0.067*
C12	0.5663 (4)	−0.0160 (3)	0.7782 (2)	0.0414 (5)
S1	0.88381 (9)	0.37619 (6)	0.71184 (5)	0.0422 (3)
O1A	0.8047 (4)	0.5126 (3)	0.7145 (2)	0.0583 (8)	0.853 (5)
O2	1.0304 (4)	0.3550 (2)	0.81033 (17)	0.0602 (6)
O3	0.7187 (5)	0.2637 (3)	0.6816 (3)	0.0894 (9)
O4A	1.0400 (4)	0.3553 (3)	0.59643 (19)	0.0545 (7)	0.853 (5)
C13	1.2319 (5)	0.4504 (4)	0.5904 (3)	0.0679 (9)
H13A	1.1875	0.5429	0.6129	0.102*
H13B	1.2884	0.4454	0.5117	0.102*
H13C	1.3507	0.4278	0.6426	0.102*
O1B	1.035 (3)	0.4806 (16)	0.6513 (14)	0.063 (5)*	0.147 (5)
O4B	0.718 (3)	0.4697 (18)	0.7705 (17)	0.069 (5)*	0.147 (5)

	U11	U22	U33	U12	U13	U23
N1	0.0301 (9)	0.0466 (11)	0.0416 (10)	0.0090 (8)	−0.0058 (8)	0.0053 (8)
N2	0.0344 (10)	0.0489 (12)	0.0471 (11)	0.0108 (8)	−0.0026 (9)	0.0032 (9)
C1	0.0416 (13)	0.0469 (13)	0.0465 (13)	0.0125 (10)	−0.0029 (11)	0.0034 (10)
C2	0.0561 (15)	0.0510 (14)	0.0457 (14)	0.0085 (12)	−0.0037 (12)	−0.0027 (11)
C3	0.0452 (14)	0.0609 (16)	0.0455 (13)	0.0025 (12)	−0.0137 (11)	0.0018 (11)
C4	0.0337 (12)	0.0571 (15)	0.0487 (13)	0.0088 (10)	−0.0081 (11)	0.0077 (11)
C5	0.0285 (10)	0.0443 (12)	0.0420 (12)	0.0061 (9)	−0.0010 (9)	0.0063 (9)
C6	0.0313 (11)	0.0426 (12)	0.0389 (11)	0.0054 (9)	−0.0021 (9)	0.0073 (9)
C7	0.0347 (11)	0.0465 (13)	0.0406 (12)	0.0027 (9)	−0.0030 (10)	0.0041 (10)
C8	0.0491 (15)	0.0617 (16)	0.0497 (14)	0.0034 (12)	−0.0147 (12)	0.0017 (12)
C9	0.0687 (19)	0.0686 (19)	0.0517 (16)	0.0006 (15)	−0.0150 (14)	−0.0065 (14)
C10	0.072 (2)	0.0604 (17)	0.0547 (16)	0.0045 (15)	0.0017 (15)	−0.0138 (13)
C11	0.0527 (15)	0.0530 (15)	0.0603 (16)	0.0112 (12)	0.0039 (13)	−0.0057 (12)
C12	0.0346 (11)	0.0471 (13)	0.0424 (12)	0.0040 (9)	0.0013 (10)	0.0029 (10)
S1	0.0289 (3)	0.0536 (4)	0.0452 (4)	0.0116 (2)	−0.0043 (2)	0.0049 (3)
O1A	0.0508 (14)	0.0665 (16)	0.0608 (15)	0.0302 (12)	−0.0018 (12)	0.0050 (12)
O2	0.0572 (12)	0.0763 (14)	0.0491 (11)	0.0274 (10)	−0.0149 (9)	0.0008 (9)
O3	0.0926 (19)	0.0844 (18)	0.0879 (18)	−0.0211 (15)	−0.0266 (16)	0.0104 (14)
O4A	0.0513 (13)	0.0639 (15)	0.0479 (13)	0.0122 (11)	0.0020 (10)	−0.0033 (10)
C13	0.0365 (13)	0.107 (3)	0.0619 (17)	0.0065 (15)	0.0059 (13)	0.0143 (17)

N1—C7	1.333 (3)	C8—H8	0.9300
N1—C6	1.347 (3)	C9—C10	1.415 (5)
N1—H101	0.8600	C9—H9	0.9300
N2—C5	1.333 (3)	C10—C11	1.353 (4)
N2—C12	1.340 (3)	C10—H10	0.9300
C1—C2	1.355 (4)	C11—C12	1.422 (4)
C1—C6	1.401 (3)	C11—H11	0.9300
C1—H100	0.9300	S1—O3	1.421 (3)
C2—C3	1.421 (4)	S1—O1A	1.423 (2)
C2—H2	0.9300	S1—O2	1.448 (2)
C3—C4	1.350 (4)	S1—O4B	1.486 (18)
C3—H3	0.9300	S1—O1B	1.516 (16)
C4—C5	1.424 (3)	S1—O4A	1.614 (2)
C4—H4	0.9300	O4A—C13	1.406 (4)
C5—C6	1.429 (3)	C13—H13A	0.9600
C7—C8	1.412 (3)	C13—H13B	0.9600
C7—C12	1.426 (4)	C13—H13C	0.9600
C8—C9	1.345 (4)
C7—N1—C6	122.4 (2)	C8—C9—C10	121.8 (3)
C7—N1—H101	118.8	C8—C9—H9	119.1
C6—N1—H101	118.8	C10—C9—H9	119.1
C5—N2—C12	118.3 (2)	C11—C10—C9	121.1 (3)
C2—C1—C6	118.8 (2)	C11—C10—H10	119.5
C2—C1—H100	120.6	C9—C10—H10	119.5
C6—C1—H100	120.6	C10—C11—C12	119.6 (3)
C1—C2—C3	121.2 (2)	C10—C11—H11	120.2
C1—C2—H2	119.4	C12—C11—H11	120.2
C3—C2—H2	119.4	N2—C12—C11	120.2 (2)
C4—C3—C2	121.2 (2)	N2—C12—C7	121.7 (2)
C4—C3—H3	119.4	C11—C12—C7	118.1 (2)
C2—C3—H3	119.4	O3—S1—O1A	116.76 (18)
C3—C4—C5	119.7 (2)	O3—S1—O2	113.70 (16)
C3—C4—H4	120.1	O1A—S1—O2	114.03 (13)
C5—C4—H4	120.1	O3—S1—O4B	95.5 (7)
N2—C5—C4	119.9 (2)	O1A—S1—O4B	37.2 (7)
N2—C5—C6	122.1 (2)	O2—S1—O4B	100.4 (7)
C4—C5—C6	118.0 (2)	O3—S1—O1B	138.7 (6)
N1—C6—C1	121.5 (2)	O1A—S1—O1B	64.2 (6)
N1—C6—C5	117.4 (2)	O2—S1—O1B	100.5 (6)
C1—C6—C5	121.1 (2)	O4B—S1—O1B	100.4 (10)
N1—C7—C8	121.1 (2)	O3—S1—O4A	97.18 (17)
N1—C7—C12	118.1 (2)	O1A—S1—O4A	106.51 (15)
C8—C7—C12	120.9 (2)	O2—S1—O4A	106.33 (13)
C9—C8—C7	118.5 (3)	O4B—S1—O4A	142.5 (8)
C9—C8—H8	120.7	O1B—S1—O4A	49.6 (6)
C7—C8—H8	120.7	C13—O4A—S1	116.1 (2)
C6—C1—C2—C3	0.4 (4)	C12—C7—C8—C9	−0.9 (4)
C1—C2—C3—C4	−2.3 (5)	C7—C8—C9—C10	0.0 (5)
C2—C3—C4—C5	2.3 (4)	C8—C9—C10—C11	1.3 (6)
C12—N2—C5—C4	−178.6 (2)	C9—C10—C11—C12	−1.6 (5)
C12—N2—C5—C6	1.0 (4)	C5—N2—C12—C11	178.9 (2)
C3—C4—C5—N2	179.2 (2)	C5—N2—C12—C7	−0.5 (4)
C3—C4—C5—C6	−0.5 (4)	C10—C11—C12—N2	−178.7 (3)
C7—N1—C6—C1	−179.6 (2)	C10—C11—C12—C7	0.7 (4)
C7—N1—C6—C5	0.3 (4)	N1—C7—C12—N2	−0.1 (4)
C2—C1—C6—N1	−178.8 (2)	C8—C7—C12—N2	180.0 (2)
C2—C1—C6—C5	1.4 (4)	N1—C7—C12—C11	−179.5 (2)
N2—C5—C6—N1	−0.9 (4)	C8—C7—C12—C11	0.6 (4)
C4—C5—C6—N1	178.8 (2)	O3—S1—O4A—C13	179.8 (2)
N2—C5—C6—C1	178.9 (2)	O1A—S1—O4A—C13	59.1 (3)
C4—C5—C6—C1	−1.4 (4)	O2—S1—O4A—C13	−62.9 (3)
C6—N1—C7—C8	−179.9 (2)	O4B—S1—O4A—C13	70.9 (11)
C6—N1—C7—C12	0.2 (4)	O1B—S1—O4A—C13	27.2 (8)
N1—C7—C8—C9	179.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H101···O2i	0.86	1.82	2.647 (5)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H101⋯O2i	0.86	1.82	2.647 (5)	161

Symmetry code: (i) .