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The asymmetric unit of the title compound, 2C
9H
8N
+·CuCl
42−·2H
2O, comprises one quinolinium cation, one water molecule and one-half of the CuCl
42− anion with the other half generated by crystallographic twofold symmetry. The water molecules are linked to the anions through O—H
Cl hydrogen bonds to form two-dimensional molecular networks parallel to (110). The cations are arranged between two networks in parallel stacks. The N—H
O, C—H
O and C—H
Cl intermolecular hydrogen bonds link the cations and the anion networks to form a three-dimensional network.
Supporting information
CCDC reference: 198304
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- Disorder in solvent or counterion
- R factor = 0.037
- wR factor = 0.100
- Data-to-parameter ratio = 15.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 40.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was obtained from Key Organics Ltd and crystals were grown from dil. HCl solution.
The C-bound H atoms were included in the refinement, at calculated positions, as riding models with C—H set to 0.95 Å. All H atoms involved in the H-bonding network were located from a difference map and both positional and isotropic displacement parameters were refined. The Cu—Cl bond lengths for the two minor Cl atom sites were restrained to be the same length as their corresponding major sites.
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: Please provide; software used to prepare material for publication: SHELXL97.
Bisquinolinium tetrachlorocopper(II) dihydrate
top
Crystal data top
2C9H8N+·Cl4Cu2+·2H2O | F(000) = 1020 |
Mr = 501.70 | Dx = 1.595 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5373 reflections |
a = 11.815 (2) Å | θ = 2.9–27.5° |
b = 9.837 (2) Å | µ = 1.57 mm−1 |
c = 18.311 (4) Å | T = 150 K |
β = 101.05 (3)° | Plate, yellow |
V = 2088.7 (7) Å3 | 0.38 × 0.36 × 0.04 mm |
Z = 4 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 2330 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2001 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −14→15 |
Absorption correction: multi-scan SORTAV (Blessing, 1995) | k = −11→12 |
Tmin = 0.586, Tmax = 0.940 | l = −23→23 |
7197 measured reflections | |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0588P)2 + 1.3968P] where P = (Fo2 + 2Fc2)/3 |
2330 reflections | (Δ/σ)max < 0.001 |
153 parameters | Δρmax = 0.47 e Å−3 |
25 restraints | Δρmin = −0.62 e Å−3 |
Crystal data top
2C9H8N+·Cl4Cu2+·2H2O | V = 2088.7 (7) Å3 |
Mr = 501.70 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.815 (2) Å | µ = 1.57 mm−1 |
b = 9.837 (2) Å | T = 150 K |
c = 18.311 (4) Å | 0.38 × 0.36 × 0.04 mm |
β = 101.05 (3)° | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 2330 independent reflections |
Absorption correction: multi-scan SORTAV (Blessing, 1995) | 2001 reflections with I > 2σ(I) |
Tmin = 0.586, Tmax = 0.940 | Rint = 0.044 |
7197 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 25 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.47 e Å−3 |
2330 reflections | Δρmin = −0.62 e Å−3 |
153 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1W | 0.35224 (17) | 0.0825 (3) | 0.22398 (9) | 0.0434 (4) | |
H1W | 0.282 (4) | 0.102 (4) | 0.226 (2) | 0.071 (11)* | |
H2W | 0.353 (4) | 0.002 (5) | 0.219 (3) | 0.101 (17)* | |
N1 | 0.43836 (17) | 0.14724 (17) | 0.10047 (11) | 0.0307 (4) | |
H1 | 0.413 (2) | 0.129 (2) | 0.1358 (16) | 0.030 (7)* | |
C2 | 0.5426 (2) | 0.1999 (2) | 0.10954 (12) | 0.0348 (5) | |
H2 | 0.5849 | 0.2164 | 0.1583 | 0.044* | |
C3 | 0.5912 (2) | 0.2317 (2) | 0.04833 (13) | 0.0345 (5) | |
H3 | 0.6665 | 0.2694 | 0.0550 | 0.043* | |
C4 | 0.52945 (19) | 0.2080 (2) | −0.02164 (12) | 0.0324 (5) | |
H4 | 0.5619 | 0.2295 | −0.0638 | 0.040* | |
C5 | 0.3486 (2) | 0.1266 (2) | −0.10220 (12) | 0.0341 (5) | |
H5 | 0.3774 | 0.1466 | −0.1460 | 0.043* | |
C6 | 0.2413 (2) | 0.0742 (2) | −0.10761 (13) | 0.0384 (5) | |
H6 | 0.1953 | 0.0583 | −0.1554 | 0.048* | |
C7 | 0.1968 (2) | 0.0430 (2) | −0.04392 (14) | 0.0386 (5) | |
H7 | 0.1215 | 0.0055 | −0.0491 | 0.048* | |
C8 | 0.2609 (2) | 0.0661 (2) | 0.02604 (13) | 0.0335 (5) | |
H8 | 0.2307 | 0.0454 | 0.0692 | 0.042* | |
C9 | 0.37158 (19) | 0.1207 (2) | 0.03205 (12) | 0.0278 (4) | |
C10 | 0.4179 (2) | 0.15173 (19) | −0.03149 (12) | 0.0282 (4) | |
Cl1 | 0.15670 (14) | 0.25888 (17) | 0.30786 (9) | 0.0367 (3) | 0.80 |
Cu1 | 0.0000 | 0.14212 (3) | 0.2500 | 0.02661 (14) | |
Cl2 | 0.07261 (9) | 0.03648 (12) | 0.16239 (6) | 0.0412 (2) | 0.80 |
Cl1' | 0.1415 (7) | 0.2949 (7) | 0.2946 (4) | 0.0424 (16) | 0.20 |
Cl2' | 0.0874 (3) | −0.0041 (4) | 0.1887 (2) | 0.0315 (8) | 0.20 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1W | 0.0328 (10) | 0.0686 (14) | 0.0298 (8) | −0.0012 (9) | 0.0087 (7) | 0.0011 (8) |
N1 | 0.0375 (11) | 0.0321 (10) | 0.0243 (9) | 0.0037 (7) | 0.0106 (8) | 0.0019 (7) |
C2 | 0.0379 (12) | 0.0354 (12) | 0.0288 (11) | 0.0036 (9) | 0.0005 (9) | 0.0005 (9) |
C3 | 0.0325 (11) | 0.0337 (11) | 0.0373 (12) | −0.0003 (9) | 0.0066 (9) | 0.0022 (9) |
C4 | 0.0379 (12) | 0.0306 (11) | 0.0312 (11) | 0.0041 (9) | 0.0129 (9) | 0.0035 (8) |
C5 | 0.0471 (14) | 0.0298 (11) | 0.0257 (10) | 0.0033 (9) | 0.0078 (9) | −0.0003 (8) |
C6 | 0.0457 (14) | 0.0312 (12) | 0.0346 (12) | 0.0004 (9) | −0.0012 (10) | −0.0069 (9) |
C7 | 0.0356 (12) | 0.0296 (11) | 0.0493 (14) | 0.0002 (9) | 0.0052 (10) | −0.0027 (9) |
C8 | 0.0354 (12) | 0.0292 (11) | 0.0384 (12) | 0.0035 (8) | 0.0133 (9) | 0.0021 (9) |
C9 | 0.0335 (11) | 0.0243 (10) | 0.0263 (10) | 0.0057 (8) | 0.0073 (8) | 0.0013 (8) |
C10 | 0.0355 (12) | 0.0234 (10) | 0.0269 (10) | 0.0044 (8) | 0.0092 (9) | 0.0002 (7) |
Cl1 | 0.0265 (5) | 0.0474 (9) | 0.0345 (8) | −0.0084 (5) | 0.0019 (5) | −0.0070 (6) |
Cu1 | 0.0214 (2) | 0.0343 (2) | 0.0244 (2) | 0.000 | 0.00508 (14) | 0.000 |
Cl2 | 0.0313 (5) | 0.0522 (6) | 0.0427 (6) | −0.0019 (4) | 0.0137 (5) | −0.0172 (4) |
Cl1' | 0.052 (3) | 0.039 (3) | 0.029 (2) | −0.015 (2) | −0.0078 (18) | 0.0123 (18) |
Cl2' | 0.0317 (16) | 0.0389 (19) | 0.0222 (17) | −0.0134 (13) | 0.0004 (13) | −0.0007 (12) |
Geometric parameters (Å, º) top
O1W—H1W | 0.86 (4) | C5—C10 | 1.415 (3) |
O1W—H2W | 0.80 (5) | C5—H5 | 0.95 |
N1—C2 | 1.317 (3) | C6—C7 | 1.402 (4) |
N1—C9 | 1.372 (3) | C6—H6 | 0.95 |
N1—H1 | 0.79 (3) | C7—C8 | 1.377 (3) |
C2—C3 | 1.390 (3) | C7—H7 | 0.95 |
C2—H2 | 0.95 | C8—C9 | 1.398 (3) |
C3—C4 | 1.368 (3) | C8—H8 | 0.95 |
C3—H3 | 0.95 | C9—C10 | 1.411 (3) |
C4—C10 | 1.409 (3) | Cu1—Cl1 | 2.2622 (18) |
C4—H4 | 0.95 | Cu1—Cl2 | 2.2174 (11) |
C5—C6 | 1.355 (4) | | |
| | | |
H1W—O1W—H2W | 105 (4) | C7—C6—H6 | 119.4 |
C2—N1—C9 | 123.4 (2) | C8—C7—C6 | 120.7 (2) |
C2—N1—H1 | 119 (2) | C8—C7—H7 | 119.7 |
C9—N1—H1 | 118 (2) | C6—C7—H7 | 119.7 |
N1—C2—C3 | 120.5 (2) | C7—C8—C9 | 118.5 (2) |
N1—C2—H2 | 119.7 | C7—C8—H8 | 120.8 |
C3—C2—H2 | 119.7 | C9—C8—H8 | 120.8 |
C4—C3—C2 | 119.2 (2) | N1—C9—C8 | 120.7 (2) |
C4—C3—H3 | 120.4 | N1—C9—C10 | 117.8 (2) |
C2—C3—H3 | 120.4 | C8—C9—C10 | 121.5 (2) |
C3—C4—C10 | 120.3 (2) | C4—C10—C9 | 118.7 (2) |
C3—C4—H4 | 119.8 | C4—C10—C5 | 123.3 (2) |
C10—C4—H4 | 119.8 | C9—C10—C5 | 118.0 (2) |
C6—C5—C10 | 120.2 (2) | Cl1—Cu1—Cl2 | 100.45 (6) |
C6—C5—H5 | 119.9 | Cl2—Cu1—Cl1i | 107.12 (5) |
C10—C5—H5 | 119.9 | Cl2—Cu1—Cl2i | 124.11 (7) |
C5—C6—C7 | 121.2 (2) | Cl1—Cu1—Cl1i | 118.98 (8) |
C5—C6—H6 | 119.4 | | |
| | | |
C9—N1—C2—C3 | −0.2 (3) | C7—C8—C9—C10 | −0.1 (3) |
N1—C2—C3—C4 | 0.2 (3) | C3—C4—C10—C9 | 0.0 (3) |
C2—C3—C4—C10 | −0.1 (3) | C3—C4—C10—C5 | 179.0 (2) |
C10—C5—C6—C7 | −0.4 (3) | N1—C9—C10—C4 | 0.0 (3) |
C5—C6—C7—C8 | 0.6 (3) | C8—C9—C10—C4 | 179.30 (18) |
C6—C7—C8—C9 | −0.3 (3) | N1—C9—C10—C5 | −178.97 (17) |
C2—N1—C9—C8 | −179.2 (2) | C8—C9—C10—C5 | 0.3 (3) |
C2—N1—C9—C10 | 0.0 (3) | C6—C5—C10—C4 | −179.0 (2) |
C7—C8—C9—N1 | 179.13 (19) | C6—C5—C10—C9 | 0.0 (3) |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.79 (3) | 1.94 (3) | 2.727 (3) | 179 (3) |
O1W—H1W···Cl1 | 0.86 (4) | 2.77 (4) | 3.474 (3) | 140 (3) |
O1W—H2W···Cl1ii | 0.80 (5) | 2.43 (5) | 3.234 (3) | 175 (4) |
O1W—H1W···Cl2 | 0.86 (4) | 2.60 (4) | 3.311 (2) | 141 (3) |
C2—H2···O1Wiii | 0.95 | 2.51 | 3.274 (3) | 137 |
C4—H4···Cl1iv | 0.95 | 2.79 | 3.730 (3) | 169 |
C7—H7···Cl2v | 0.95 | 2.81 | 3.578 (3) | 138 |
C8—H8···Cl2 | 0.95 | 2.76 | 3.660 (3) | 158 |
Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, y, −z+1/2; (iv) x+1/2, −y+1/2, z−1/2; (v) −x, −y, −z. |
Experimental details
Crystal data |
Chemical formula | 2C9H8N+·Cl4Cu2+·2H2O |
Mr | 501.70 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 11.815 (2), 9.837 (2), 18.311 (4) |
β (°) | 101.05 (3) |
V (Å3) | 2088.7 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.57 |
Crystal size (mm) | 0.38 × 0.36 × 0.04 |
|
Data collection |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan SORTAV (Blessing, 1995) |
Tmin, Tmax | 0.586, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7197, 2330, 2001 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.100, 1.04 |
No. of reflections | 2330 |
No. of parameters | 153 |
No. of restraints | 25 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.62 |
Selected bond angles (º) topCl1—Cu1—Cl2 | 100.45 (6) | Cl2—Cu1—Cl2i | 124.11 (7) |
Cl2—Cu1—Cl1i | 107.12 (5) | Cl1—Cu1—Cl1i | 118.98 (8) |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.79 (3) | 1.94 (3) | 2.727 (3) | 179 (3) |
O1W—H1W···Cl1 | 0.86 (4) | 2.77 (4) | 3.474 (3) | 140 (3) |
O1W—H2W···Cl1ii | 0.80 (5) | 2.43 (5) | 3.234 (3) | 175 (4) |
O1W—H1W···Cl2 | 0.86 (4) | 2.60 (4) | 3.311 (2) | 141 (3) |
C2—H2···O1Wiii | 0.95 | 2.51 | 3.274 (3) | 137 |
C4—H4···Cl1iv | 0.95 | 2.79 | 3.730 (3) | 169 |
C7—H7···Cl2v | 0.95 | 2.81 | 3.578 (3) | 138 |
C8—H8···Cl2 | 0.95 | 2.76 | 3.660 (3) | 158 |
Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, y, −z+1/2; (iv) x+1/2, −y+1/2, z−1/2; (v) −x, −y, −z. |
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Crystals of the title compound, (I), were obtained after several days from the cooled reaction solution following the heating of CuCl2 and E-2-acetylbenzene-8-quinonylhydrazone in dilute HCl. We are currently studying the derivatives of both quinonylhydrazones (Lynch & McClenaghan, 2001a) and pyrrolo[3,2-h]quinolines (Lynch & McClenaghan, 2001b) and it was our intention to prepare the copper(II) complex of E-2-acetylbenzene-8- quinonylhydrazone before proceeding with the Cu complex of the corresponding pyrrolo[3,2-h]quinoline. However, the acidic conditions used to solublize the hydrazone were also sufficient to hydrolyse this compound back to the quinonylhydrazine and then the presence of Cu2+ and air oxidized the hydrazine to quinoline itself; the latter process was reported by Timmons (1970).
The structure of (I) consists of one quinolinium cation, one water molecule and one half of the CuCl42− anion (the other half is generated by crystallographic twofold symmetry) in the asymmetric unit. The Cu atom in the distorted tetrahedral anion (Table 1) lies on a twofold axis and the two independent Cl atoms are both disordered over two sites with main site occupancies of 80%. The anions and the water molecules form two-dimensional hydrogen-bonding networks parallel to (110), in which one of the water H atoms, H1W, is involved in three-centered hydrogen bonds with Cl1 and Cl2 atoms (Table 2). The cations are arranged between two anion-water networks in parallel stacks with their centroids alternatively separated by 3.685 (3) and 4.057 (3) Å, respectively (Fig. 2). The cations are linked to the anion-water networks through N—H···O, C—H···O and C—H···Cl intermolecular hydrogen bonds (Table 2), to form a three-dimensional molecular network. A previously reported structure, similar to (I), is bis[cinchonium tetrachlorocuprate(II)] trihydrate (Dyrek et al., 1987).