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In the crystal structure of the title compound, C12H9N2+·ClO4, paired C—H...N inter­actions link the phenazinium cations into centrosymmetric R22(8) dimers. The cations are also associated by nearly symmetrical bifurcated N—H...O hydrogen bonds via perchlorate anions. The resulting hydrogen-bond system generates sheets running parallel to the (12\overline{1}) plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680701759X/xu2240sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680701759X/xu2240Isup2.hkl
Contains datablock I

CCDC reference: 647599

Key indicators

  • Single-crystal X-ray study
  • T = 297 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.034
  • wR factor = 0.101
  • Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for Cl1 PLAT430_ALERT_2_B Short Inter D...A Contact O1 .. O1 .. 2.74 Ang.
Alert level C PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 Cl O4
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound, (I), was investigated as part of a structural study on hydrogen-bonding patterns in N-heterocyclic perchlorate salts (Sieroń, 2005, 2007a,b).

In (I), the asymmetric unit is composed of one monoprotonated phenazinium cation and one perchlorate anion (Fig. 1). The bond lengths and angles are within normal ranges (Allen et al., 1987) (Table 1). In the crystal structure, pairs of cations are connected into centrosymmetric dimers of R22(8) graph-set (Etter et al., 1990) via C–H···N hydrogen bonds (Table 2). In addition the perchlorate ions involve phenazinium cations into bifurcated N–H···O hydrogen bonds, generating a ring of graph-set motif R22(4). The combination of N–H···O and C–H···O hydrogen bonds forms sheets parallel to the (121) plane, as shown in Fig. 2.

Related literature top

For related literature, see: Allen et al. (1987); Etter et al. (1990); Sieroń (2005, 2007a, 2007b).

Experimental top

Phenazine was dissolved in hot perchloric acid (60%). The solution was allowed to cool to room temperature, and crystals formed after a few days.

Refinement top

H bonded to N atom was located in a difference Fourier map and refined isotropically. Remaining H atoms were positioned geometrically and refined using a riding model, with C–H = 0.93 Å and with Uiso(H) = 1.2 times Ueq(C).

Structure description top

The title compound, (I), was investigated as part of a structural study on hydrogen-bonding patterns in N-heterocyclic perchlorate salts (Sieroń, 2005, 2007a,b).

In (I), the asymmetric unit is composed of one monoprotonated phenazinium cation and one perchlorate anion (Fig. 1). The bond lengths and angles are within normal ranges (Allen et al., 1987) (Table 1). In the crystal structure, pairs of cations are connected into centrosymmetric dimers of R22(8) graph-set (Etter et al., 1990) via C–H···N hydrogen bonds (Table 2). In addition the perchlorate ions involve phenazinium cations into bifurcated N–H···O hydrogen bonds, generating a ring of graph-set motif R22(4). The combination of N–H···O and C–H···O hydrogen bonds forms sheets parallel to the (121) plane, as shown in Fig. 2.

For related literature, see: Allen et al. (1987); Etter et al. (1990); Sieroń (2005, 2007a, 2007b).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 40% probability displacement ellipsoids for non-H atoms. The dashed line indicates a hydrogen bond.
[Figure 2] Fig. 2. The packing of (I), showing molecules connected by N—H···O and C—H···N hydrogen bonds (dashed lines) into sheets approximately parallel to the (121) plane.
Phenazinium perchlorate top
Crystal data top
C12H9N2+·ClO4Z = 2
Mr = 280.66F(000) = 288
Triclinic, P1Dx = 1.568 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2025 (5) ÅCell parameters from 5148 reflections
b = 7.8494 (4) Åθ = 1.8–28.1°
c = 11.1564 (8) ŵ = 0.33 mm1
α = 81.463 (5)°T = 297 K
β = 80.539 (6)°Prism, orange
γ = 74.005 (5)°0.45 × 0.25 × 0.15 mm
V = 594.52 (7) Å3
Data collection top
Kuma KM-4-CCD
diffractometer
2097 independent reflections
Radiation source: CX-Mo12x0.4-S Seifert Mo tube1900 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.013
Detector resolution: 8.2356 pixels mm-1θmax = 25.0°, θmin = 2.7°
ω scansh = 88
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
k = 99
Tmin = 0.865, Tmax = 0.950l = 1313
6587 measured reflections
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.034 w = 1/[σ2(Fo2) + (0.0558P)2 + 0.2208P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.101(Δ/σ)max = 0.001
S = 1.07Δρmax = 0.31 e Å3
2097 reflectionsΔρmin = 0.31 e Å3
177 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.022 (4)
Primary atom site location: structure-invariant direct methods
Crystal data top
C12H9N2+·ClO4γ = 74.005 (5)°
Mr = 280.66V = 594.52 (7) Å3
Triclinic, P1Z = 2
a = 7.2025 (5) ÅMo Kα radiation
b = 7.8494 (4) ŵ = 0.33 mm1
c = 11.1564 (8) ÅT = 297 K
α = 81.463 (5)°0.45 × 0.25 × 0.15 mm
β = 80.539 (6)°
Data collection top
Kuma KM-4-CCD
diffractometer
2097 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)
1900 reflections with I > 2σ(I)
Tmin = 0.865, Tmax = 0.950Rint = 0.013
6587 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.101H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.31 e Å3
2097 reflectionsΔρmin = 0.31 e Å3
177 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
xyzUiso*/Ueq
N10.6217 (2)0.8228 (2)0.81292 (14)0.0418 (5)
N20.7501 (2)0.6529 (2)0.60495 (13)0.0443 (5)
C10.4979 (3)0.8473 (2)0.73018 (16)0.0395 (5)
C20.3079 (3)0.9601 (3)0.74564 (19)0.0515 (7)
C30.1933 (3)0.9828 (3)0.6566 (2)0.0581 (7)
C40.2608 (3)0.8939 (3)0.5497 (2)0.0578 (7)
C50.4414 (3)0.7845 (3)0.53331 (18)0.0521 (7)
C60.5686 (3)0.7577 (2)0.62308 (16)0.0402 (6)
C70.8674 (3)0.6333 (2)0.68953 (16)0.0399 (5)
C81.0604 (3)0.5229 (3)0.67312 (19)0.0529 (7)
C91.1803 (3)0.5048 (3)0.7581 (2)0.0568 (7)
C101.1178 (3)0.5957 (3)0.86372 (19)0.0530 (7)
C110.9341 (3)0.7022 (3)0.88447 (18)0.0488 (6)
C120.8059 (3)0.7209 (2)0.79850 (16)0.0381 (5)
Cl10.31140 (6)0.76238 (6)1.13972 (4)0.0419 (2)
O10.4337 (4)0.8615 (3)1.06518 (17)0.1046 (9)
O20.3034 (2)0.7936 (2)1.26274 (13)0.0665 (6)
O30.1211 (3)0.8186 (3)1.1070 (2)0.1135 (10)
O40.3889 (3)0.5803 (2)1.12356 (17)0.0731 (7)
H10.579 (3)0.875 (3)0.880 (2)0.061 (7)*
H20.262001.018100.815700.0620*
H30.068101.057800.665700.0700*
H40.179200.911500.490000.0690*
H50.482900.726300.463100.0630*
H81.104400.463100.603800.0630*
H91.306000.431300.746900.0680*
H101.203900.582300.920100.0640*
H110.894400.761500.954200.0590*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0466 (9)0.0448 (9)0.0345 (8)0.0086 (7)0.0008 (7)0.0169 (7)
N20.0458 (9)0.0518 (9)0.0327 (8)0.0059 (7)0.0011 (7)0.0134 (7)
C10.0427 (10)0.0418 (9)0.0345 (9)0.0115 (8)0.0001 (7)0.0098 (7)
C20.0454 (11)0.0575 (12)0.0478 (11)0.0046 (9)0.0026 (9)0.0195 (9)
C30.0400 (11)0.0689 (14)0.0597 (13)0.0029 (10)0.0037 (9)0.0133 (11)
C40.0459 (11)0.0786 (15)0.0480 (12)0.0101 (10)0.0119 (9)0.0092 (10)
C50.0518 (11)0.0679 (13)0.0368 (10)0.0104 (10)0.0063 (8)0.0153 (9)
C60.0417 (10)0.0450 (10)0.0326 (9)0.0094 (8)0.0000 (7)0.0092 (7)
C70.0444 (10)0.0418 (9)0.0324 (9)0.0092 (8)0.0019 (7)0.0077 (7)
C80.0488 (11)0.0608 (12)0.0431 (11)0.0006 (9)0.0013 (9)0.0176 (9)
C90.0457 (11)0.0633 (13)0.0555 (13)0.0012 (10)0.0088 (9)0.0096 (10)
C100.0539 (12)0.0579 (12)0.0492 (12)0.0125 (10)0.0164 (9)0.0054 (9)
C110.0579 (12)0.0524 (11)0.0400 (10)0.0144 (9)0.0105 (9)0.0126 (8)
C120.0429 (10)0.0369 (9)0.0351 (9)0.0113 (7)0.0011 (7)0.0084 (7)
Cl10.0474 (3)0.0426 (3)0.0362 (3)0.0103 (2)0.0031 (2)0.0113 (2)
O10.180 (2)0.0876 (13)0.0610 (11)0.0859 (14)0.0580 (13)0.0385 (9)
O20.0791 (11)0.0886 (12)0.0354 (8)0.0252 (9)0.0031 (7)0.0162 (7)
O30.0760 (13)0.143 (2)0.1173 (18)0.0260 (13)0.0527 (12)0.0599 (15)
O40.0818 (12)0.0451 (9)0.0905 (13)0.0117 (8)0.0028 (9)0.0197 (8)
Geometric parameters (Å, º) top
Cl1—O11.420 (3)C7—C81.420 (3)
Cl1—O21.4188 (15)C7—C121.432 (2)
Cl1—O31.411 (2)C8—C91.351 (3)
Cl1—O41.4109 (16)C9—C101.414 (3)
N1—C11.344 (3)C10—C111.360 (3)
N1—C121.345 (3)C11—C121.403 (3)
N2—C61.340 (2)C2—H20.9300
N2—C71.332 (2)C3—H30.9300
N1—H10.88 (2)C4—H40.9300
C1—C21.409 (3)C5—H50.9300
C1—C61.426 (2)C8—H80.9300
C2—C31.355 (3)C9—H90.9300
C3—C41.420 (3)C10—H100.9300
C4—C51.348 (3)C11—H110.9300
C5—C61.421 (3)
O1—Cl1—O2107.90 (11)N2—C7—C12122.13 (18)
O1—Cl1—O3110.73 (14)C7—C8—C9120.1 (2)
O1—Cl1—O4108.76 (13)C7—C12—C11121.01 (19)
O2—Cl1—O3108.73 (11)C8—C7—C12117.82 (18)
O2—Cl1—O4111.68 (10)C8—C9—C10121.1 (2)
O3—Cl1—O4109.05 (13)C9—C10—C11121.3 (2)
C1—N1—C12123.35 (16)C10—C11—C12118.67 (19)
C6—N2—C7118.69 (15)C1—C2—H2121.00
C12—N1—H1118.7 (15)C3—C2—H2121.00
C1—N1—H1118.0 (15)C2—C3—H3119.00
N1—C1—C2122.11 (16)C4—C3—H3119.00
N1—C1—C6117.11 (18)C5—C4—H4119.00
C2—C1—C6120.76 (18)C3—C4—H4120.00
C1—C2—C3118.85 (19)C4—C5—H5120.00
C2—C3—C4121.2 (2)C6—C5—H5120.00
C3—C4—C5121.0 (2)C7—C8—H8120.00
C4—C5—C6120.15 (19)C9—C8—H8120.00
C1—C6—C5118.04 (18)C10—C9—H9119.00
N1—C12—C7116.80 (18)C8—C9—H9119.00
N1—C12—C11122.19 (17)C9—C10—H10119.00
N2—C6—C1121.92 (18)C11—C10—H10119.00
N2—C6—C5120.04 (16)C12—C11—H11121.00
N2—C7—C8120.05 (16)C10—C11—H11121.00
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.88 (2)2.16 (2)2.936 (3)148 (2)
N1—H1···O1i0.88 (2)2.22 (2)2.903 (3)135 (2)
C8—H8···N2ii0.932.583.497 (3)170
Symmetry codes: (i) x+1, y+2, z+2; (ii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC12H9N2+·ClO4
Mr280.66
Crystal system, space groupTriclinic, P1
Temperature (K)297
a, b, c (Å)7.2025 (5), 7.8494 (4), 11.1564 (8)
α, β, γ (°)81.463 (5), 80.539 (6), 74.005 (5)
V3)594.52 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.45 × 0.25 × 0.15
Data collection
DiffractometerKuma KM-4-CCD
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.865, 0.950
No. of measured, independent and
observed [I > 2σ(I)] reflections
6587, 2097, 1900
Rint0.013
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.101, 1.07
No. of reflections2097
No. of parameters177
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.31, 0.31

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXTL (Sheldrick, 2001), SHELXTL and Mercury (Macrae et al., 2006), PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
Cl1—O11.420 (3)N1—C11.344 (3)
Cl1—O21.4188 (15)N1—C121.345 (3)
Cl1—O31.411 (2)N2—C61.340 (2)
Cl1—O41.4109 (16)N2—C71.332 (2)
O1—Cl1—O2107.90 (11)N1—C1—C2122.11 (16)
O1—Cl1—O3110.73 (14)N1—C1—C6117.11 (18)
O1—Cl1—O4108.76 (13)N1—C12—C7116.80 (18)
O2—Cl1—O3108.73 (11)N1—C12—C11122.19 (17)
O2—Cl1—O4111.68 (10)N2—C6—C1121.92 (18)
O3—Cl1—O4109.05 (13)N2—C6—C5120.04 (16)
C1—N1—C12123.35 (16)N2—C7—C8120.05 (16)
C6—N2—C7118.69 (15)N2—C7—C12122.13 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.88 (2)2.16 (2)2.936 (3)148 (2)
N1—H1···O1i0.88 (2)2.22 (2)2.903 (3)135 (2)
C8—H8···N2ii0.932.583.497 (3)170
Symmetry codes: (i) x+1, y+2, z+2; (ii) x+2, y+1, z+1.
 

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