Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680201735X/cf6202sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680201735X/cf6202Isup2.hkl |
CCDC reference: 198975
The title compound was obtained from Key Organics Ltd and crystals were grown from an ethanol solution.
All aromatic H atoms were included in the refinement, at calculated positions, as riding models, with C—H set to 0.95 Å. All water H atoms were initially located in a difference synthesis, but were then restrained to a distance of 0.83 Å, with riding displacement parameters. The remaining N-attached H atom was located in a difference synthesis; its positional and displacement parameters were refined. In the absence of significant anomalous scattering effects, the absolute structure can not be determined; Friedel pairs were merged.
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: PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.
C17H12N2·2H2O | Dx = 1.294 Mg m−3 |
Mr = 280.32 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4 | Cell parameters from 5959 reflections |
Hall symbol: I -4 | θ = 2.9–27.5° |
a = 24.758 (4) Å | µ = 0.09 mm−1 |
c = 4.6952 (9) Å | T = 150 K |
V = 2878.1 (8) Å3 | Block, colourless |
Z = 8 | 0.20 × 0.10 × 0.10 mm |
F(000) = 1184 |
Bruker–Nonius KappaCCD area-detector diffractometer | 1838 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 1205 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans | h = −32→32 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −32→32 |
Tmin = 0.983, Tmax = 0.991 | l = −6→5 |
8208 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0339P)2] where P = (Fo2 + 2Fc2)/3 |
1838 reflections | (Δ/σ)max < 0.001 |
206 parameters | Δρmax = 0.16 e Å−3 |
4 restraints | Δρmin = −0.20 e Å−3 |
C17H12N2·2H2O | Z = 8 |
Mr = 280.32 | Mo Kα radiation |
Tetragonal, I4 | µ = 0.09 mm−1 |
a = 24.758 (4) Å | T = 150 K |
c = 4.6952 (9) Å | 0.20 × 0.10 × 0.10 mm |
V = 2878.1 (8) Å3 |
Bruker–Nonius KappaCCD area-detector diffractometer | 1838 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 1205 reflections with I > 2σ(I) |
Tmin = 0.983, Tmax = 0.991 | Rint = 0.079 |
8208 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 4 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.16 e Å−3 |
1838 reflections | Δρmin = −0.20 e Å−3 |
206 parameters |
Geometry. Mean plane data ex SHELXL97 ########################### Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 17.1210 (0.0201) x + 0.9558 (0.0275) y + 3.3868 (0.0037) z = 1.0174 (0.0063) * 0.0098 (0.0017) N1 * −0.0048 (0.0020) C2 * −0.0034 (0.0020) C3 * 0.0065 (0.0020) C4 * −0.0015 (0.0018) C4A * −0.0065 (0.0017) C9B Rms deviation of fitted atoms = 0.0060 − 14.9176 (0.0246) x + 6.7625 (0.0306) y − 3.5209 (0.0037) z = 0.5527 (0.0111) Angle to previous plane (with approximate e.s.d.) = 18.73 (0.14) * −0.0032 (0.0019) C81 * 0.0019 (0.0019) C82 * 0.0023 (0.0020) C83 * 0.0003 (0.0021) C84 * −0.0012 (0.0022) C85 * −0.0001 (0.0021) C86 Rms deviation of fitted atoms = 0.0019 |
x | y | z | Uiso*/Ueq | ||
N1 | 0.04022 (9) | 0.26216 (9) | 0.0260 (5) | 0.0316 (6) | |
H1 | −0.0452 (12) | 0.2835 (12) | 0.426 (7) | 0.057 (11)* | |
C2 | 0.07861 (12) | 0.26321 (13) | −0.1727 (7) | 0.0399 (8) | |
H2 | 0.0899 | 0.2974 | −0.2429 | 0.050* | |
C3 | 0.10310 (11) | 0.21740 (13) | −0.2832 (7) | 0.0399 (8) | |
H3 | 0.1305 | 0.2205 | −0.4241 | 0.050* | |
C4 | 0.08743 (11) | 0.16766 (12) | −0.1869 (7) | 0.0366 (8) | |
H4 | 0.1042 | 0.1360 | −0.2592 | 0.046* | |
C4A | 0.04655 (10) | 0.16353 (11) | 0.0185 (6) | 0.0311 (7) | |
C5 | 0.02781 (11) | 0.11305 (11) | 0.1295 (7) | 0.0341 (7) | |
H5 | 0.0436 | 0.0805 | 0.0622 | 0.043* | |
C6 | −0.01200 (10) | 0.11030 (11) | 0.3284 (7) | 0.0332 (7) | |
H6 | −0.0237 | 0.0763 | 0.3986 | 0.041* | |
C6A | −0.03598 (10) | 0.15882 (10) | 0.4307 (6) | 0.0274 (7) | |
C7 | −0.07682 (10) | 0.17015 (10) | 0.6335 (6) | 0.0278 (7) | |
H7 | −0.0968 | 0.1443 | 0.7396 | 0.035* | |
C8 | −0.08244 (10) | 0.22546 (10) | 0.6493 (6) | 0.0263 (6) | |
N9 | −0.04610 (9) | 0.24847 (10) | 0.4606 (5) | 0.0270 (6) | |
C9A | −0.01770 (10) | 0.20845 (11) | 0.3252 (6) | 0.0268 (6) | |
C9B | 0.02350 (10) | 0.21262 (11) | 0.1197 (6) | 0.0277 (7) | |
C81 | −0.11683 (10) | 0.25757 (11) | 0.8336 (6) | 0.0286 (7) | |
C82 | −0.10611 (11) | 0.31220 (11) | 0.8917 (7) | 0.0366 (8) | |
H82 | −0.0768 | 0.3298 | 0.7999 | 0.046* | |
C83 | −0.16051 (11) | 0.23337 (12) | 0.9706 (7) | 0.0359 (8) | |
H83 | −0.1687 | 0.1966 | 0.9331 | 0.045* | |
C84 | −0.13813 (13) | 0.34066 (13) | 1.0825 (7) | 0.0461 (9) | |
H84 | −0.1305 | 0.3776 | 1.1209 | 0.058* | |
C85 | −0.18091 (14) | 0.31576 (14) | 1.2163 (7) | 0.0487 (9) | |
H85 | −0.2027 | 0.3354 | 1.3468 | 0.061* | |
C86 | −0.19216 (12) | 0.26215 (14) | 1.1607 (7) | 0.0447 (8) | |
H86 | −0.2217 | 0.2450 | 1.2530 | 0.056* | |
O1W | 0.00569 (10) | 0.35901 (8) | 0.2749 (5) | 0.0458 (6) | |
H1W | 0.0192 (12) | 0.3296 (9) | 0.205 (7) | 0.057* | |
H2W | 0.0023 (14) | 0.3797 (11) | 0.136 (5) | 0.057* | |
O2W | 0.00206 (9) | 0.41992 (8) | −0.2372 (5) | 0.0424 (6) | |
H3W | 0.0275 (9) | 0.4414 (10) | −0.228 (8) | 0.053* | |
H4W | 0.0047 (14) | 0.4002 (11) | −0.384 (5) | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0285 (13) | 0.0382 (14) | 0.0281 (14) | −0.0063 (11) | −0.0052 (12) | 0.0025 (12) |
C2 | 0.0356 (17) | 0.0506 (19) | 0.0335 (19) | −0.0082 (15) | −0.0038 (17) | 0.0070 (17) |
C3 | 0.0285 (16) | 0.060 (2) | 0.0311 (17) | −0.0034 (15) | 0.0030 (15) | −0.0033 (17) |
C4 | 0.0293 (16) | 0.0493 (19) | 0.0312 (19) | 0.0022 (14) | −0.0051 (15) | −0.0096 (17) |
C4A | 0.0242 (15) | 0.0392 (17) | 0.0298 (17) | 0.0035 (13) | −0.0083 (15) | −0.0021 (15) |
C5 | 0.0300 (16) | 0.0323 (16) | 0.040 (2) | 0.0049 (13) | −0.0077 (16) | −0.0061 (16) |
C6 | 0.0330 (16) | 0.0279 (15) | 0.0386 (18) | −0.0009 (13) | −0.0027 (16) | 0.0012 (15) |
C6A | 0.0258 (15) | 0.0285 (15) | 0.0278 (17) | −0.0005 (12) | −0.0075 (13) | −0.0028 (13) |
C7 | 0.0272 (15) | 0.0280 (15) | 0.0283 (17) | −0.0035 (12) | −0.0008 (14) | 0.0025 (14) |
C8 | 0.0233 (14) | 0.0300 (15) | 0.0255 (15) | −0.0001 (12) | −0.0073 (14) | 0.0009 (14) |
N9 | 0.0285 (13) | 0.0257 (13) | 0.0268 (14) | −0.0011 (11) | −0.0025 (11) | 0.0007 (12) |
C9A | 0.0227 (14) | 0.0297 (15) | 0.0278 (15) | 0.0018 (12) | −0.0074 (13) | −0.0013 (14) |
C9B | 0.0245 (14) | 0.0363 (16) | 0.0222 (16) | −0.0025 (12) | −0.0088 (13) | 0.0001 (14) |
C81 | 0.0308 (15) | 0.0324 (16) | 0.0227 (16) | 0.0042 (13) | −0.0076 (14) | −0.0013 (14) |
C82 | 0.0401 (17) | 0.0352 (16) | 0.0345 (19) | 0.0071 (14) | −0.0070 (16) | 0.0008 (15) |
C83 | 0.0327 (16) | 0.0377 (17) | 0.0371 (19) | 0.0038 (13) | −0.0027 (15) | −0.0004 (16) |
C84 | 0.058 (2) | 0.0399 (19) | 0.040 (2) | 0.0129 (17) | −0.0138 (19) | −0.0109 (17) |
C85 | 0.050 (2) | 0.059 (2) | 0.037 (2) | 0.0256 (19) | −0.0044 (19) | −0.0102 (18) |
C86 | 0.0387 (18) | 0.062 (2) | 0.033 (2) | 0.0122 (16) | 0.0023 (16) | −0.0013 (19) |
O1W | 0.0617 (15) | 0.0379 (14) | 0.0379 (14) | 0.0026 (12) | −0.0016 (12) | −0.0008 (11) |
O2W | 0.0496 (14) | 0.0365 (14) | 0.0412 (13) | −0.0047 (10) | 0.0001 (12) | −0.0056 (12) |
N1—C2 | 1.332 (4) | C8—C81 | 1.451 (4) |
N1—C9B | 1.367 (3) | N9—C9A | 1.371 (3) |
C2—C3 | 1.387 (4) | N9—H1 | 0.88 (3) |
C2—H2 | 0.95 | C9A—C9B | 1.408 (4) |
C3—C4 | 1.368 (4) | C81—C83 | 1.394 (4) |
C3—H3 | 0.95 | C81—C82 | 1.405 (4) |
C4—C4A | 1.402 (4) | C82—C84 | 1.388 (4) |
C4—H4 | 0.95 | C82—H82 | 0.95 |
C4A—C9B | 1.424 (4) | C83—C86 | 1.385 (4) |
C4A—C5 | 1.432 (4) | C83—H83 | 0.95 |
C5—C6 | 1.359 (4) | C84—C85 | 1.377 (4) |
C5—H5 | 0.95 | C84—H84 | 0.95 |
C6—C6A | 1.423 (4) | C85—C86 | 1.381 (4) |
C6—H6 | 0.95 | C85—H85 | 0.95 |
C6A—C9A | 1.400 (4) | C86—H86 | 0.95 |
C6A—C7 | 1.417 (4) | O1W—H1W | 0.865 (17) |
C7—C8 | 1.378 (3) | O1W—H2W | 0.833 (18) |
C7—H7 | 0.95 | O2W—H3W | 0.825 (17) |
C8—N9 | 1.386 (3) | O2W—H4W | 0.849 (18) |
C2—N1—C9B | 117.3 (2) | C9A—N9—H1 | 128 (2) |
N1—C2—C3 | 123.9 (3) | C8—N9—H1 | 123 (2) |
N1—C2—H2 | 118.0 | N9—C9A—C6A | 107.7 (2) |
C3—C2—H2 | 118.0 | N9—C9A—C9B | 129.5 (3) |
C4—C3—C2 | 119.2 (3) | C6A—C9A—C9B | 122.8 (3) |
C4—C3—H3 | 120.4 | N1—C9B—C9A | 120.4 (2) |
C2—C3—H3 | 120.4 | N1—C9B—C4A | 122.5 (2) |
C3—C4—C4A | 119.8 (3) | C9A—C9B—C4A | 117.2 (3) |
C3—C4—H4 | 120.1 | C83—C81—C82 | 118.1 (3) |
C4A—C4—H4 | 120.1 | C83—C81—C8 | 119.7 (2) |
C4—C4A—C9B | 117.2 (3) | C82—C81—C8 | 122.2 (3) |
C4—C4A—C5 | 123.2 (3) | C84—C82—C81 | 120.4 (3) |
C9B—C4A—C5 | 119.6 (3) | C84—C82—H82 | 119.8 |
C6—C5—C4A | 121.9 (3) | C81—C82—H82 | 119.8 |
C6—C5—H5 | 119.0 | C86—C83—C81 | 121.0 (3) |
C4A—C5—H5 | 119.0 | C86—C83—H83 | 119.5 |
C5—C6—C6A | 119.5 (3) | C81—C83—H83 | 119.5 |
C5—C6—H6 | 120.3 | C85—C84—C82 | 120.4 (3) |
C6A—C6—H6 | 120.3 | C85—C84—H84 | 119.8 |
C9A—C6A—C7 | 107.1 (2) | C82—C84—H84 | 119.8 |
C9A—C6A—C6 | 119.1 (3) | C86—C85—C84 | 119.9 (3) |
C7—C6A—C6 | 133.7 (3) | C86—C85—H85 | 120.0 |
C8—C7—C6A | 107.8 (2) | C84—C85—H85 | 120.0 |
C8—C7—H7 | 126.1 | C85—C86—C83 | 120.2 (3) |
C6A—C7—H7 | 126.1 | C85—C86—H86 | 119.9 |
C7—C8—N9 | 108.0 (2) | C83—C86—H86 | 119.9 |
C7—C8—C81 | 129.5 (3) | H1W—O1W—H2W | 105 (3) |
N9—C8—C81 | 122.5 (2) | H3W—O2W—H4W | 111 (3) |
C9A—N9—C8 | 109.4 (2) | ||
C9B—N1—C2—C3 | −1.6 (4) | C2—N1—C9B—C9A | −178.7 (2) |
N1—C2—C3—C4 | 0.3 (5) | C2—N1—C9B—C4A | 1.7 (4) |
C2—C3—C4—C4A | 0.8 (4) | N9—C9A—C9B—N1 | −0.5 (4) |
C3—C4—C4A—C9B | −0.6 (4) | C6A—C9A—C9B—N1 | −179.3 (2) |
C3—C4—C4A—C5 | 179.9 (3) | N9—C9A—C9B—C4A | 179.0 (3) |
C4—C4A—C5—C6 | −179.9 (3) | C6A—C9A—C9B—C4A | 0.2 (4) |
C9B—C4A—C5—C6 | 0.6 (4) | C4—C4A—C9B—N1 | −0.7 (4) |
C4A—C5—C6—C6A | 0.0 (4) | C5—C4A—C9B—N1 | 178.9 (2) |
C5—C6—C6A—C9A | −0.5 (4) | C4—C4A—C9B—C9A | 179.8 (2) |
C5—C6—C6A—C7 | −179.3 (3) | C5—C4A—C9B—C9A | −0.7 (4) |
C9A—C6A—C7—C8 | −0.3 (3) | C7—C8—C81—C83 | −17.8 (4) |
C6—C6A—C7—C8 | 178.6 (3) | N9—C8—C81—C83 | 165.7 (3) |
C6A—C7—C8—N9 | 0.1 (3) | C7—C8—C81—C82 | 158.8 (3) |
C6A—C7—C8—C81 | −176.8 (3) | N9—C8—C81—C82 | −17.7 (4) |
C7—C8—N9—C9A | 0.2 (3) | C83—C81—C82—C84 | 0.6 (4) |
C81—C8—N9—C9A | 177.3 (2) | C8—C81—C82—C84 | −176.1 (3) |
C8—N9—C9A—C6A | −0.4 (3) | C82—C81—C83—C86 | −0.6 (4) |
C8—N9—C9A—C9B | −179.3 (3) | C8—C81—C83—C86 | 176.2 (3) |
C7—C6A—C9A—N9 | 0.4 (3) | C81—C82—C84—C85 | −0.2 (4) |
C6—C6A—C9A—N9 | −178.7 (2) | C82—C84—C85—C86 | −0.1 (5) |
C7—C6A—C9A—C9B | 179.5 (2) | C84—C85—C86—C83 | 0.0 (5) |
C6—C6A—C9A—C9B | 0.3 (4) | C81—C83—C86—C85 | 0.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H1···O1W | 0.88 (3) | 2.36 (3) | 3.145 (3) | 148 (3) |
O2W—H3W···O2Wi | 0.83 (2) | 1.99 (2) | 2.807 (3) | 168 (3) |
O2W—H4W···O1Wii | 0.85 (2) | 1.90 (2) | 2.744 (3) | 175 (3) |
O1W—H1W···N1 | 0.87 (2) | 1.94 (2) | 2.801 (3) | 172 (3) |
O1W—H2W···O2W | 0.83 (2) | 2.02 (2) | 2.840 (3) | 170 (3) |
Symmetry codes: (i) −y+1/2, x+1/2, −z−1/2; (ii) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C17H12N2·2H2O |
Mr | 280.32 |
Crystal system, space group | Tetragonal, I4 |
Temperature (K) | 150 |
a, c (Å) | 24.758 (4), 4.6952 (9) |
V (Å3) | 2878.1 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.983, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8208, 1838, 1205 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.093, 1.05 |
No. of reflections | 1838 |
No. of parameters | 206 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.20 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H1···O1W | 0.88 (3) | 2.36 (3) | 3.145 (3) | 148 (3) |
O2W—H3W···O2Wi | 0.83 (2) | 1.99 (2) | 2.807 (3) | 168 (3) |
O2W—H4W···O1Wii | 0.85 (2) | 1.90 (2) | 2.744 (3) | 175 (3) |
O1W—H1W···N1 | 0.87 (2) | 1.94 (2) | 2.801 (3) | 172 (3) |
O1W—H2W···O2W | 0.83 (2) | 2.02 (2) | 2.840 (3) | 170 (3) |
Symmetry codes: (i) −y+1/2, x+1/2, −z−1/2; (ii) x, y, z−1. |
The title compound, (I), was prepared from a two-stage procedure starting with the reaction of 8-hydrazinoquinoline dihydrochloride hydrate and acetophenone, followed by the cyclization of the intermediate product (E)-2-acetylbenzene-8-quinonylhydrozone. A structural example of this intermediate, as the thiophene derivative, has been previously published (Lynch & McClenaghan, 2001a). Furthermore, the structure of 2-(4-pyridyl)pyrrolo[3,2-h]quinoline, a product analogous to the title compound, has also been reported (Lynch & McClenaghan, 2001b). We are currently studying the structural aspects of derivatives of both 8-quinonylhydrozone and pyrrolo[3,2-h]quinoline before studying their potential as metal-chelating agents.
The molecule of (I) (Fig. 1) is essentially flat, with the phenyl ring being inclined at 18.7 (1)° to the plane of the pyrrolo[2,3-h]quinoline moiety. It crystallizes with two water molecules per asymmetric unit. One O—H site from one water molecule resides in an hydrogen-bonded triangular arrangement with both pyrrolo-NH and quinoline-N sites. The other O—H site, in conjunction with the second water molecule and their symmetry-related analogues, then forms an hydrogen-bonded "Chinese lantern" arrangement (Fig. 2).