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The asymmetric unit of the title compound, 2C9H8N+·CuCl42−·2H2O, comprises one quinolinium cation, one water mol­ecule and one-half of the CuCl42− 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016537/ci6159sup1.cif
Contains datablocks I, default

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016537/ci6159Isup2.hkl
Contains datablock I

CCDC reference: 198304

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](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


Yellow Alert 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

Comment top

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).

Experimental top

The title compound was obtained from Key Organics Ltd and crystals were grown from dil. HCl solution.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Molecular configuration and atom-numbering scheme for the title compound, showing 50% probability ellipsoids. One of the two H atoms attached to the water O atom is hidden.
[Figure 2] Fig. 2. Packing diagram viewed down the a axis. H-bonding interactions and Cu—Cl bonds are shown as dotted lines.
Bisquinolinium tetrachlorocopper(II) dihydrate top
Crystal data top
2C9H8N+·Cl4Cu2+·2H2OF(000) = 1020
Mr = 501.70Dx = 1.595 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5373 reflections
a = 11.815 (2) Åθ = 2.9–27.5°
b = 9.837 (2) ŵ = 1.57 mm1
c = 18.311 (4) ÅT = 150 K
β = 101.05 (3)°Plate, yellow
V = 2088.7 (7) Å30.38 × 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 anode2001 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scansh = 1415
Absorption correction: multi-scan
SORTAV (Blessing, 1995)
k = 1112
Tmin = 0.586, Tmax = 0.940l = 2323
7197 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H 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 parametersΔρmax = 0.47 e Å3
25 restraintsΔρmin = 0.62 e Å3
Crystal data top
2C9H8N+·Cl4Cu2+·2H2OV = 2088.7 (7) Å3
Mr = 501.70Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.815 (2) ŵ = 1.57 mm1
b = 9.837 (2) ÅT = 150 K
c = 18.311 (4) Å0.38 × 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 = 0.940Rint = 0.044
7197 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03725 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.47 e Å3
2330 reflectionsΔρmin = 0.62 e Å3
153 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O1W0.35224 (17)0.0825 (3)0.22398 (9)0.0434 (4)
H1W0.282 (4)0.102 (4)0.226 (2)0.071 (11)*
H2W0.353 (4)0.002 (5)0.219 (3)0.101 (17)*
N10.43836 (17)0.14724 (17)0.10047 (11)0.0307 (4)
H10.413 (2)0.129 (2)0.1358 (16)0.030 (7)*
C20.5426 (2)0.1999 (2)0.10954 (12)0.0348 (5)
H20.58490.21640.15830.044*
C30.5912 (2)0.2317 (2)0.04833 (13)0.0345 (5)
H30.66650.26940.05500.043*
C40.52945 (19)0.2080 (2)0.02164 (12)0.0324 (5)
H40.56190.22950.06380.040*
C50.3486 (2)0.1266 (2)0.10220 (12)0.0341 (5)
H50.37740.14660.14600.043*
C60.2413 (2)0.0742 (2)0.10761 (13)0.0384 (5)
H60.19530.05830.15540.048*
C70.1968 (2)0.0430 (2)0.04392 (14)0.0386 (5)
H70.12150.00550.04910.048*
C80.2609 (2)0.0661 (2)0.02604 (13)0.0335 (5)
H80.23070.04540.06920.042*
C90.37158 (19)0.1207 (2)0.03205 (12)0.0278 (4)
C100.4179 (2)0.15173 (19)0.03149 (12)0.0282 (4)
Cl10.15670 (14)0.25888 (17)0.30786 (9)0.0367 (3)0.80
Cu10.00000.14212 (3)0.25000.02661 (14)
Cl20.07261 (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
U11U22U33U12U13U23
O1W0.0328 (10)0.0686 (14)0.0298 (8)0.0012 (9)0.0087 (7)0.0011 (8)
N10.0375 (11)0.0321 (10)0.0243 (9)0.0037 (7)0.0106 (8)0.0019 (7)
C20.0379 (12)0.0354 (12)0.0288 (11)0.0036 (9)0.0005 (9)0.0005 (9)
C30.0325 (11)0.0337 (11)0.0373 (12)0.0003 (9)0.0066 (9)0.0022 (9)
C40.0379 (12)0.0306 (11)0.0312 (11)0.0041 (9)0.0129 (9)0.0035 (8)
C50.0471 (14)0.0298 (11)0.0257 (10)0.0033 (9)0.0078 (9)0.0003 (8)
C60.0457 (14)0.0312 (12)0.0346 (12)0.0004 (9)0.0012 (10)0.0069 (9)
C70.0356 (12)0.0296 (11)0.0493 (14)0.0002 (9)0.0052 (10)0.0027 (9)
C80.0354 (12)0.0292 (11)0.0384 (12)0.0035 (8)0.0133 (9)0.0021 (9)
C90.0335 (11)0.0243 (10)0.0263 (10)0.0057 (8)0.0073 (8)0.0013 (8)
C100.0355 (12)0.0234 (10)0.0269 (10)0.0044 (8)0.0092 (9)0.0002 (7)
Cl10.0265 (5)0.0474 (9)0.0345 (8)0.0084 (5)0.0019 (5)0.0070 (6)
Cu10.0214 (2)0.0343 (2)0.0244 (2)0.0000.00508 (14)0.000
Cl20.0313 (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—H1W0.86 (4)C5—C101.415 (3)
O1W—H2W0.80 (5)C5—H50.95
N1—C21.317 (3)C6—C71.402 (4)
N1—C91.372 (3)C6—H60.95
N1—H10.79 (3)C7—C81.377 (3)
C2—C31.390 (3)C7—H70.95
C2—H20.95C8—C91.398 (3)
C3—C41.368 (3)C8—H80.95
C3—H30.95C9—C101.411 (3)
C4—C101.409 (3)Cu1—Cl12.2622 (18)
C4—H40.95Cu1—Cl22.2174 (11)
C5—C61.355 (4)
H1W—O1W—H2W105 (4)C7—C6—H6119.4
C2—N1—C9123.4 (2)C8—C7—C6120.7 (2)
C2—N1—H1119 (2)C8—C7—H7119.7
C9—N1—H1118 (2)C6—C7—H7119.7
N1—C2—C3120.5 (2)C7—C8—C9118.5 (2)
N1—C2—H2119.7C7—C8—H8120.8
C3—C2—H2119.7C9—C8—H8120.8
C4—C3—C2119.2 (2)N1—C9—C8120.7 (2)
C4—C3—H3120.4N1—C9—C10117.8 (2)
C2—C3—H3120.4C8—C9—C10121.5 (2)
C3—C4—C10120.3 (2)C4—C10—C9118.7 (2)
C3—C4—H4119.8C4—C10—C5123.3 (2)
C10—C4—H4119.8C9—C10—C5118.0 (2)
C6—C5—C10120.2 (2)Cl1—Cu1—Cl2100.45 (6)
C6—C5—H5119.9Cl2—Cu1—Cl1i107.12 (5)
C10—C5—H5119.9Cl2—Cu1—Cl2i124.11 (7)
C5—C6—C7121.2 (2)Cl1—Cu1—Cl1i118.98 (8)
C5—C6—H6119.4
C9—N1—C2—C30.2 (3)C7—C8—C9—C100.1 (3)
N1—C2—C3—C40.2 (3)C3—C4—C10—C90.0 (3)
C2—C3—C4—C100.1 (3)C3—C4—C10—C5179.0 (2)
C10—C5—C6—C70.4 (3)N1—C9—C10—C40.0 (3)
C5—C6—C7—C80.6 (3)C8—C9—C10—C4179.30 (18)
C6—C7—C8—C90.3 (3)N1—C9—C10—C5178.97 (17)
C2—N1—C9—C8179.2 (2)C8—C9—C10—C50.3 (3)
C2—N1—C9—C100.0 (3)C6—C5—C10—C4179.0 (2)
C7—C8—C9—N1179.13 (19)C6—C5—C10—C90.0 (3)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1W0.79 (3)1.94 (3)2.727 (3)179 (3)
O1W—H1W···Cl10.86 (4)2.77 (4)3.474 (3)140 (3)
O1W—H2W···Cl1ii0.80 (5)2.43 (5)3.234 (3)175 (4)
O1W—H1W···Cl20.86 (4)2.60 (4)3.311 (2)141 (3)
C2—H2···O1Wiii0.952.513.274 (3)137
C4—H4···Cl1iv0.952.793.730 (3)169
C7—H7···Cl2v0.952.813.578 (3)138
C8—H8···Cl20.952.763.660 (3)158
Symmetry codes: (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y, z+1/2; (iv) x+1/2, y+1/2, z1/2; (v) x, y, z.

Experimental details

Crystal data
Chemical formula2C9H8N+·Cl4Cu2+·2H2O
Mr501.70
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)11.815 (2), 9.837 (2), 18.311 (4)
β (°) 101.05 (3)
V3)2088.7 (7)
Z4
Radiation typeMo Kα
µ (mm1)1.57
Crystal size (mm)0.38 × 0.36 × 0.04
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
SORTAV (Blessing, 1995)
Tmin, Tmax0.586, 0.940
No. of measured, independent and
observed [I > 2σ(I)] reflections
7197, 2330, 2001
Rint0.044
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.100, 1.04
No. of reflections2330
No. of parameters153
No. of restraints25
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.47, 0.62

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Please provide, SHELXL97.

Selected bond angles (º) top
Cl1—Cu1—Cl2100.45 (6)Cl2—Cu1—Cl2i124.11 (7)
Cl2—Cu1—Cl1i107.12 (5)Cl1—Cu1—Cl1i118.98 (8)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1W0.79 (3)1.94 (3)2.727 (3)179 (3)
O1W—H1W···Cl10.86 (4)2.77 (4)3.474 (3)140 (3)
O1W—H2W···Cl1ii0.80 (5)2.43 (5)3.234 (3)175 (4)
O1W—H1W···Cl20.86 (4)2.60 (4)3.311 (2)141 (3)
C2—H2···O1Wiii0.952.513.274 (3)137
C4—H4···Cl1iv0.952.793.730 (3)169
C7—H7···Cl2v0.952.813.578 (3)138
C8—H8···Cl20.952.763.660 (3)158
Symmetry codes: (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y, z+1/2; (iv) x+1/2, y+1/2, z1/2; (v) x, y, z.
 

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