Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803002009/wn6136sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803002009/wn6136Isup2.hkl |
CCDC reference: 204720
The crystals of (I) were obtained as the result of the attempted recrystallization from moist, i.e. not specifically anhydrous, ethanol of the product obtained by reaction, over an extended period in ethanol solution, of dimethyltin dibromide and 1,10-phenanthroline-5,6-dione. The adventitious water has clearly brought about protonation of the intrinsically extremely basic dione ligand to provide the cation, and a degree of hydrolysis of the tin compound to provide the bromide counter-anion.
All H atoms were placed in calculated positions, with C—H and N—H distances of 0.95 and 0.88 Å, respectively, and were refined with a riding model, with Uiso values equal to 1.2Ueq of the non-H atom to which they are attached.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 1990).
C12H7N2O2+·Br− | Dx = 1.752 Mg m−3 |
Mr = 291.11 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 10916 reflections |
a = 14.2379 (3) Å | θ = 2.9–27.5° |
b = 6.2978 (1) Å | µ = 3.71 mm−1 |
c = 12.3110 (3) Å | T = 120 K |
V = 1103.90 (4) Å3 | Block, orange |
Z = 4 | 0.30 × 0.28 × 0.08 mm |
F(000) = 576 |
Enraf-Nonius KappaCCD area-detector diffractometer | 1376 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1259 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans | h = −18→18 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −8→8 |
Tmin = 0.248, Tmax = 0.283 | l = −15→15 |
15272 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0421P)2 + 0.8806P] where P = (Fo2 + 2Fc2)/3 |
1376 reflections | (Δ/σ)max < 0.001 |
103 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
C12H7N2O2+·Br− | V = 1103.90 (4) Å3 |
Mr = 291.11 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 14.2379 (3) Å | µ = 3.71 mm−1 |
b = 6.2978 (1) Å | T = 120 K |
c = 12.3110 (3) Å | 0.30 × 0.28 × 0.08 mm |
Enraf-Nonius KappaCCD area-detector diffractometer | 1376 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 1259 reflections with I > 2σ(I) |
Tmin = 0.248, Tmax = 0.283 | Rint = 0.052 |
15272 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.69 e Å−3 |
1376 reflections | Δρmin = −0.59 e Å−3 |
103 parameters |
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 | ||
Br1 | 0.28493 (2) | 0.2500 | 0.51188 (2) | 0.02273 (13) | |
O1 | 0.33230 (16) | 0.2500 | −0.12867 (18) | 0.0322 (5) | |
O2 | 0.35374 (17) | 0.2500 | 0.09181 (19) | 0.0397 (6) | |
N1 | 0.00332 (17) | 0.2500 | −0.0857 (2) | 0.0201 (5) | |
H1N | −0.0445 | 0.2500 | −0.0404 | 0.024* | |
N2 | 0.02030 (18) | 0.2500 | 0.1310 (2) | 0.0229 (5) | |
C1 | −0.0144 (2) | 0.2500 | −0.1923 (2) | 0.0250 (6) | |
H1 | −0.0775 | 0.2500 | −0.2175 | 0.030* | |
C2 | 0.0585 (2) | 0.2500 | −0.2656 (2) | 0.0272 (7) | |
H2 | 0.0465 | 0.2500 | −0.3415 | 0.033* | |
C3 | 0.1499 (2) | 0.2500 | −0.2268 (2) | 0.0246 (6) | |
H3 | 0.2012 | 0.2500 | −0.2761 | 0.030* | |
C4 | 0.1664 (2) | 0.2500 | −0.1149 (2) | 0.0208 (6) | |
C5 | 0.2640 (2) | 0.2500 | −0.0705 (2) | 0.0236 (6) | |
C6 | 0.2757 (2) | 0.2500 | 0.0540 (3) | 0.0258 (7) | |
C7 | 0.1897 (2) | 0.2500 | 0.1221 (2) | 0.0215 (6) | |
C8 | 0.1952 (2) | 0.2500 | 0.2350 (2) | 0.0256 (7) | |
H8 | 0.2545 | 0.2500 | 0.2704 | 0.031* | |
C9 | 0.1131 (2) | 0.2500 | 0.2946 (2) | 0.0276 (7) | |
H9 | 0.1150 | 0.2500 | 0.3718 | 0.033* | |
C10 | 0.0275 (2) | 0.2500 | 0.2400 (2) | 0.0263 (7) | |
H10 | −0.0286 | 0.2500 | 0.2817 | 0.032* | |
C11 | 0.1004 (2) | 0.2500 | 0.0749 (2) | 0.0189 (6) | |
C12 | 0.0906 (2) | 0.2500 | −0.0442 (2) | 0.0191 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0238 (2) | 0.0269 (2) | 0.01745 (18) | 0.000 | −0.00096 (10) | 0.000 |
O1 | 0.0252 (12) | 0.0466 (14) | 0.0247 (11) | 0.000 | 0.0065 (9) | 0.000 |
O2 | 0.0241 (12) | 0.0686 (18) | 0.0263 (12) | 0.000 | −0.0046 (10) | 0.000 |
N1 | 0.0218 (12) | 0.0208 (12) | 0.0176 (11) | 0.000 | 0.0003 (9) | 0.000 |
N2 | 0.0264 (13) | 0.0248 (13) | 0.0175 (12) | 0.000 | 0.0040 (10) | 0.000 |
C1 | 0.0295 (16) | 0.0244 (15) | 0.0210 (14) | 0.000 | −0.0081 (12) | 0.000 |
C2 | 0.0385 (19) | 0.0288 (16) | 0.0143 (13) | 0.000 | −0.0057 (12) | 0.000 |
C3 | 0.0316 (16) | 0.0257 (15) | 0.0165 (14) | 0.000 | 0.0025 (12) | 0.000 |
C4 | 0.0232 (15) | 0.0223 (14) | 0.0169 (13) | 0.000 | 0.0003 (11) | 0.000 |
C5 | 0.0240 (15) | 0.0286 (15) | 0.0184 (14) | 0.000 | 0.0023 (11) | 0.000 |
C6 | 0.0222 (15) | 0.0345 (17) | 0.0208 (15) | 0.000 | −0.0013 (11) | 0.000 |
C7 | 0.0256 (14) | 0.0228 (14) | 0.0160 (13) | 0.000 | −0.0007 (11) | 0.000 |
C8 | 0.0304 (17) | 0.0276 (16) | 0.0187 (15) | 0.000 | −0.0042 (11) | 0.000 |
C9 | 0.0413 (18) | 0.0279 (15) | 0.0136 (13) | 0.000 | 0.0001 (12) | 0.000 |
C10 | 0.0350 (18) | 0.0264 (15) | 0.0174 (14) | 0.000 | 0.0075 (12) | 0.000 |
C11 | 0.0238 (14) | 0.0179 (13) | 0.0151 (12) | 0.000 | 0.0005 (10) | 0.000 |
C12 | 0.0229 (14) | 0.0179 (13) | 0.0165 (12) | 0.000 | −0.0022 (11) | 0.000 |
O1—C5 | 1.208 (4) | C4—C12 | 1.386 (4) |
O2—C6 | 1.205 (4) | C4—C5 | 1.493 (4) |
N1—C1 | 1.337 (4) | C5—C6 | 1.542 (4) |
N1—C12 | 1.344 (4) | C6—C7 | 1.485 (4) |
N1—H1N | 0.8800 | C7—C8 | 1.392 (4) |
N2—C11 | 1.334 (4) | C7—C11 | 1.397 (4) |
N2—C10 | 1.345 (4) | C8—C9 | 1.381 (5) |
C1—C2 | 1.376 (5) | C8—H8 | 0.9500 |
C1—H1 | 0.9500 | C9—C10 | 1.392 (5) |
C2—C3 | 1.386 (5) | C9—H9 | 0.9500 |
C2—H2 | 0.9500 | C10—H10 | 0.9500 |
C3—C4 | 1.397 (4) | C11—C12 | 1.473 (4) |
C3—H3 | 0.9500 | ||
C1—N1—C12 | 123.2 (3) | O2—C6—C5 | 119.0 (3) |
C1—N1—H1N | 118.4 | C7—C6—C5 | 118.2 (2) |
C12—N1—H1N | 118.4 | C8—C7—C11 | 117.9 (3) |
C11—N2—C10 | 116.8 (3) | C8—C7—C6 | 121.1 (3) |
N1—C1—C2 | 120.1 (3) | C11—C7—C6 | 121.0 (3) |
N1—C1—H1 | 120.0 | C9—C8—C7 | 118.8 (3) |
C2—C1—H1 | 120.0 | C9—C8—H8 | 120.6 |
C1—C2—C3 | 118.9 (3) | C7—C8—H8 | 120.6 |
C1—C2—H2 | 120.6 | C8—C9—C10 | 119.0 (3) |
C3—C2—H2 | 120.6 | C8—C9—H9 | 120.5 |
C2—C3—C4 | 119.8 (3) | C10—C9—H9 | 120.5 |
C2—C3—H3 | 120.1 | N2—C10—C9 | 123.3 (3) |
C4—C3—H3 | 120.1 | N2—C10—H10 | 118.3 |
C12—C4—C3 | 119.2 (3) | C9—C10—H10 | 118.3 |
C12—C4—C5 | 119.6 (3) | N2—C11—C7 | 124.2 (3) |
C3—C4—C5 | 121.1 (3) | N2—C11—C12 | 115.8 (2) |
O1—C5—C4 | 122.2 (3) | C7—C11—C12 | 120.0 (3) |
O1—C5—C6 | 120.1 (3) | N1—C12—C4 | 118.8 (3) |
C4—C5—C6 | 117.7 (2) | N1—C12—C11 | 117.8 (2) |
O2—C6—C7 | 122.8 (3) | C4—C12—C11 | 123.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Br1i | 0.88 | 2.45 | 3.239 (2) | 149 |
C1—H1···O1ii | 0.95 | 2.29 | 3.102 (4) | 143 |
C3—H3···Br1iii | 0.95 | 2.87 | 3.748 (3) | 154 |
C10—H10···O2i | 0.95 | 2.29 | 3.227 (4) | 170 |
C8—H8···Br1 | 0.95 | 3.00 | 3.640 (3) | 126 |
C9—H9···Br1 | 0.95 | 2.97 | 3.625 (3) | 127 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z−1/2; (iii) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C12H7N2O2+·Br− |
Mr | 291.11 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 120 |
a, b, c (Å) | 14.2379 (3), 6.2978 (1), 12.3110 (3) |
V (Å3) | 1103.90 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.71 |
Crystal size (mm) | 0.30 × 0.28 × 0.08 |
Data collection | |
Diffractometer | Enraf-Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.248, 0.283 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15272, 1376, 1259 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.077, 1.11 |
No. of reflections | 1376 |
No. of parameters | 103 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.69, −0.59 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97 and PLATON (Spek, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Br1i | 0.88 | 2.45 | 3.239 (2) | 149 |
C1—H1···O1ii | 0.95 | 2.29 | 3.102 (4) | 143 |
C3—H3···Br1iii | 0.95 | 2.87 | 3.748 (3) | 154 |
C10—H10···O2i | 0.95 | 2.29 | 3.227 (4) | 170 |
C8—H8···Br1 | 0.95 | 3.00 | 3.640 (3) | 126 |
C9—H9···Br1 | 0.95 | 2.97 | 3.625 (3) | 127 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z−1/2; (iii) x, y, z−1. |
Hpdona | pdonb | ||
Molecule 1 | Molecule 2 | ||
C12—N1 | 1.344 (4) | 1.343 (3) | 1.339 (3) |
N1—C1 | 1.337 (4) | 1.336 (3) | 1.336 (3) |
C1—C2 | 1.376 (5) | 1.379 (4) | 1.369 (4) |
C2—C3 | 1.386 (5) | 1.370 (4) | 1.371 (4) |
C3—C4 | 1.397 (4) | 1.391 (4) | 1.385 (4) |
C4—C5 | 1.493 (4) | 1.476 (4) | 1.477 (4) |
C4—C12 | 1.386 (4) | 1.395 (4) | 1.402 (3) |
C5—C6 | 1.542 (4) | 1.529 (4) | 1.539 (4) |
C5—O1 | 1.208 (4) | 1.214 (3) | 1.207 (3) |
C6—C7 | 1.485 (4) | 1.476 (4) | 1.469 (4) |
C6—O2 | 1.205 (4) | 1.208 (3) | 1.209 (3) |
C7—C8 | 1.392 (4) | 1.391 (4) | 1.389 (4) |
C7—C11 | 1.397 (4) | 1.401 (3) | 1.393 (4) |
C8—C9 | 1.381 (5) | 1.371 (4) | 1.365 (4) |
C9—C10 | 1.392 (5) | 1.369 (4) | 1.376 (4) |
C10—N2 | 1.345 (4) | 1.339 (3) | 1.338 (3) |
N2—C11 | 1.334 (4) | 1.339 (3) | 1.343 (3) |
C11—C12 | 1.473 (4) | 1.489 (4) | 1.494 (3) |
C12—N1—C1c | 123.2 (3) | 116.7 (2) | 116.7 (2) |
N1—C1—C2c | 120.1 (3) | 125.0 (2) | 125.2 (3) |
C1—C2—C3 | 118.9 (3) | 118.0 (3) | 117.9 (3) |
C2—C3—C4 | 119.8 (3) | 118.8 (3) | 119.3 (2) |
C3—C4—C5 | 121.1 (3) | 123.1 (3) | 120.2 (2) |
C3—C4—C12 | 119.2 (3) | 119.2 (2) | 118.6 (2) |
C5—C4—C12 | 119.6 (3) | 120.8 (2) | 121.2 (2) |
C4—C5—C6 | 117.7 (2) | 118.1 (2) | 117.9 (2) |
C4—C5—O1 | 122.2 (3) | 123.1 (3) | 123.0 (2) |
C6—C5—O1 | 120.1 (3) | 118.8 (2) | 119.1 (2) |
C5—C6—C7 | 118.2 (2) | 118.2 (2) | 117.9 (2) |
C5—C6—O2 | 119.0 (3) | 119.5 (2) | 118.9 (2) |
C7—C6—O2 | 122.8 (3) | 122.3 (2) | 123.3 (3) |
C6—C7—C8 | 121.1 (3) | 120.0 (2) | 119.4 (2) |
C6—C7—C11 | 121.0 (3) | 121.0 (2) | 121.8 (2) |
C8—C7—C11 | 117.9 (3) | 119.0 (2) | 118.9 (2) |
C7—C8—C9 | 118.8 (3) | 118.6 (2) | 119.3 (3) |
C8—C9—C10 | 119.0 (3) | 118.5 (3) | 118.3 (3) |
C9—C10—N2 | 123.3 (3) | 124.7 (3) | 124.2 (2) |
C10—N2—C11 | 116.8 (3) | 117.0 (2) | 117.3 (2) |
N2—C11—C12 | 115.8 (2) | 117.4 (2) | 117.3 (2) |
N2—C11—C7 | 124.2 (3) | 122.1 (2) | 122.1 (2) |
C12—C11—C7 | 120.0 (3) | 120.6 (2) | 120.6 (2) |
C11—C12—N1 | 117.8 (2) | 116.6 (2) | 117.0 (2) |
C11—C12—C4 | 123.5 (3) | 121.2 (2) | 120.6 (2) |
N1—C12—C4c | 118.8 (3) | 122.2 (2) | 122.4 (2) |
O1—C5—C6—O2 | 0 | 3.4 (4) | -0.6 (4) |
Notes: (q) atom designations as for Hpdon in Fig. 1; (b) values obtained with PLATON (Spek, 1990) from CSD CIF data (MEJWED; Calderazzo et al., 1999); (c) entries showing particularly marked differences between Hpdon and pdon. |
A search of the current issue (Version 24) of the Cambridge Structural Database (Allen, 2002) reveals 144 structures containing the well known 1,10-phenanthroline (C12H8N2, phen) moiety and a further 50 containing the related mono-N-protonated species (C12H9N2+, Hphen). In contrast, only three entries other than that corresponding to the ligand itself (MEJWED; Calderazzo et al., 1999) are found for complexes containing the related 1,10-phenanthroline-5,6-dione (C12H6N2O2, pdon), and none at all for the corresponding N-protonated cation (C12H7N2O2+, Hpdon). This is the basis for the claimed novelty of the structure of the compound, (I), described here, which is simply the Hpdon cation with a bromide counter-anion, i.e (Hpdon)Br, (I).
The asymmetric unit and atom-labelling scheme for (I) are shown in Fig. 1. A l l of the atoms lie on a crystallographic mirror plane. As a consequence, the cation, Hpdon, is completely planar. The comparatively high Ueq values of O1 and O2, ~1.5Ueq of the other non-H atoms of the cation, suggests that the crystallographically induced planarity introduces a degree of simplification into the structural model because the planarity completely precludes displacement of O1 and O2 from the plane of the cation which might relieve any strain caused by intramolecular steric effects. However, the O1—C5—C6—O2 torsion angles of 3.4 (4) and −0.6 (4)° for the unconstrained unprotonated pdon molecules in Table 1 suggest that the displacement is likely to be small and the consequent degree of simplification negligible.
The remaining bond lengths and angles in Table 1 show that protonation to form the cation has no significant effect upon the bond lengths and that the only significant differences in the geometries of Hpdon and pdon are the angles at protonated atom N1 and the adjacent atoms C1 and C12. Comparison of the molecular geometries of the analogous 1,10-phenanthroline species, phen (OPENAN; Nishigaki et al., 1978) and (Hphen)Cl (CUZDIK; Hensen et al., 2000), shows precisely the same effect, which is therefore presumed to be likely to occur in other N-aryl heterocyclic systems.
Because all of the atoms lie on crystallographic mirror planes of the space group Pnma, the constituent ions of (I) are found in well defined layers parallel to (010) (Fig. 2), b/2 [3.14890 (5) Å] apart. As shown in Fig. 2 and Table 2, a variety of N—H···Br, C—H···O and C—H···Br contacts occur within each layer. There are, however, no similar interlayer contacts. The layers, stacked in the direction of b, are related one to the next by the operation of crystallographic centres of symmetry (Fig. 3), in such a way that the cations overlap Br in adjacent layers but not, to any significant extent, one another. That is, there is no π–π interaction between the layers, presumably because the interlayer separation (see above) is too small to accommodate it. Also discernible in Fig. 3 are channels parallel to b, centred on row vectors 1/2,y,0 and 0,y,1/2, which, being unoccupied, account for the void space of 46.7 Å3 per cell, ~4.2%, noted in the checkCIF report.