The crystal and molecular structures of two phenanthroline hydrochlorides have been determined at 173 K. 1,10-Phenanthrolin-1-ium chloride, C
12H
9N
2+·Cl
-, crystallizes in two stacks of exactly planar molecules. Both stacks are approximately parallel to the (
02) plane and the planes composing the different stacks enclose an angle of 13.29 (3)°. Tris(1,10-phenanthrolin-1-ium) dichloride (hydrogen chloride) chloride chloroform solvate, 3C
12H
9N
2+·2Cl
-·HCl·Cl
-·CHCl
3, displays an interesting network of Cl
- mediated hydrogen bonds between the two different phenanthrolinium moieties and between a phenanthrolinium and the chloroform solvate. In addition, a hydrogen bond between the HCl and the third Cl
- ion is formed. The C-N-C angle at the protonated N atoms is, in all phenanthrolinium units of both structures, significantly larger than the C-N-C angle at the non-protonated N atom.
Supporting information
CCDC references: 142756; 142757
Preparation of (I): methyltrichlorosilane (1 mmol) and 1,10-phenanthroline (2 mmol) were mixed. The mixture was heated above the melting point of phenanthroline (390 K). During cooling to 298 K a white solid precipitated. The clear solution was removed by a syringe. The solid was dried in vacuo (2–3 mbar for 8 h), the powder was transferred into a glove box under nitrogen. Crystals of (I) were obtained by sublimation at (2–3 mbar; 1 mbar = 100 Pa) and 315 K.
Preparation of (II): methyltrichlorosilane (1 mmol) was dissolved in 20 ml CHCl3. During continuous stirring, a solution of 1,10-phenanthroline (2 mmol) in chloroform was added. The solvent was slowly removed in vacuo (2–3 mbar) at 300 K. Crystals were obtained after a few days.
All H atoms were located by difference Fourier synthesis and the H atoms bonded to carbon were refined with fixed individual displacement parameters [U(H) = 1.2 Ueq(C)] using a riding model with C—H(aromatic) = 0.95 or C—H(tertiary) = 1.00, respectively. H atoms bonded to N and Cl were refined freely.
Data collection: SMART (Siemens, 1995) for (I); SMART (Siemens, 1994) for (II). For both compounds, cell refinement: SMART. Data reduction: SAINT (Siemens, 1995) for (I); SAINT (Siemens, 1994) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994).
Crystal data top
C12H9N2+·Cl− | F(000) = 448 |
Mr = 216.66 | Dx = 1.385 Mg m−3 Dm = N/A Mg m−3 Dm measured by not measured |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.877 (1) Å | Cell parameters from 1982 reflections |
b = 9.787 (1) Å | θ = 1.0–25.0° |
c = 15.547 (2) Å | µ = 0.33 mm−1 |
β = 96.91 (2)° | T = 173 K |
V = 1038.8 (2) Å3 | Plate, colourless |
Z = 4 | 0.25 × 0.20 × 0.10 mm |
Data collection top
Siemens CCD three circle diffractometer | 1884 independent reflections |
Radiation source: fine-focus sealed tube | 1093 reflections with I > 2σ(I) |
Highly oriented graphite crystal monochromator | Rint = 0.083 |
ω scans | θmax = 26.0°, θmin = 2.5° |
Absorption correction: empirical SADABS (Sheldrick, 1996) | h = −8→8 |
Tmin = 0.922, Tmax = 0.968 | k = −10→11 |
7686 measured reflections | l = −18→18 |
Refinement top
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0535P)2 + 0.6383P] where P = (Fo2 + 2Fc2)/3 |
1884 reflections | (Δ/σ)max < 0.001 |
140 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
C12H9N2+·Cl− | V = 1038.8 (2) Å3 |
Mr = 216.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.877 (1) Å | µ = 0.33 mm−1 |
b = 9.787 (1) Å | T = 173 K |
c = 15.547 (2) Å | 0.25 × 0.20 × 0.10 mm |
β = 96.91 (2)° | |
Data collection top
Siemens CCD three circle diffractometer | 1884 independent reflections |
Absorption correction: empirical SADABS (Sheldrick, 1996) | 1093 reflections with I > 2σ(I) |
Tmin = 0.922, Tmax = 0.968 | Rint = 0.083 |
7686 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.56 e Å−3 |
1884 reflections | Δρmin = −0.31 e Å−3 |
140 parameters | |
Special details top
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. The data collection nominally covered a sphere of reciprocal space, by a combination of six [for (I)] and seven [for (II)] sets of exposures; each set had a different ϕ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 6.0 cm. Coverage of the unique set is over 97% complete to at least 25° in θ [for (I)] and to 26.4° [for (II)]. Crystal decay was monitored by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.31541 (18) | 0.05264 (11) | 0.37599 (6) | 0.0564 (4) | |
N1 | 0.2924 (4) | 0.2822 (3) | 0.5009 (2) | 0.0342 (8) | |
H1 | 0.275 (6) | 0.239 (4) | 0.446 (3) | 0.066 (14)* | |
C2 | 0.3453 (6) | 0.2038 (5) | 0.5697 (2) | 0.0453 (11) | |
H2 | 0.3623 | 0.1082 | 0.5630 | 0.054* | |
C3 | 0.3757 (6) | 0.2635 (5) | 0.6517 (3) | 0.0505 (13) | |
H3 | 0.4105 | 0.2082 | 0.7014 | 0.061* | |
C4 | 0.3556 (6) | 0.4011 (6) | 0.6606 (3) | 0.0519 (13) | |
H4 | 0.3772 | 0.4416 | 0.7164 | 0.062* | |
C5 | 0.3034 (5) | 0.4829 (5) | 0.5880 (3) | 0.0418 (11) | |
C6 | 0.2845 (6) | 0.6278 (5) | 0.5927 (3) | 0.0550 (13) | |
H6 | 0.3078 | 0.6723 | 0.6473 | 0.066* | |
C7 | 0.2336 (6) | 0.7028 (5) | 0.5202 (3) | 0.0538 (13) | |
H7 | 0.2233 | 0.7992 | 0.5249 | 0.065* | |
C8 | 0.1953 (5) | 0.6404 (4) | 0.4376 (3) | 0.0406 (11) | |
C9 | 0.1382 (6) | 0.7142 (4) | 0.3612 (3) | 0.0499 (12) | |
H9 | 0.1261 | 0.8108 | 0.3631 | 0.060* | |
C10 | 0.1003 (6) | 0.6471 (4) | 0.2845 (3) | 0.0467 (12) | |
H10 | 0.0577 | 0.6955 | 0.2328 | 0.056* | |
C11 | 0.1253 (5) | 0.5058 (4) | 0.2833 (3) | 0.0407 (11) | |
H11 | 0.1008 | 0.4606 | 0.2290 | 0.049* | |
N12 | 0.1805 (4) | 0.4303 (3) | 0.35232 (19) | 0.0358 (8) | |
C13 | 0.2125 (5) | 0.4983 (4) | 0.4292 (2) | 0.0320 (9) | |
C14 | 0.2694 (5) | 0.4212 (4) | 0.5061 (2) | 0.0340 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0929 (10) | 0.0341 (6) | 0.0378 (6) | 0.0029 (6) | −0.0099 (5) | −0.0012 (6) |
N1 | 0.032 (2) | 0.039 (2) | 0.0319 (19) | −0.0022 (16) | 0.0022 (15) | −0.0001 (17) |
C2 | 0.041 (3) | 0.056 (3) | 0.039 (2) | −0.006 (2) | 0.0047 (19) | 0.010 (2) |
C3 | 0.033 (3) | 0.084 (4) | 0.034 (2) | −0.010 (3) | 0.0010 (18) | 0.010 (3) |
C4 | 0.035 (3) | 0.084 (4) | 0.036 (2) | −0.011 (2) | 0.0046 (19) | −0.017 (2) |
C5 | 0.024 (2) | 0.061 (3) | 0.040 (3) | −0.010 (2) | 0.0049 (18) | −0.018 (2) |
C6 | 0.035 (3) | 0.067 (4) | 0.064 (3) | −0.010 (3) | 0.011 (2) | −0.035 (3) |
C7 | 0.037 (3) | 0.040 (3) | 0.084 (4) | −0.004 (2) | 0.010 (3) | −0.031 (3) |
C8 | 0.026 (2) | 0.033 (3) | 0.064 (3) | −0.0056 (19) | 0.010 (2) | −0.012 (2) |
C9 | 0.031 (3) | 0.031 (3) | 0.088 (4) | −0.004 (2) | 0.006 (2) | −0.001 (3) |
C10 | 0.035 (3) | 0.037 (3) | 0.067 (3) | −0.001 (2) | 0.002 (2) | 0.020 (2) |
C11 | 0.036 (2) | 0.036 (3) | 0.049 (3) | −0.0033 (19) | 0.001 (2) | 0.001 (2) |
N12 | 0.0335 (19) | 0.037 (2) | 0.0369 (18) | −0.0010 (16) | 0.0038 (15) | 0.0051 (17) |
C13 | 0.023 (2) | 0.033 (2) | 0.040 (2) | −0.0038 (17) | 0.0029 (17) | −0.0046 (18) |
C14 | 0.019 (2) | 0.039 (3) | 0.045 (2) | −0.0046 (18) | 0.0085 (17) | −0.009 (2) |
Geometric parameters (Å, º) top
N1—C2 | 1.331 (5) | C7—C8 | 1.418 (5) |
N1—C14 | 1.373 (5) | C8—C13 | 1.404 (5) |
C2—C3 | 1.395 (6) | C8—C9 | 1.405 (6) |
C3—C4 | 1.363 (6) | C9—C10 | 1.358 (6) |
C4—C5 | 1.394 (6) | C10—C11 | 1.394 (6) |
C5—C14 | 1.404 (5) | C11—N12 | 1.321 (5) |
C5—C6 | 1.427 (6) | N12—C13 | 1.362 (5) |
C6—C7 | 1.355 (6) | C13—C14 | 1.428 (5) |
| | | |
C2—N1—C14 | 123.1 (4) | C9—C8—C7 | 123.2 (4) |
N1—C2—C3 | 119.3 (4) | C10—C9—C8 | 119.9 (4) |
C4—C3—C2 | 120.0 (4) | C9—C10—C11 | 118.8 (4) |
C3—C4—C5 | 120.3 (4) | N12—C11—C10 | 124.6 (4) |
C4—C5—C14 | 119.0 (4) | C11—N12—C13 | 116.1 (3) |
C4—C5—C6 | 123.1 (4) | N12—C13—C8 | 124.0 (4) |
C14—C5—C6 | 117.9 (4) | N12—C13—C14 | 118.4 (3) |
C7—C6—C5 | 120.8 (4) | C8—C13—C14 | 117.6 (4) |
C6—C7—C8 | 121.4 (4) | N1—C14—C5 | 118.2 (4) |
C13—C8—C9 | 116.6 (4) | N1—C14—C13 | 119.7 (3) |
C13—C8—C7 | 120.2 (4) | C5—C14—C13 | 122.1 (4) |
| | | |
C14—N1—C2—C3 | 1.3 (6) | C11—N12—C13—C14 | 179.0 (3) |
N1—C2—C3—C4 | −1.5 (6) | C9—C8—C13—N12 | 1.1 (6) |
C2—C3—C4—C5 | 0.4 (6) | C7—C8—C13—N12 | −179.3 (3) |
C3—C4—C5—C14 | 0.9 (6) | C9—C8—C13—C14 | −179.7 (3) |
C3—C4—C5—C6 | −178.5 (4) | C7—C8—C13—C14 | −0.1 (5) |
C4—C5—C6—C7 | 179.9 (4) | C2—N1—C14—C5 | 0.0 (5) |
C14—C5—C6—C7 | 0.5 (6) | C2—N1—C14—C13 | 179.9 (3) |
C5—C6—C7—C8 | 0.7 (6) | C4—C5—C14—N1 | −1.1 (5) |
C6—C7—C8—C13 | −0.9 (6) | C6—C5—C14—N1 | 178.3 (3) |
C6—C7—C8—C9 | 178.6 (4) | C4—C5—C14—C13 | 179.0 (4) |
C13—C8—C9—C10 | 0.9 (6) | C6—C5—C14—C13 | −1.6 (5) |
C7—C8—C9—C10 | −178.7 (4) | N12—C13—C14—N1 | 0.7 (5) |
C8—C9—C10—C11 | −2.0 (6) | C8—C13—C14—N1 | −178.6 (3) |
C9—C10—C11—N12 | 1.3 (6) | N12—C13—C14—C5 | −179.4 (3) |
C10—C11—N12—C13 | 0.6 (5) | C8—C13—C14—C5 | 1.4 (5) |
C11—N12—C13—C8 | −1.8 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.95 (4) | 2.16 (4) | 2.986 (4) | 145 (4) |
C2—H2···Cl1i | 0.95 | 2.79 | 3.462 (4) | 128 |
C4—H4···Cl1ii | 0.95 | 2.57 | 3.424 (4) | 150 |
C9—H9···Cl1iii | 0.95 | 2.70 | 3.527 (4) | 146 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, y+1, z. |
Crystal data top
3C12H9N2+·2Cl−·HCl·Cl−·CHCl3 | F(000) = 1648 |
Mr = 805.81 | Dx = 1.464 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 26.017 (3) Å | Cell parameters from 8192 reflections |
b = 7.222 (1) Å | θ = 1–25° |
c = 19.461 (2) Å | µ = 0.58 mm−1 |
β = 90.77 (1)° | T = 173 K |
V = 3656.3 (8) Å3 | Plate, colourless |
Z = 4 | 0.46 × 0.34 × 0.18 mm |
Data collection top
Siemens CCD three-circle diffractometer | 7983 independent reflections |
Radiation source: fine-focus sealed tube | 5433 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
ω scans | θmax = 27.9°, θmin = 2.1° |
Absorption correction: empirical SADABS (Sheldrick, 1996) | h = −32→32 |
Tmin = 0.776, Tmax = 0.903 | k = −9→9 |
52608 measured reflections | l = −25→24 |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0279P)2 + 2.6109P] where P = (Fo2 + 2Fc2)/3 |
7983 reflections | (Δ/σ)max = 0.002 |
467 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
3C12H9N2+·2Cl−·HCl·Cl−·CHCl3 | V = 3656.3 (8) Å3 |
Mr = 805.81 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 26.017 (3) Å | µ = 0.58 mm−1 |
b = 7.222 (1) Å | T = 173 K |
c = 19.461 (2) Å | 0.46 × 0.34 × 0.18 mm |
β = 90.77 (1)° | |
Data collection top
Siemens CCD three-circle diffractometer | 7983 independent reflections |
Absorption correction: empirical SADABS (Sheldrick, 1996) | 5433 reflections with I > 2σ(I) |
Tmin = 0.776, Tmax = 0.903 | Rint = 0.058 |
52608 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.27 e Å−3 |
7983 reflections | Δρmin = −0.28 e Å−3 |
467 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.67394 (9) | 0.3968 (3) | 0.75826 (10) | 0.0290 (5) | |
H1 | 0.6423 (10) | 0.409 (4) | 0.7657 (13) | 0.039 (8)* | |
C1 | 0.70605 (10) | 0.4347 (4) | 0.81055 (12) | 0.0335 (6) | |
H1A | 0.6926 | 0.4714 | 0.8536 | 0.040* | |
C2 | 0.75904 (10) | 0.4208 (4) | 0.80262 (13) | 0.0371 (6) | |
H2 | 0.7818 | 0.4476 | 0.8398 | 0.044* | |
C3 | 0.77771 (10) | 0.3675 (4) | 0.73978 (13) | 0.0358 (6) | |
H3A | 0.8138 | 0.3586 | 0.7335 | 0.043* | |
C4 | 0.74401 (9) | 0.3259 (3) | 0.68459 (12) | 0.0302 (6) | |
C5 | 0.76184 (10) | 0.2664 (4) | 0.61825 (13) | 0.0374 (6) | |
H5A | 0.7977 | 0.2528 | 0.6109 | 0.045* | |
C6 | 0.72817 (10) | 0.2299 (4) | 0.56638 (13) | 0.0365 (6) | |
H6 | 0.7408 | 0.1904 | 0.5232 | 0.044* | |
C7 | 0.67352 (10) | 0.2496 (3) | 0.57518 (12) | 0.0298 (6) | |
C8 | 0.63744 (10) | 0.2128 (3) | 0.52182 (12) | 0.0353 (6) | |
H8 | 0.6487 | 0.1744 | 0.4778 | 0.042* | |
C9 | 0.58573 (10) | 0.2333 (4) | 0.53437 (12) | 0.0363 (6) | |
H9 | 0.5609 | 0.2090 | 0.4993 | 0.044* | |
C10 | 0.57028 (10) | 0.2910 (4) | 0.60013 (12) | 0.0354 (6) | |
H10 | 0.5345 | 0.3044 | 0.6079 | 0.042* | |
N2 | 0.60266 (7) | 0.3282 (3) | 0.65236 (10) | 0.0302 (5) | |
C11 | 0.65390 (9) | 0.3063 (3) | 0.63960 (11) | 0.0264 (5) | |
C12 | 0.69029 (9) | 0.3426 (3) | 0.69481 (12) | 0.0267 (5) | |
N3 | 0.47600 (8) | 0.4367 (3) | 0.78823 (10) | 0.0270 (5) | |
H3 | 0.4991 (10) | 0.425 (4) | 0.8197 (13) | 0.032 (7)* | |
C21 | 0.49118 (9) | 0.5005 (3) | 0.72722 (12) | 0.0305 (6) | |
H21 | 0.5266 | 0.5243 | 0.7197 | 0.037* | |
C22 | 0.45536 (9) | 0.5319 (3) | 0.67478 (12) | 0.0316 (6) | |
H22 | 0.4660 | 0.5785 | 0.6316 | 0.038* | |
C23 | 0.40413 (9) | 0.4945 (3) | 0.68635 (12) | 0.0307 (6) | |
H23 | 0.3793 | 0.5168 | 0.6510 | 0.037* | |
C24 | 0.38837 (9) | 0.4233 (3) | 0.75018 (11) | 0.0259 (5) | |
C25 | 0.33535 (9) | 0.3823 (3) | 0.76522 (12) | 0.0298 (6) | |
H25 | 0.3096 | 0.3989 | 0.7306 | 0.036* | |
C26 | 0.32193 (9) | 0.3201 (3) | 0.82843 (12) | 0.0300 (6) | |
H26 | 0.2868 | 0.2944 | 0.8373 | 0.036* | |
C27 | 0.35977 (8) | 0.2921 (3) | 0.88227 (11) | 0.0257 (5) | |
C28 | 0.34683 (9) | 0.2341 (3) | 0.94941 (12) | 0.0320 (6) | |
H28 | 0.3121 | 0.2079 | 0.9605 | 0.038* | |
C29 | 0.38523 (10) | 0.2162 (4) | 0.99822 (13) | 0.0374 (6) | |
H29 | 0.3774 | 0.1794 | 1.0438 | 0.045* | |
C30 | 0.43631 (10) | 0.2532 (4) | 0.97970 (13) | 0.0400 (7) | |
H30 | 0.4623 | 0.2397 | 1.0142 | 0.048* | |
N4 | 0.45087 (7) | 0.3059 (3) | 0.91730 (10) | 0.0330 (5) | |
C31 | 0.41235 (8) | 0.3273 (3) | 0.86944 (11) | 0.0248 (5) | |
C32 | 0.42588 (8) | 0.3945 (3) | 0.80225 (12) | 0.0244 (5) | |
N5 | 0.98791 (8) | 0.3167 (3) | 0.60652 (9) | 0.0247 (4) | |
H5 | 0.9611 (9) | 0.352 (3) | 0.6273 (12) | 0.030 (7)* | |
C41 | 1.02952 (9) | 0.2931 (3) | 0.64643 (12) | 0.0299 (6) | |
H41 | 1.0278 | 0.3165 | 0.6944 | 0.036* | |
C42 | 1.07568 (9) | 0.2340 (4) | 0.61754 (12) | 0.0334 (6) | |
H42 | 1.1054 | 0.2164 | 0.6458 | 0.040* | |
C43 | 1.07775 (9) | 0.2014 (3) | 0.54782 (12) | 0.0298 (5) | |
H43 | 1.1092 | 0.1645 | 0.5278 | 0.036* | |
C44 | 1.03312 (8) | 0.2226 (3) | 0.50592 (11) | 0.0245 (5) | |
C45 | 1.03239 (9) | 0.1868 (3) | 0.43322 (12) | 0.0294 (5) | |
H45 | 1.0631 | 0.1492 | 0.4114 | 0.035* | |
C46 | 0.98869 (9) | 0.2056 (3) | 0.39518 (12) | 0.0293 (5) | |
H46 | 0.9892 | 0.1795 | 0.3474 | 0.035* | |
C47 | 0.94148 (9) | 0.2646 (3) | 0.42619 (11) | 0.0243 (5) | |
C48 | 0.89476 (9) | 0.2859 (4) | 0.38838 (12) | 0.0320 (6) | |
H48 | 0.8931 | 0.2562 | 0.3409 | 0.038* | |
C49 | 0.85202 (9) | 0.3501 (4) | 0.42166 (12) | 0.0339 (6) | |
H49 | 0.8205 | 0.3661 | 0.3973 | 0.041* | |
C50 | 0.85548 (9) | 0.3920 (4) | 0.49235 (12) | 0.0317 (6) | |
H50 | 0.8257 | 0.4389 | 0.5140 | 0.038* | |
N6 | 0.89790 (7) | 0.3699 (3) | 0.53073 (9) | 0.0269 (4) | |
C51 | 0.94038 (8) | 0.3068 (3) | 0.49759 (11) | 0.0216 (5) | |
C52 | 0.98720 (8) | 0.2823 (3) | 0.53726 (11) | 0.0216 (5) | |
Cl1 | 0.58166 (2) | 0.49634 (9) | 0.85282 (3) | 0.03607 (16) | |
Cl2 | 0.92728 (2) | 0.47185 (9) | 0.72848 (3) | 0.03194 (15) | |
Cl3 | 1.28210 (2) | 0.51611 (10) | 0.59651 (3) | 0.04031 (17) | |
Cl4 | 1.22226 (3) | 0.16575 (10) | 0.54186 (3) | 0.04516 (18) | |
H4 | 1.2497 (12) | 0.330 (5) | 0.5704 (16) | 0.086 (11)* | |
C1L | 0.85087 (9) | 0.8395 (4) | 0.70304 (12) | 0.0304 (6) | |
H1L | 0.8725 | 0.7292 | 0.7147 | 0.037* | |
Cl11 | 0.82194 (2) | 0.80530 (10) | 0.62080 (3) | 0.03980 (17) | |
Cl12 | 0.80329 (2) | 0.86691 (10) | 0.76726 (3) | 0.03851 (17) | |
Cl13 | 0.89046 (2) | 1.03978 (10) | 0.70288 (3) | 0.04006 (17) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0290 (12) | 0.0289 (12) | 0.0291 (11) | −0.0010 (10) | 0.0024 (9) | 0.0021 (9) |
C1 | 0.0408 (15) | 0.0310 (15) | 0.0287 (13) | −0.0027 (12) | −0.0011 (11) | 0.0023 (11) |
C2 | 0.0380 (15) | 0.0350 (15) | 0.0380 (15) | −0.0042 (12) | −0.0042 (12) | 0.0031 (12) |
C3 | 0.0308 (14) | 0.0311 (15) | 0.0455 (16) | −0.0006 (11) | −0.0001 (12) | 0.0067 (13) |
C4 | 0.0323 (13) | 0.0221 (13) | 0.0362 (13) | 0.0022 (11) | 0.0056 (11) | 0.0065 (11) |
C5 | 0.0340 (14) | 0.0369 (16) | 0.0414 (15) | 0.0092 (12) | 0.0095 (12) | 0.0068 (13) |
C6 | 0.0413 (15) | 0.0345 (15) | 0.0338 (14) | 0.0109 (12) | 0.0115 (12) | 0.0028 (12) |
C7 | 0.0423 (15) | 0.0210 (13) | 0.0263 (12) | 0.0033 (11) | 0.0048 (11) | 0.0026 (10) |
C8 | 0.0525 (17) | 0.0262 (14) | 0.0273 (13) | 0.0052 (13) | 0.0030 (12) | 0.0006 (11) |
C9 | 0.0450 (16) | 0.0338 (15) | 0.0298 (13) | 0.0021 (13) | −0.0063 (12) | −0.0003 (12) |
C10 | 0.0346 (14) | 0.0364 (16) | 0.0350 (14) | 0.0019 (12) | −0.0005 (11) | 0.0025 (12) |
N2 | 0.0315 (11) | 0.0295 (12) | 0.0296 (11) | 0.0016 (9) | 0.0000 (9) | 0.0018 (9) |
C11 | 0.0316 (13) | 0.0193 (12) | 0.0282 (12) | 0.0026 (10) | 0.0025 (10) | 0.0041 (10) |
C12 | 0.0351 (13) | 0.0176 (12) | 0.0275 (12) | 0.0010 (10) | 0.0032 (10) | 0.0039 (10) |
N3 | 0.0234 (11) | 0.0275 (12) | 0.0301 (11) | 0.0020 (9) | 0.0011 (9) | 0.0026 (9) |
C21 | 0.0291 (13) | 0.0266 (14) | 0.0360 (14) | −0.0001 (11) | 0.0096 (10) | 0.0045 (11) |
C22 | 0.0383 (14) | 0.0297 (14) | 0.0270 (13) | 0.0002 (11) | 0.0058 (11) | 0.0027 (11) |
C23 | 0.0347 (14) | 0.0304 (14) | 0.0270 (12) | 0.0022 (12) | 0.0007 (10) | −0.0052 (11) |
C24 | 0.0274 (12) | 0.0222 (13) | 0.0281 (12) | 0.0019 (10) | 0.0013 (10) | −0.0069 (10) |
C25 | 0.0244 (12) | 0.0324 (14) | 0.0324 (13) | 0.0001 (11) | −0.0029 (10) | −0.0060 (11) |
C26 | 0.0241 (12) | 0.0289 (14) | 0.0371 (14) | −0.0032 (11) | 0.0045 (10) | −0.0057 (11) |
C27 | 0.0255 (12) | 0.0213 (12) | 0.0303 (12) | −0.0006 (10) | 0.0045 (10) | −0.0021 (10) |
C28 | 0.0274 (13) | 0.0299 (14) | 0.0390 (14) | −0.0009 (11) | 0.0108 (11) | 0.0004 (12) |
C29 | 0.0394 (15) | 0.0383 (16) | 0.0346 (14) | 0.0006 (13) | 0.0094 (12) | 0.0092 (12) |
C30 | 0.0366 (15) | 0.0463 (18) | 0.0371 (15) | 0.0028 (13) | 0.0000 (12) | 0.0116 (13) |
N4 | 0.0268 (11) | 0.0387 (13) | 0.0336 (11) | 0.0033 (10) | 0.0013 (9) | 0.0075 (10) |
C31 | 0.0242 (12) | 0.0210 (13) | 0.0293 (12) | 0.0019 (10) | 0.0018 (10) | 0.0000 (10) |
C32 | 0.0237 (12) | 0.0190 (12) | 0.0307 (12) | 0.0013 (10) | 0.0037 (10) | −0.0006 (10) |
N5 | 0.0239 (11) | 0.0271 (11) | 0.0232 (10) | 0.0006 (9) | 0.0021 (9) | 0.0002 (9) |
C41 | 0.0326 (13) | 0.0325 (14) | 0.0243 (12) | −0.0006 (11) | −0.0066 (10) | 0.0013 (11) |
C42 | 0.0292 (13) | 0.0364 (16) | 0.0342 (14) | 0.0018 (11) | −0.0106 (11) | 0.0011 (12) |
C43 | 0.0223 (12) | 0.0284 (14) | 0.0388 (14) | 0.0004 (10) | 0.0021 (10) | 0.0022 (12) |
C44 | 0.0229 (12) | 0.0216 (12) | 0.0290 (12) | −0.0014 (10) | 0.0034 (10) | 0.0032 (10) |
C45 | 0.0271 (13) | 0.0312 (14) | 0.0302 (13) | 0.0013 (11) | 0.0094 (10) | −0.0020 (11) |
C46 | 0.0344 (14) | 0.0317 (14) | 0.0220 (12) | 0.0006 (11) | 0.0049 (10) | −0.0011 (11) |
C47 | 0.0281 (12) | 0.0218 (13) | 0.0232 (11) | −0.0027 (10) | 0.0007 (10) | 0.0025 (10) |
C48 | 0.0369 (14) | 0.0358 (15) | 0.0232 (12) | −0.0019 (12) | −0.0058 (10) | 0.0017 (11) |
C49 | 0.0270 (13) | 0.0377 (16) | 0.0368 (14) | −0.0013 (11) | −0.0067 (11) | 0.0071 (12) |
C50 | 0.0234 (12) | 0.0354 (15) | 0.0365 (14) | 0.0021 (11) | 0.0034 (10) | 0.0064 (12) |
N6 | 0.0229 (10) | 0.0309 (12) | 0.0270 (10) | 0.0014 (9) | 0.0034 (8) | 0.0029 (9) |
C51 | 0.0223 (11) | 0.0191 (12) | 0.0235 (11) | −0.0019 (9) | 0.0025 (9) | 0.0018 (10) |
C52 | 0.0246 (12) | 0.0184 (12) | 0.0219 (11) | −0.0024 (9) | 0.0014 (9) | 0.0025 (10) |
Cl1 | 0.0309 (3) | 0.0442 (4) | 0.0331 (3) | −0.0072 (3) | 0.0011 (3) | −0.0042 (3) |
Cl2 | 0.0368 (3) | 0.0333 (3) | 0.0258 (3) | 0.0050 (3) | 0.0025 (2) | −0.0011 (3) |
Cl3 | 0.0297 (3) | 0.0542 (4) | 0.0370 (3) | 0.0038 (3) | −0.0015 (3) | −0.0024 (3) |
Cl4 | 0.0445 (4) | 0.0515 (5) | 0.0394 (4) | 0.0007 (3) | −0.0007 (3) | −0.0010 (3) |
C1L | 0.0275 (13) | 0.0330 (15) | 0.0308 (13) | 0.0009 (11) | −0.0006 (10) | −0.0025 (11) |
Cl11 | 0.0334 (3) | 0.0526 (4) | 0.0333 (3) | 0.0006 (3) | −0.0026 (3) | −0.0104 (3) |
Cl12 | 0.0337 (3) | 0.0492 (4) | 0.0327 (3) | −0.0056 (3) | 0.0044 (3) | 0.0014 (3) |
Cl13 | 0.0350 (3) | 0.0461 (4) | 0.0393 (3) | −0.0104 (3) | 0.0076 (3) | −0.0090 (3) |
Geometric parameters (Å, º) top
N1—C1 | 1.336 (3) | C27—C28 | 1.417 (3) |
N1—C12 | 1.369 (3) | C28—C29 | 1.375 (3) |
C1—C2 | 1.393 (4) | C29—C30 | 1.407 (3) |
C2—C3 | 1.377 (3) | C30—N4 | 1.332 (3) |
C3—C4 | 1.410 (3) | N4—C31 | 1.368 (3) |
C4—C12 | 1.419 (3) | C31—C32 | 1.443 (3) |
C4—C5 | 1.443 (3) | N5—C41 | 1.335 (3) |
C5—C6 | 1.353 (4) | N5—C52 | 1.370 (3) |
C6—C7 | 1.441 (3) | C41—C42 | 1.400 (3) |
C7—C8 | 1.416 (3) | C42—C43 | 1.379 (3) |
C7—C11 | 1.420 (3) | C43—C44 | 1.418 (3) |
C8—C9 | 1.379 (4) | C44—C52 | 1.416 (3) |
C9—C10 | 1.410 (3) | C44—C45 | 1.438 (3) |
C10—N2 | 1.339 (3) | C45—C46 | 1.355 (3) |
N2—C11 | 1.369 (3) | C46—C47 | 1.440 (3) |
C11—C12 | 1.446 (3) | C47—C48 | 1.421 (3) |
N3—C21 | 1.338 (3) | C47—C51 | 1.423 (3) |
N3—C32 | 1.370 (3) | C48—C49 | 1.375 (3) |
C21—C22 | 1.391 (3) | C49—C50 | 1.410 (3) |
C22—C23 | 1.382 (3) | C50—N6 | 1.334 (3) |
C23—C24 | 1.410 (3) | N6—C51 | 1.365 (3) |
C24—C32 | 1.413 (3) | C51—C52 | 1.444 (3) |
C24—C25 | 1.445 (3) | C1L—Cl13 | 1.776 (3) |
C25—C26 | 1.360 (3) | C1L—Cl11 | 1.777 (2) |
C26—C27 | 1.442 (3) | C1L—Cl12 | 1.782 (2) |
C27—C31 | 1.417 (3) | | |
| | | |
C1—N1—C12 | 123.2 (2) | C28—C29—C30 | 119.0 (2) |
N1—C1—C2 | 120.7 (2) | N4—C30—C29 | 124.7 (2) |
C3—C2—C1 | 118.7 (2) | C30—N4—C31 | 116.0 (2) |
C2—C3—C4 | 120.9 (2) | N4—C31—C27 | 124.1 (2) |
C3—C4—C12 | 118.6 (2) | N4—C31—C32 | 118.0 (2) |
C3—C4—C5 | 122.7 (2) | C27—C31—C32 | 117.9 (2) |
C12—C4—C5 | 118.7 (2) | N3—C32—C24 | 118.3 (2) |
C6—C5—C4 | 120.8 (2) | N3—C32—C31 | 120.0 (2) |
C5—C6—C7 | 121.5 (2) | C24—C32—C31 | 121.7 (2) |
C8—C7—C11 | 117.3 (2) | C41—N5—C52 | 123.3 (2) |
C8—C7—C6 | 122.7 (2) | N5—C41—C42 | 119.9 (2) |
C11—C7—C6 | 120.0 (2) | C43—C42—C41 | 119.5 (2) |
C9—C8—C7 | 119.3 (2) | C42—C43—C44 | 120.3 (2) |
C8—C9—C10 | 118.9 (2) | C52—C44—C43 | 118.3 (2) |
N2—C10—C9 | 124.4 (2) | C52—C44—C45 | 118.6 (2) |
C10—N2—C11 | 116.3 (2) | C43—C44—C45 | 123.1 (2) |
N2—C11—C7 | 123.8 (2) | C46—C45—C44 | 121.3 (2) |
N2—C11—C12 | 118.3 (2) | C45—C46—C47 | 121.0 (2) |
C7—C11—C12 | 117.9 (2) | C48—C47—C51 | 117.0 (2) |
N1—C12—C4 | 118.0 (2) | C48—C47—C46 | 122.9 (2) |
N1—C12—C11 | 120.9 (2) | C51—C47—C46 | 120.1 (2) |
C4—C12—C11 | 121.1 (2) | C49—C48—C47 | 119.0 (2) |
C21—N3—C32 | 123.1 (2) | C48—C49—C50 | 119.4 (2) |
N3—C21—C22 | 120.3 (2) | N6—C50—C49 | 124.2 (2) |
C23—C22—C21 | 119.1 (2) | C50—N6—C51 | 116.38 (19) |
C22—C23—C24 | 120.5 (2) | N6—C51—C47 | 124.0 (2) |
C23—C24—C32 | 118.6 (2) | N6—C51—C52 | 118.08 (19) |
C23—C24—C25 | 122.9 (2) | C47—C51—C52 | 117.89 (19) |
C32—C24—C25 | 118.5 (2) | N5—C52—C44 | 118.6 (2) |
C26—C25—C24 | 120.6 (2) | N5—C52—C51 | 120.24 (19) |
C25—C26—C27 | 121.5 (2) | C44—C52—C51 | 121.16 (19) |
C31—C27—C28 | 117.2 (2) | Cl13—C1L—Cl11 | 110.49 (13) |
C31—C27—C26 | 119.9 (2) | Cl13—C1L—Cl12 | 108.60 (13) |
C28—C27—C26 | 122.9 (2) | Cl11—C1L—Cl12 | 110.94 (13) |
C29—C28—C27 | 119.0 (2) | | |
| | | |
C12—N1—C1—C2 | 0.2 (4) | C30—N4—C31—C32 | 176.4 (2) |
N1—C1—C2—C3 | 0.1 (4) | C28—C27—C31—N4 | 1.0 (4) |
C1—C2—C3—C4 | −0.6 (4) | C26—C27—C31—N4 | 179.6 (2) |
C2—C3—C4—C12 | 0.9 (4) | C28—C27—C31—C32 | −177.2 (2) |
C2—C3—C4—C5 | −178.9 (2) | C26—C27—C31—C32 | 1.3 (3) |
C3—C4—C5—C6 | −179.3 (2) | C21—N3—C32—C24 | −1.3 (3) |
C12—C4—C5—C6 | 1.0 (4) | C21—N3—C32—C31 | −179.7 (2) |
C4—C5—C6—C7 | 0.3 (4) | C23—C24—C32—N3 | −0.2 (3) |
C5—C6—C7—C8 | 179.8 (2) | C25—C24—C32—N3 | −178.9 (2) |
C5—C6—C7—C11 | −0.8 (4) | C23—C24—C32—C31 | 178.2 (2) |
C11—C7—C8—C9 | 0.0 (4) | C25—C24—C32—C31 | −0.5 (3) |
C6—C7—C8—C9 | 179.5 (2) | N4—C31—C32—N3 | −0.7 (3) |
C7—C8—C9—C10 | 0.2 (4) | C27—C31—C32—N3 | 177.7 (2) |
C8—C9—C10—N2 | 0.1 (4) | N4—C31—C32—C24 | −179.0 (2) |
C9—C10—N2—C11 | −0.5 (4) | C27—C31—C32—C24 | −0.6 (3) |
C10—N2—C11—C7 | 0.7 (3) | C52—N5—C41—C42 | 1.3 (4) |
C10—N2—C11—C12 | −179.2 (2) | N5—C41—C42—C43 | 0.3 (4) |
C8—C7—C11—N2 | −0.5 (4) | C41—C42—C43—C44 | −1.7 (4) |
C6—C7—C11—N2 | −179.9 (2) | C42—C43—C44—C52 | 1.6 (3) |
C8—C7—C11—C12 | 179.4 (2) | C42—C43—C44—C45 | −178.6 (2) |
C6—C7—C11—C12 | 0.0 (3) | C52—C44—C45—C46 | −1.4 (4) |
C1—N1—C12—C4 | 0.1 (3) | C43—C44—C45—C46 | 178.8 (2) |
C1—N1—C12—C11 | −178.9 (2) | C44—C45—C46—C47 | 0.8 (4) |
C3—C4—C12—N1 | −0.6 (3) | C45—C46—C47—C48 | −179.9 (2) |
C5—C4—C12—N1 | 179.2 (2) | C45—C46—C47—C51 | 0.9 (4) |
C3—C4—C12—C11 | 178.4 (2) | C51—C47—C48—C49 | 1.8 (3) |
C5—C4—C12—C11 | −1.8 (3) | C46—C47—C48—C49 | −177.4 (2) |
N2—C11—C12—N1 | 0.2 (3) | C47—C48—C49—C50 | −0.4 (4) |
C7—C11—C12—N1 | −179.7 (2) | C48—C49—C50—N6 | −1.5 (4) |
N2—C11—C12—C4 | −178.8 (2) | C49—C50—N6—C51 | 1.7 (4) |
C7—C11—C12—C4 | 1.3 (3) | C50—N6—C51—C47 | −0.1 (3) |
C32—N3—C21—C22 | 1.8 (4) | C50—N6—C51—C52 | 179.6 (2) |
N3—C21—C22—C23 | −0.7 (4) | C48—C47—C51—N6 | −1.7 (3) |
C21—C22—C23—C24 | −0.7 (4) | C46—C47—C51—N6 | 177.6 (2) |
C22—C23—C24—C32 | 1.1 (4) | C48—C47—C51—C52 | 178.7 (2) |
C22—C23—C24—C25 | 179.8 (2) | C46—C47—C51—C52 | −2.1 (3) |
C23—C24—C25—C26 | −177.7 (2) | C41—N5—C52—C44 | −1.4 (3) |
C32—C24—C25—C26 | 1.0 (3) | C41—N5—C52—C51 | 178.6 (2) |
C24—C25—C26—C27 | −0.3 (4) | C43—C44—C52—N5 | −0.1 (3) |
C25—C26—C27—C31 | −0.9 (4) | C45—C44—C52—N5 | −179.9 (2) |
C25—C26—C27—C28 | 177.6 (2) | C43—C44—C52—C51 | 180.0 (2) |
C31—C27—C28—C29 | 0.5 (3) | C45—C44—C52—C51 | 0.1 (3) |
C26—C27—C28—C29 | −178.1 (2) | N6—C51—C52—N5 | 1.9 (3) |
C27—C28—C29—C30 | −1.0 (4) | C47—C51—C52—N5 | −178.4 (2) |
C28—C29—C30—N4 | 0.2 (4) | N6—C51—C52—C44 | −178.1 (2) |
C29—C30—N4—C31 | 1.2 (4) | C47—C51—C52—C44 | 1.5 (3) |
C30—N4—C31—C27 | −1.8 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Cl1 | 0.95 | 2.89 | 3.380 (3) | 113 |
C21—H21···Cl1 | 0.95 | 2.95 | 3.371 (3) | 108 |
C46—H46···Cl2i | 0.95 | 3.01 | 3.818 (2) | 144 |
C48—H48···Cl2i | 0.95 | 2.89 | 3.733 (3) | 149 |
C23—H23···Cl3ii | 0.95 | 2.73 | 3.607 (3) | 154 |
C25—H25···Cl3ii | 0.95 | 2.83 | 3.676 (3) | 149 |
C29—H29···Cl3iii | 0.95 | 3.04 | 3.716 (3) | 129 |
C49—H49···Cl3iv | 0.95 | 2.80 | 3.633 (3) | 146 |
C2—H2···Cl4v | 0.95 | 2.79 | 3.534 (3) | 136 |
C6—H6···Cl4vi | 0.95 | 3.03 | 3.787 (3) | 138 |
C45—H45···Cl11iv | 0.95 | 3.08 | 3.947 (2) | 152 |
C26—H26···Cl11vii | 0.95 | 2.96 | 3.886 (2) | 166 |
C25—H25···Cl12vii | 0.95 | 2.95 | 3.655 (2) | 132 |
C42—H42···Cl12viii | 0.95 | 3.10 | 3.959 (2) | 152 |
C45—H45···Cl13iv | 0.95 | 2.89 | 3.723 (2) | 147 |
C48—H48···Cl13ix | 0.95 | 3.06 | 3.824 (2) | 138 |
N1—H1···Cl1 | 0.84 (3) | 2.42 (3) | 3.128 (2) | 143 (2) |
N3—H3···Cl1 | 0.86 (2) | 2.29 (3) | 3.038 (2) | 146 (2) |
C1L—H1L···Cl2 | 1.00 | 2.35 | 3.349 (3) | 173 |
N5—H5···Cl2 | 0.85 (2) | 2.33 (2) | 3.079 (2) | 146 (2) |
Cl4—H4···Cl3 | 1.49 (3) | 1.67 (3) | 3.1485 (11) | 176 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) x−1, −y+1/2, z+1/2; (iv) −x+2, −y+1, −z+1; (v) −x+2, y+1/2, −z+3/2; (vi) −x+2, −y, −z+1; (vii) −x+1, y−1/2, −z+3/2; (viii) −x+2, y−1/2, −z+3/2; (ix) x, −y+3/2, z−1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C12H9N2+·Cl− | 3C12H9N2+·2Cl−·HCl·Cl−·CHCl3 |
Mr | 216.66 | 805.81 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 6.877 (1), 9.787 (1), 15.547 (2) | 26.017 (3), 7.222 (1), 19.461 (2) |
β (°) | 96.91 (2) | 90.77 (1) |
V (Å3) | 1038.8 (2) | 3656.3 (8) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.58 |
Crystal size (mm) | 0.25 × 0.20 × 0.10 | 0.46 × 0.34 × 0.18 |
|
Data collection |
Diffractometer | Siemens CCD three circle diffractometer | Siemens CCD three-circle diffractometer |
Absorption correction | Empirical SADABS (Sheldrick, 1996) | Empirical SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.922, 0.968 | 0.776, 0.903 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7686, 1884, 1093 | 52608, 7983, 5433 |
Rint | 0.083 | 0.058 |
(sin θ/λ)max (Å−1) | 0.617 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.150, 1.05 | 0.043, 0.090, 1.05 |
No. of reflections | 1884 | 7983 |
No. of parameters | 140 | 467 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.56, −0.31 | 0.27, −0.28 |
Selected geometric parameters (Å, º) for (I) topN1—C2 | 1.331 (5) | C11—N12 | 1.321 (5) |
N1—C14 | 1.373 (5) | N12—C13 | 1.362 (5) |
| | | |
C2—N1—C14 | 123.1 (4) | C11—N12—C13 | 116.1 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.95 (4) | 2.16 (4) | 2.986 (4) | 145 (4) |
C2—H2···Cl1i | 0.95 | 2.79 | 3.462 (4) | 128.4 |
C4—H4···Cl1ii | 0.95 | 2.57 | 3.424 (4) | 150.1 |
C9—H9···Cl1iii | 0.95 | 2.70 | 3.527 (4) | 146.4 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x, y+1, z. |
Selected geometric parameters (Å, º) for (II) topN1—C1 | 1.336 (3) | C30—N4 | 1.332 (3) |
N1—C12 | 1.369 (3) | N4—C31 | 1.368 (3) |
C10—N2 | 1.339 (3) | N5—C41 | 1.335 (3) |
N2—C11 | 1.369 (3) | N5—C52 | 1.370 (3) |
N3—C21 | 1.338 (3) | C50—N6 | 1.334 (3) |
N3—C32 | 1.370 (3) | N6—C51 | 1.365 (3) |
| | | |
C1—N1—C12 | 123.2 (2) | C30—N4—C31 | 116.0 (2) |
C10—N2—C11 | 116.3 (2) | C41—N5—C52 | 123.3 (2) |
C21—N3—C32 | 123.1 (2) | C50—N6—C51 | 116.38 (19) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Cl1 | 0.95 | 2.89 | 3.380 (3) | 113.1 |
C21—H21···Cl1 | 0.95 | 2.95 | 3.371 (3) | 108.2 |
C46—H46···Cl2i | 0.95 | 3.01 | 3.818 (2) | 144.3 |
C48—H48···Cl2i | 0.95 | 2.89 | 3.733 (3) | 148.8 |
C23—H23···Cl3ii | 0.95 | 2.73 | 3.607 (3) | 153.8 |
C25—H25···Cl3ii | 0.95 | 2.83 | 3.676 (3) | 149.2 |
C29—H29···Cl3iii | 0.95 | 3.04 | 3.716 (3) | 129.1 |
C49—H49···Cl3iv | 0.95 | 2.80 | 3.633 (3) | 146.3 |
C2—H2···Cl4v | 0.95 | 2.79 | 3.534 (3) | 135.5 |
C6—H6···Cl4vi | 0.95 | 3.03 | 3.787 (3) | 137.8 |
C45—H45···Cl11iv | 0.95 | 3.08 | 3.947 (2) | 152.4 |
C26—H26···Cl11vii | 0.95 | 2.96 | 3.886 (2) | 166.2 |
C25—H25···Cl12vii | 0.95 | 2.95 | 3.655 (2) | 132.3 |
C42—H42···Cl12viii | 0.95 | 3.10 | 3.959 (2) | 151.8 |
C45—H45···Cl13iv | 0.95 | 2.89 | 3.723 (2) | 147.3 |
C48—H48···Cl13ix | 0.95 | 3.06 | 3.824 (2) | 138.2 |
N1—H1···Cl1 | 0.84 (3) | 2.42 (3) | 3.128 (2) | 143 (2) |
N3—H3···Cl1 | 0.86 (2) | 2.29 (3) | 3.038 (2) | 146 (2) |
C1L—H1L···Cl2 | 1.00 | 2.35 | 3.349 (3) | 173.1 |
N5—H5···Cl2 | 0.85 (2) | 2.33 (2) | 3.079 (2) | 146 (2) |
Cl4—H4···Cl3 | 1.49 (3) | 1.67 (3) | 3.1485 (11) | 176 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x−1, y, z; (iii) x−1, −y+1/2, z+1/2; (iv) −x+2, −y+1, −z+1; (v) −x+2, y+1/2, −z+3/2; (vi) −x+2, −y, −z+1; (vii) −x+1, y−1/2, −z+3/2; (viii) −x+2, y−1/2, −z+3/2; (ix) x, −y+3/2, z−1/2. |
As a Lewis acid, trichloromethylsilane forms a complex with the Lewis bases 3,4-dimethylpyridine (Hensen et al., 1990) and 3,5-dimethylpyridine (Hensen et al., 1989; Burger et al., 1992). According to the result of Kummer (1977), who prepared bis-phenanthroline-complexes of diiodosilanes with different substituents, we tried to synthesize a complex of MeSiCl3 with the Lewis base 1,10-phenanthroline. The two obtained structures, however, are products of hydrolyses of a mixture of methyltrichlorosilane and 1,10-phenanthroline.
1,10-Phenanthrolin-1-ium chloride, (I) (Fig. 1), is the first structure of the pure 1:1 compound between 1,10-phenanthroline and HCl. It consists of a protonated phenanthroline molecule and a chloride ion. Bond lengths and angles are in the usual ranges, compared with similar structures retrieved from the Cambridge Crystallographic Database (Version 5.16, October 1998; Allen & Kennard, 1993). The finding of Hensen et al. (1998) that the C—N—C angle at the protonated N atom is significantly larger [C14—N1—C2 123.1 (4)°] than at the non-protonated N atom [C11—N12—C13 116.1 (3)°] is confirmed with this structure. The phenanthroline moiety is essentially planar and the chloride ion which is hydrogen bonded to N1 deviates by only 0.400 (4) Å from this plane. Three further short Cl···H contacts to aromatic hydrogen atoms are found, so that the Cl ion is approximately tetrahedrally coordinated. The phenanthroline moieties crystallize in stacks of exactly coplanar molecules, but two differently oriented stacks can be identified (Fig. 2). Although the layers in both stacks are formed approximately parallel to the ¯(202) plane, these two layers are tilted by an angle of 13.29 (3)° respective to each other.
The crystal structure of tris(1,10-phenanthrolin-1-ium) dichloride (hydrogen chloride) chloride chloroform solvate, (II) (Fig. 3), consists of three discrete protonated phenanthroline molecules, three chloride ions, a HCl molecule and a chloroform solvate. Bond lengths and angles of the phenanthrolinium units are in the usual ranges, compared with similar structures retrieved from the Cambridge Crystallographic Database (Version 5.16, October 1998; Allen & Kennard, 1993), and the C—N—C angles show the values in the same range as already found for (I). In contrast to other structures [C12H9N2+·NO3−·C12H8N2·H2O (Thevenet & Rodier, 1981), C24H17N4+·ClO4− (Maresca et al., 1989), C12H9N2+·C5H10I2NS2Te−·C12H8N2 and C12H9N2+·C5H10Br2NS2Te−·C12H8N2 (Krishnakumar et al., 1996) and C12H9N2+·Cl−·2C12H8N2 (Hensen et al., 1998)] the protonated phenanthrolines do not form a hydrogen bond to a second phenanthroline. Two phenanthrolinium molecules form a hydrogen bond to the same Cl− ion, namely Cl1. The third phenanthrolinium and the chloroform are both connected via hydrogen bonds to Cl2, whereas the third Cl− ion, Cl3, forms a hydrogen bond to the HCl molecule. It might be surprising that the Cl− is protonated and not an additional nitrogen of the phenanthrolines, because Cl− (pKa = −6) is a weaker base than phenanthroline (pKa = 4.48). However, a comparable structural motif was found 30 times in the Cambridge Structural Database (Version 5.16, October 1998; Allen & Kennard, 1993) with the following mean geometric parameters: Cl—H 1.3 (2) Å, H···Cl 2.1 (2) Å, Cl—H···Cl 166 (16)° Cl···Cl 3.3 (2) Å. Compared with the mean values extracted from the data base, the distances between the two Cl atoms and the hydrogen bridging them are more equal in (II), but since the determination of H atoms by means of X-ray structure analysis is a difficult chapter, we do not want to overemphasize this point. Furthermore, the Cl···Cl distance in (II) is slightly shorter than the mean distance in the database structures, but this might be partially due to the fact that (II) was measured at low temperature. The geometric parameters of all these hydrogen bonds are summarized in Table 4. The sum of the bond angles at all protonated nitrogen atoms in both structures is exactly 360°. Furthermore, the crystal packing is stabilized by several short Cl···H—C contacts. The phenanthrolinium molecules of (II) also form stacks. One is built up by exactly coplanar layers of the phenanthrolinium which is hydrogen bonded to the chloroform solvate. The other one is formed by intermittant layers [tilted by 5.1 (1)° against each other] of the remaining two phenanthroline units. Furthermore, there is a short Cl···Cl distance, Cl13···Cl2(x, 1 + y,z) 3.300 (1) Å.