Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680701759X/xu2240sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680701759X/xu2240Isup2.hkl |
CCDC reference: 647599
Phenazine was dissolved in hot perchloric acid (60%). The solution was allowed to cool to room temperature, and crystals formed after a few days.
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).
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).
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).
C12H9N2+·ClO4− | Z = 2 |
Mr = 280.66 | F(000) = 288 |
Triclinic, P1 | Dx = 1.568 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2025 (5) Å | Cell parameters from 5148 reflections |
b = 7.8494 (4) Å | θ = 1.8–28.1° |
c = 11.1564 (8) Å | µ = 0.33 mm−1 |
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 |
Kuma KM-4-CCD diffractometer | 2097 independent reflections |
Radiation source: CX-Mo12x0.4-S Seifert Mo tube | 1900 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
Detector resolution: 8.2356 pixels mm-1 | θmax = 25.0°, θmin = 2.7° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | k = −9→9 |
Tmin = 0.865, Tmax = 0.950 | l = −13→13 |
6587 measured reflections |
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | H 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 = 1.07 | Δρmax = 0.31 e Å−3 |
2097 reflections | Δρmin = −0.31 e Å−3 |
177 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.022 (4) |
Primary atom site location: structure-invariant direct methods |
C12H9N2+·ClO4− | γ = 74.005 (5)° |
Mr = 280.66 | V = 594.52 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2025 (5) Å | Mo Kα radiation |
b = 7.8494 (4) Å | µ = 0.33 mm−1 |
c = 11.1564 (8) Å | T = 297 K |
α = 81.463 (5)° | 0.45 × 0.25 × 0.15 mm |
β = 80.539 (6)° |
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 = 0.950 | Rint = 0.013 |
6587 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.31 e Å−3 |
2097 reflections | Δρmin = −0.31 e Å−3 |
177 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.6217 (2) | 0.8228 (2) | 0.81292 (14) | 0.0418 (5) | |
N2 | 0.7501 (2) | 0.6529 (2) | 0.60495 (13) | 0.0443 (5) | |
C1 | 0.4979 (3) | 0.8473 (2) | 0.73018 (16) | 0.0395 (5) | |
C2 | 0.3079 (3) | 0.9601 (3) | 0.74564 (19) | 0.0515 (7) | |
C3 | 0.1933 (3) | 0.9828 (3) | 0.6566 (2) | 0.0581 (7) | |
C4 | 0.2608 (3) | 0.8939 (3) | 0.5497 (2) | 0.0578 (7) | |
C5 | 0.4414 (3) | 0.7845 (3) | 0.53331 (18) | 0.0521 (7) | |
C6 | 0.5686 (3) | 0.7577 (2) | 0.62308 (16) | 0.0402 (6) | |
C7 | 0.8674 (3) | 0.6333 (2) | 0.68953 (16) | 0.0399 (5) | |
C8 | 1.0604 (3) | 0.5229 (3) | 0.67312 (19) | 0.0529 (7) | |
C9 | 1.1803 (3) | 0.5048 (3) | 0.7581 (2) | 0.0568 (7) | |
C10 | 1.1178 (3) | 0.5957 (3) | 0.86372 (19) | 0.0530 (7) | |
C11 | 0.9341 (3) | 0.7022 (3) | 0.88447 (18) | 0.0488 (6) | |
C12 | 0.8059 (3) | 0.7209 (2) | 0.79850 (16) | 0.0381 (5) | |
Cl1 | 0.31140 (6) | 0.76238 (6) | 1.13972 (4) | 0.0419 (2) | |
O1 | 0.4337 (4) | 0.8615 (3) | 1.06518 (17) | 0.1046 (9) | |
O2 | 0.3034 (2) | 0.7936 (2) | 1.26274 (13) | 0.0665 (6) | |
O3 | 0.1211 (3) | 0.8186 (3) | 1.1070 (2) | 0.1135 (10) | |
O4 | 0.3889 (3) | 0.5803 (2) | 1.12356 (17) | 0.0731 (7) | |
H1 | 0.579 (3) | 0.875 (3) | 0.880 (2) | 0.061 (7)* | |
H2 | 0.26200 | 1.01810 | 0.81570 | 0.0620* | |
H3 | 0.06810 | 1.05780 | 0.66570 | 0.0700* | |
H4 | 0.17920 | 0.91150 | 0.49000 | 0.0690* | |
H5 | 0.48290 | 0.72630 | 0.46310 | 0.0630* | |
H8 | 1.10440 | 0.46310 | 0.60380 | 0.0630* | |
H9 | 1.30600 | 0.43130 | 0.74690 | 0.0680* | |
H10 | 1.20390 | 0.58230 | 0.92010 | 0.0640* | |
H11 | 0.89440 | 0.76150 | 0.95420 | 0.0590* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0466 (9) | 0.0448 (9) | 0.0345 (8) | −0.0086 (7) | −0.0008 (7) | −0.0169 (7) |
N2 | 0.0458 (9) | 0.0518 (9) | 0.0327 (8) | −0.0059 (7) | −0.0011 (7) | −0.0134 (7) |
C1 | 0.0427 (10) | 0.0418 (9) | 0.0345 (9) | −0.0115 (8) | −0.0001 (7) | −0.0098 (7) |
C2 | 0.0454 (11) | 0.0575 (12) | 0.0478 (11) | −0.0046 (9) | 0.0026 (9) | −0.0195 (9) |
C3 | 0.0400 (11) | 0.0689 (14) | 0.0597 (13) | −0.0029 (10) | −0.0037 (9) | −0.0133 (11) |
C4 | 0.0459 (11) | 0.0786 (15) | 0.0480 (12) | −0.0101 (10) | −0.0119 (9) | −0.0092 (10) |
C5 | 0.0518 (11) | 0.0679 (13) | 0.0368 (10) | −0.0104 (10) | −0.0063 (8) | −0.0153 (9) |
C6 | 0.0417 (10) | 0.0450 (10) | 0.0326 (9) | −0.0094 (8) | 0.0000 (7) | −0.0092 (7) |
C7 | 0.0444 (10) | 0.0418 (9) | 0.0324 (9) | −0.0092 (8) | −0.0019 (7) | −0.0077 (7) |
C8 | 0.0488 (11) | 0.0608 (12) | 0.0431 (11) | −0.0006 (9) | −0.0013 (9) | −0.0176 (9) |
C9 | 0.0457 (11) | 0.0633 (13) | 0.0555 (13) | −0.0012 (10) | −0.0088 (9) | −0.0096 (10) |
C10 | 0.0539 (12) | 0.0579 (12) | 0.0492 (12) | −0.0125 (10) | −0.0164 (9) | −0.0054 (9) |
C11 | 0.0579 (12) | 0.0524 (11) | 0.0400 (10) | −0.0144 (9) | −0.0105 (9) | −0.0126 (8) |
C12 | 0.0429 (10) | 0.0369 (9) | 0.0351 (9) | −0.0113 (7) | −0.0011 (7) | −0.0084 (7) |
Cl1 | 0.0474 (3) | 0.0426 (3) | 0.0362 (3) | −0.0103 (2) | −0.0031 (2) | −0.0113 (2) |
O1 | 0.180 (2) | 0.0876 (13) | 0.0610 (11) | −0.0859 (14) | 0.0580 (13) | −0.0385 (9) |
O2 | 0.0791 (11) | 0.0886 (12) | 0.0354 (8) | −0.0252 (9) | −0.0031 (7) | −0.0162 (7) |
O3 | 0.0760 (13) | 0.143 (2) | 0.1173 (18) | 0.0260 (13) | −0.0527 (12) | −0.0599 (15) |
O4 | 0.0818 (12) | 0.0451 (9) | 0.0905 (13) | −0.0117 (8) | −0.0028 (9) | −0.0197 (8) |
Cl1—O1 | 1.420 (3) | C7—C8 | 1.420 (3) |
Cl1—O2 | 1.4188 (15) | C7—C12 | 1.432 (2) |
Cl1—O3 | 1.411 (2) | C8—C9 | 1.351 (3) |
Cl1—O4 | 1.4109 (16) | C9—C10 | 1.414 (3) |
N1—C1 | 1.344 (3) | C10—C11 | 1.360 (3) |
N1—C12 | 1.345 (3) | C11—C12 | 1.403 (3) |
N2—C6 | 1.340 (2) | C2—H2 | 0.9300 |
N2—C7 | 1.332 (2) | C3—H3 | 0.9300 |
N1—H1 | 0.88 (2) | C4—H4 | 0.9300 |
C1—C2 | 1.409 (3) | C5—H5 | 0.9300 |
C1—C6 | 1.426 (2) | C8—H8 | 0.9300 |
C2—C3 | 1.355 (3) | C9—H9 | 0.9300 |
C3—C4 | 1.420 (3) | C10—H10 | 0.9300 |
C4—C5 | 1.348 (3) | C11—H11 | 0.9300 |
C5—C6 | 1.421 (3) | ||
O1—Cl1—O2 | 107.90 (11) | N2—C7—C12 | 122.13 (18) |
O1—Cl1—O3 | 110.73 (14) | C7—C8—C9 | 120.1 (2) |
O1—Cl1—O4 | 108.76 (13) | C7—C12—C11 | 121.01 (19) |
O2—Cl1—O3 | 108.73 (11) | C8—C7—C12 | 117.82 (18) |
O2—Cl1—O4 | 111.68 (10) | C8—C9—C10 | 121.1 (2) |
O3—Cl1—O4 | 109.05 (13) | C9—C10—C11 | 121.3 (2) |
C1—N1—C12 | 123.35 (16) | C10—C11—C12 | 118.67 (19) |
C6—N2—C7 | 118.69 (15) | C1—C2—H2 | 121.00 |
C12—N1—H1 | 118.7 (15) | C3—C2—H2 | 121.00 |
C1—N1—H1 | 118.0 (15) | C2—C3—H3 | 119.00 |
N1—C1—C2 | 122.11 (16) | C4—C3—H3 | 119.00 |
N1—C1—C6 | 117.11 (18) | C5—C4—H4 | 119.00 |
C2—C1—C6 | 120.76 (18) | C3—C4—H4 | 120.00 |
C1—C2—C3 | 118.85 (19) | C4—C5—H5 | 120.00 |
C2—C3—C4 | 121.2 (2) | C6—C5—H5 | 120.00 |
C3—C4—C5 | 121.0 (2) | C7—C8—H8 | 120.00 |
C4—C5—C6 | 120.15 (19) | C9—C8—H8 | 120.00 |
C1—C6—C5 | 118.04 (18) | C10—C9—H9 | 119.00 |
N1—C12—C7 | 116.80 (18) | C8—C9—H9 | 119.00 |
N1—C12—C11 | 122.19 (17) | C9—C10—H10 | 119.00 |
N2—C6—C1 | 121.92 (18) | C11—C10—H10 | 119.00 |
N2—C6—C5 | 120.04 (16) | C12—C11—H11 | 121.00 |
N2—C7—C8 | 120.05 (16) | C10—C11—H11 | 121.00 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.88 (2) | 2.16 (2) | 2.936 (3) | 148 (2) |
N1—H1···O1i | 0.88 (2) | 2.22 (2) | 2.903 (3) | 135 (2) |
C8—H8···N2ii | 0.93 | 2.58 | 3.497 (3) | 170 |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H9N2+·ClO4− |
Mr | 280.66 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 594.52 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.45 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Kuma KM-4-CCD |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.865, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6587, 2097, 1900 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.101, 1.07 |
No. of reflections | 2097 |
No. of parameters | 177 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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).
Cl1—O1 | 1.420 (3) | N1—C1 | 1.344 (3) |
Cl1—O2 | 1.4188 (15) | N1—C12 | 1.345 (3) |
Cl1—O3 | 1.411 (2) | N2—C6 | 1.340 (2) |
Cl1—O4 | 1.4109 (16) | N2—C7 | 1.332 (2) |
O1—Cl1—O2 | 107.90 (11) | N1—C1—C2 | 122.11 (16) |
O1—Cl1—O3 | 110.73 (14) | N1—C1—C6 | 117.11 (18) |
O1—Cl1—O4 | 108.76 (13) | N1—C12—C7 | 116.80 (18) |
O2—Cl1—O3 | 108.73 (11) | N1—C12—C11 | 122.19 (17) |
O2—Cl1—O4 | 111.68 (10) | N2—C6—C1 | 121.92 (18) |
O3—Cl1—O4 | 109.05 (13) | N2—C6—C5 | 120.04 (16) |
C1—N1—C12 | 123.35 (16) | N2—C7—C8 | 120.05 (16) |
C6—N2—C7 | 118.69 (15) | N2—C7—C12 | 122.13 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.88 (2) | 2.16 (2) | 2.936 (3) | 148 (2) |
N1—H1···O1i | 0.88 (2) | 2.22 (2) | 2.903 (3) | 135 (2) |
C8—H8···N2ii | 0.93 | 2.58 | 3.497 (3) | 170 |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+2, −y+1, −z+1. |
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.