Phenazin-5-ium hydrogen sulfate monohydrate.

The crystal structure of the title salt, C12H9N2 (+)·HSO4 (-)·H2O, comprises inversion-related pairs of phenazinium ions linked by C-H⋯N hydrogen bonds. The phenazinium N-H atoms are hydrogen bonded to the bis-ulfate anions. The bis-ulfate anions and water mol-ecules are linked by O-H⋯O hydrogen-bonding inter-actions into a structural ladder motif parallel to the a axis.

Related literature

For related structures, see: Sieroń (2007 ▶) [phenazinium perchlorate]; Plasseraud et al. (2009 ▶) [phenazinium trifluoro­methane­sulfonate]; Braga et al. (2010 ▶) [phenazinium chloride and phenazine monohydrate]; G.-X. Zhang et al. (2012 ▶) [phenazinium bromide]; N.-Q. Zhang et al. (2012 ▶) [phenazinium methane­sulfonate]. For copper(II) salts of phenazine, see: Schneider et al. (2007 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C12H9N2 +·HSO4 −·H2O

M = 296.30

Triclinic,

a = 5.6565 (4) Å

b = 10.4019 (6) Å

c = 10.9500 (5) Å

α = 89.693 (4)°

β = 87.202 (5)°

γ = 76.412 (5)°

V = 625.49 (6) Å3

Z = 2

Cu Kα radiation

μ = 2.53 mm−1

T = 120 K

0.45 × 0.40 × 0.30 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.786, T max = 1.000

3789 measured reflections

2341 independent reflections

2276 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.088

S = 1.09

2341 reflections

193 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.39 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶), enCIFer (Allen et al., 2004 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681300562X/sj5299sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300562X/sj5299Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681300562X/sj5299Isup3.cml

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

C12H9N2+·HSO4−·H2O	Z = 2
Mr = 296.30	F(000) = 308
Triclinic, P1	Dx = 1.573 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 5.6565 (4) Å	Cell parameters from 3015 reflections
b = 10.4019 (6) Å	θ = 4.0–73.7°
c = 10.9500 (5) Å	µ = 2.53 mm−1
α = 89.693 (4)°	T = 120 K
β = 87.202 (5)°	Prism, red
γ = 76.412 (5)°	0.45 × 0.40 × 0.30 mm
V = 625.49 (6) Å3

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2341 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2276 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.013
Detector resolution: 10.6501 pixels mm-1	θmax = 70.1°, θmin = 4.0°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→12
Tmin = 0.786, Tmax = 1.000	l = −13→10
3789 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0466P)2 + 0.3904P] where P = (Fo2 + 2Fc2)/3
2341 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

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
N1	−0.2593 (2)	0.82964 (13)	0.67912 (12)	0.0146 (3)
H1	−0.121 (4)	0.782 (2)	0.6983 (18)	0.018*
C2	−0.3721 (3)	0.78622 (15)	0.58835 (14)	0.0147 (3)
C3	−0.2635 (3)	0.66885 (16)	0.52306 (15)	0.0196 (3)
H3	−0.1104	0.6194	0.5420	0.024*
C4	−0.3861 (3)	0.62898 (17)	0.43183 (15)	0.0223 (4)
H4	−0.3161	0.5514	0.3890	0.027*
C5	−0.6203 (3)	0.70454 (17)	0.40110 (15)	0.0217 (4)
H5	−0.6999	0.6760	0.3379	0.026*
C6	−0.7286 (3)	0.81763 (17)	0.46292 (15)	0.0192 (3)
H6	−0.8810	0.8660	0.4416	0.023*
C7	−0.6090 (3)	0.86222 (15)	0.56042 (14)	0.0152 (3)
N8	−0.7194 (2)	0.97138 (13)	0.62387 (12)	0.0170 (3)
C9	−0.6022 (3)	1.00957 (15)	0.71603 (14)	0.0156 (3)
C10	−0.7157 (3)	1.12367 (16)	0.78748 (15)	0.0195 (3)
H10	−0.8713	1.1714	0.7708	0.023*
C11	−0.5958 (3)	1.16250 (16)	0.88007 (15)	0.0211 (4)
H11	−0.6713	1.2364	0.9269	0.025*
C12	−0.3575 (3)	1.09182 (16)	0.90608 (15)	0.0209 (4)
H12	−0.2782	1.1214	0.9688	0.025*
C13	−0.2415 (3)	0.98128 (16)	0.84123 (15)	0.0186 (3)
H13	−0.0857	0.9352	0.8597	0.022*
C14	−0.3633 (3)	0.93855 (15)	0.74565 (14)	0.0142 (3)
S1	0.28595 (6)	0.63836 (3)	0.83817 (3)	0.01403 (14)
O1	0.1783 (2)	0.67614 (11)	0.72006 (10)	0.0209 (3)
O2	0.3077 (2)	0.48835 (11)	0.85361 (11)	0.0193 (3)
H2	0.155 (4)	0.469 (2)	0.8530 (18)	0.023*
O3	0.1275 (2)	0.70674 (11)	0.93855 (11)	0.0214 (3)
O4	0.5331 (2)	0.65395 (12)	0.84063 (12)	0.0247 (3)
O1S	−0.0979 (2)	0.42771 (13)	0.84748 (11)	0.0207 (3)
H1A	−0.221 (4)	0.498 (2)	0.8448 (19)	0.025*
H1B	−0.120 (4)	0.387 (2)	0.912 (2)	0.025*

	U11	U22	U33	U12	U13	U23
N1	0.0135 (6)	0.0134 (6)	0.0161 (6)	−0.0012 (5)	−0.0020 (5)	0.0022 (5)
C2	0.0157 (7)	0.0149 (7)	0.0140 (7)	−0.0043 (6)	−0.0002 (6)	0.0024 (6)
C3	0.0195 (8)	0.0184 (8)	0.0189 (8)	−0.0002 (6)	−0.0016 (6)	−0.0003 (6)
C4	0.0276 (9)	0.0197 (8)	0.0190 (8)	−0.0043 (7)	−0.0006 (7)	−0.0036 (6)
C5	0.0248 (9)	0.0272 (9)	0.0158 (8)	−0.0108 (7)	−0.0044 (6)	−0.0006 (6)
C6	0.0170 (8)	0.0238 (8)	0.0179 (8)	−0.0062 (6)	−0.0041 (6)	0.0040 (6)
C7	0.0144 (7)	0.0163 (7)	0.0154 (7)	−0.0045 (6)	−0.0005 (6)	0.0033 (6)
N8	0.0152 (7)	0.0173 (7)	0.0183 (7)	−0.0030 (5)	−0.0017 (5)	0.0022 (5)
C9	0.0152 (7)	0.0147 (7)	0.0169 (7)	−0.0035 (6)	−0.0008 (6)	0.0028 (6)
C10	0.0182 (8)	0.0150 (8)	0.0229 (8)	0.0007 (6)	0.0006 (6)	0.0011 (6)
C11	0.0264 (9)	0.0137 (8)	0.0215 (8)	−0.0019 (6)	0.0011 (7)	−0.0012 (6)
C12	0.0276 (9)	0.0181 (8)	0.0183 (8)	−0.0074 (7)	−0.0039 (7)	−0.0013 (6)
C13	0.0184 (8)	0.0181 (8)	0.0196 (8)	−0.0040 (6)	−0.0048 (6)	0.0016 (6)
C14	0.0159 (7)	0.0115 (7)	0.0150 (7)	−0.0034 (6)	0.0007 (6)	0.0020 (6)
S1	0.0126 (2)	0.0130 (2)	0.0160 (2)	−0.00190 (14)	−0.00241 (14)	0.00158 (14)
O1	0.0199 (6)	0.0211 (6)	0.0178 (6)	0.0032 (5)	−0.0026 (5)	0.0026 (4)
O2	0.0169 (6)	0.0131 (6)	0.0272 (6)	−0.0019 (4)	−0.0025 (5)	0.0015 (4)
O3	0.0240 (6)	0.0181 (6)	0.0201 (6)	−0.0012 (5)	0.0001 (5)	−0.0022 (4)
O4	0.0172 (6)	0.0248 (6)	0.0338 (7)	−0.0080 (5)	−0.0048 (5)	0.0066 (5)
O1S	0.0175 (6)	0.0211 (6)	0.0223 (6)	−0.0022 (5)	−0.0007 (5)	0.0008 (5)

N1—C2	1.342 (2)	C9—C14	1.431 (2)
N1—C14	1.347 (2)	C10—C11	1.360 (2)
N1—H1	0.86 (2)	C10—H10	0.9300
C2—C3	1.412 (2)	C11—C12	1.417 (2)
C2—C7	1.433 (2)	C11—H11	0.9300
C3—C4	1.363 (2)	C12—C13	1.366 (2)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.428 (2)	C13—C14	1.410 (2)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.359 (2)	S1—O4	1.4465 (12)
C5—H5	0.9300	S1—O3	1.4595 (12)
C6—C7	1.427 (2)	S1—O1	1.4685 (12)
C6—H6	0.9300	S1—O2	1.5452 (11)
C7—N8	1.340 (2)	O2—H2	0.93 (2)
N8—C9	1.345 (2)	O1S—H1A	0.89 (2)
C9—C10	1.427 (2)	O1S—H1B	0.84 (2)
C2—N1—C14	122.42 (14)	C10—C9—C14	118.10 (14)
C2—N1—H1	117.8 (13)	C11—C10—C9	119.91 (15)
C14—N1—H1	119.6 (13)	C11—C10—H10	120.0
N1—C2—C3	121.43 (14)	C9—C10—H10	120.0
N1—C2—C7	117.80 (14)	C10—C11—C12	120.87 (15)
C3—C2—C7	120.77 (14)	C10—C11—H11	119.6
C4—C3—C2	119.09 (15)	C12—C11—H11	119.6
C4—C3—H3	120.5	C13—C12—C11	121.57 (15)
C2—C3—H3	120.5	C13—C12—H12	119.2
C3—C4—C5	121.01 (15)	C11—C12—H12	119.2
C3—C4—H4	119.5	C12—C13—C14	118.48 (15)
C5—C4—H4	119.5	C12—C13—H13	120.8
C6—C5—C4	120.90 (15)	C14—C13—H13	120.8
C6—C5—H5	119.5	N1—C14—C13	121.24 (14)
C4—C5—H5	119.5	N1—C14—C9	117.71 (14)
C5—C6—C7	120.12 (15)	C13—C14—C9	121.05 (14)
C5—C6—H6	119.9	O4—S1—O3	113.27 (7)
C7—C6—H6	119.9	O4—S1—O1	112.32 (7)
N8—C7—C6	120.05 (14)	O3—S1—O1	110.75 (7)
N8—C7—C2	121.85 (14)	O4—S1—O2	104.85 (7)
C6—C7—C2	118.09 (14)	O3—S1—O2	107.93 (7)
C7—N8—C9	118.37 (14)	O1—S1—O2	107.28 (7)
N8—C9—C10	120.09 (14)	S1—O2—H2	111.1 (13)
N8—C9—C14	121.81 (14)	H1A—O1S—H1B	107 (2)
C14—N1—C2—C3	−177.42 (14)	C7—N8—C9—C10	−178.66 (14)
C14—N1—C2—C7	1.9 (2)	C7—N8—C9—C14	1.3 (2)
N1—C2—C3—C4	179.87 (15)	N8—C9—C10—C11	−179.55 (15)
C7—C2—C3—C4	0.6 (2)	C14—C9—C10—C11	0.5 (2)
C2—C3—C4—C5	0.5 (3)	C9—C10—C11—C12	0.7 (2)
C3—C4—C5—C6	−0.7 (3)	C10—C11—C12—C13	−1.3 (3)
C4—C5—C6—C7	−0.3 (3)	C11—C12—C13—C14	0.6 (2)
C5—C6—C7—N8	−177.83 (15)	C2—N1—C14—C13	179.42 (14)
C5—C6—C7—C2	1.4 (2)	C2—N1—C14—C9	−0.6 (2)
N1—C2—C7—N8	−1.6 (2)	C12—C13—C14—N1	−179.43 (15)
C3—C2—C7—N8	177.64 (15)	C12—C13—C14—C9	0.6 (2)
N1—C2—C7—C6	179.15 (13)	N8—C9—C14—N1	−1.1 (2)
C3—C2—C7—C6	−1.6 (2)	C10—C9—C14—N1	178.86 (14)
C6—C7—N8—C9	179.27 (14)	N8—C9—C14—C13	178.92 (14)
C2—C7—N8—C9	0.1 (2)	C10—C9—C14—C13	−1.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86 (2)	1.81 (2)	2.6685 (18)	173.3 (19)
O2—H2···O1S	0.93 (2)	1.59 (2)	2.5223 (16)	177 (2)
O1S—H1A···O4i	0.89 (2)	1.87 (2)	2.7577 (18)	176 (2)
O1S—H1B···O3ii	0.84 (2)	1.90 (2)	2.7405 (18)	173 (2)
C6—H6···N8iii	0.93	2.61	3.538 (2)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86 (2)	1.81 (2)	2.6685 (18)	173.3 (19)
O2—H2⋯O1S	0.93 (2)	1.59 (2)	2.5223 (16)	177 (2)
O1S—H1A⋯O4i	0.89 (2)	1.87 (2)	2.7577 (18)	176 (2)
O1S—H1B⋯O3ii	0.84 (2)	1.90 (2)	2.7405 (18)	173 (2)
C6—H6⋯N8iii	0.93	2.61	3.538 (2)	172

Symmetry codes: (i) ; (ii) ; (iii) .