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Acta Cryst. (2008). E64, m853-m854    [ doi:10.1107/S1600536808015778 ]

Tetrakis(4-aminopyridine-[kappa]N1)dichloridocopper(II) monohydrate

H.-K. Fun, A. Sinthya, S. R. Jebas and S. Devadasan

Abstract top

The asymmetric unit of the title compound, [CuCl2(C5H6N2)4]·H2O, contains two crystallographically independent complex molecules and two water molecules. The CuII ion in each molecule is six-coordinated in an elongated octahedral geometry, with the equatorial plane defined by four pyridine N atoms of four aminopyridine ligands and the axial positions occupied by two Cl atoms. In the crystal structure, molecules are linked into a three-dimensional framework by C-H...Cl, O-H...Cl, N-H...O, N-H...Cl and N-H...N hydrogen bonds and C/N-H...[pi] interactions involving the pyridine rings.

Comment top

4-Aminopyridine (Fampridine) is used clinically in Lambert–Eaton myasthenic syndrome and multiple sclerosis because by blocking potassium channels it prolongs action potentials thereby increasing transmitter release at the neuromuscular junctions (Judge & Bever, 2006; Schwid et al.,1997; Strupp et al., 2004).

The asymmetric unit of the title compound contains two crystallographically independent complex molecules and two water molecules (Fig. 1). The CuII ion in each molecule is six-coordinated in an elongated octahedral geometry formed by four pyridine N atoms from four aminopyridine ligands and two Cl atoms. The two Cl atoms are located at apical positions and the four N atoms form the basal plane. The Jahn–Teller elongation observed in Cu1—Cl1 [3.2185 (4) Å] and Cu2—Cl3 [3.1884 (4) Å] distances are consistent with those reported earlier (Moncol et al., 2004). The average Cu—N bond length of 2.0205 (11) Å agree well with that reported for a copper complex (Zaleski et al., 2005). The bond lengths and angles in the 4-aminopyridine units agree well with those reported earlier (Anderson et al., 2005).

The crystal packing is consolidated by intermolecular O—H···Cl, N—H···O, N—H···N, N—H···Cl and C—H···Cl hydrogen bonds, and and C/N—H···π interactions (Table 2) involving the pyridine rings to form a three-dimensional framework.

Related literature top

For related literature on 4-aminopyridine, see: Judge & Bever (2006); Schwid et al. (1997); Strupp et al. (2004). For bond lengths, see: Moncol et al. (2004); Zaleski et al. (2005); Anderson et al. (2005).

Experimental top

A solution of 4-aminopyridine (0.376 g) in water (20 ml) was added to a solution of CuCl2.2H2O (0.170 g) in water (20 ml) and the mixture was stirred at 303 K for 6 h. The clear blue solution obtained was filtered and allowed to evaporate slowly. Blue crystals of the title compound were obtained after a month.

Refinement top

H atoms of the water molecules were located in a difference map and refined with O—H and H···H distance restraints of 0.84 (1) and 1.37 (2) Å, respectively. The remaining H atoms were positioned geometrically [C—H = 0.93 Å and N—H = 0.86 Å] and refined using a riding model, with Uiso(H) = 1.2Ueq(C,N)].

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms are omitted for clarity.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines.
Tetrakis(4-aminopyridine-κN1)dichloridocopper(II) monohydrate top
Crystal data top
[CuCl2(C5H6N2)4]·H2OZ = 4
Mr = 528.93F000 = 1092
Triclinic, P1Dx = 1.496 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.5430 (2) ÅCell parameters from 9885 reflections
b = 14.1606 (2) Åθ = 2.5–34.6º
c = 17.4662 (3) ŵ = 1.19 mm−1
α = 88.463 (1)ºT = 100.0 (1) K
β = 86.075 (1)ºPlate, purple
γ = 85.781 (1)º0.51 × 0.40 × 0.12 mm
V = 2347.81 (7) Å3
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		24484 independent reflections
Radiation source: fine-focus sealed tube17417 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
T = 100.0(1) Kθmax = 37.5º
φ and ω scansθmin = 1.2º
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −16→15
Tmin = 0.583, Tmax = 0.871k = −23→24
106511 measured reflectionsl = −29→29
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.104  w = 1/[σ2(Fo2) + (0.0446P)2 + 0.3682P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
24484 reflectionsΔρmax = 0.92 e Å−3
593 parametersΔρmin = −1.11 e Å−3
6 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[CuCl2(C5H6N2)4]·H2Oγ = 85.781 (1)º
Mr = 528.93V = 2347.81 (7) Å3
Triclinic, P1Z = 4
a = 9.5430 (2) ÅMo Kα
b = 14.1606 (2) ŵ = 1.19 mm−1
c = 17.4662 (3) ÅT = 100.0 (1) K
α = 88.463 (1)º0.51 × 0.40 × 0.12 mm
β = 86.075 (1)º
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		24484 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		17417 reflections with I > 2σ(I)
Tmin = 0.583, Tmax = 0.871Rint = 0.047
106511 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0416 restraints
wR(F2) = 0.104H atoms treated by a mixture of
independent and constrained refinement
S = 1.07Δρmax = 0.92 e Å−3
24484 reflectionsΔρmin = −1.11 e Å−3
593 parameters
Special details top

Experimental. The data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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
xyzUiso*/Ueq
Cu10.438175 (17)0.078184 (11)0.230903 (9)0.01546 (4)
N10.42808 (11)−0.05177 (8)0.18839 (6)0.01482 (18)
N20.37359 (14)−0.31516 (8)0.09807 (7)0.0227 (2)
H2A0.3669−0.32040.04950.027*
H2B0.3679−0.36410.12810.027*
N30.58224 (11)0.02793 (7)0.30393 (6)0.01460 (18)
N40.88631 (12)−0.05810 (9)0.45634 (7)0.0204 (2)
H4A0.9675−0.08250.43960.025*
H4B0.8678−0.05080.50480.025*
N50.42913 (11)0.20525 (7)0.28145 (6)0.01477 (18)
N60.40879 (14)0.45962 (9)0.39775 (8)0.0280 (3)
H6A0.32930.48290.41780.034*
H6B0.48400.48820.40260.034*
N70.27731 (11)0.12641 (8)0.16710 (6)0.01593 (19)
N8−0.06992 (13)0.23308 (10)0.05134 (8)0.0276 (3)
H8A−0.06170.27690.01670.033*
H8B−0.15040.21060.06230.033*
C10.41925 (13)−0.06352 (9)0.11226 (7)0.0155 (2)
H10.4246−0.01050.07990.019*
C20.40285 (13)−0.14884 (9)0.07986 (7)0.0154 (2)
H20.3983−0.15270.02700.018*
C30.39299 (13)−0.23054 (9)0.12703 (7)0.0160 (2)
C40.40297 (14)−0.21872 (9)0.20635 (7)0.0172 (2)
H40.3979−0.27040.24010.021*
C50.42019 (13)−0.13030 (9)0.23353 (7)0.0162 (2)
H50.4268−0.12430.28600.019*
C60.70980 (14)−0.01180 (9)0.27928 (7)0.0173 (2)
H60.7287−0.01930.22680.021*
C70.81305 (14)−0.04176 (10)0.32694 (7)0.0180 (2)
H70.8989−0.06880.30670.022*
C80.78850 (13)−0.03145 (9)0.40679 (7)0.0144 (2)
C90.65482 (13)0.00904 (9)0.43265 (7)0.0158 (2)
H90.63240.01690.48490.019*
C100.55757 (13)0.03684 (9)0.38032 (7)0.0159 (2)
H100.47000.06320.39870.019*
C110.54513 (13)0.25191 (9)0.28928 (8)0.0175 (2)
H110.63100.22550.26850.021*
C120.54381 (14)0.33629 (9)0.32624 (8)0.0190 (2)
H120.62700.36570.33000.023*
C130.41553 (14)0.37788 (9)0.35848 (8)0.0176 (2)
C140.29433 (13)0.32995 (9)0.34973 (8)0.0168 (2)
H140.20690.35490.36960.020*
C150.30574 (13)0.24571 (9)0.31143 (7)0.0159 (2)
H150.22420.21510.30590.019*
C160.28786 (14)0.19626 (9)0.11362 (8)0.0180 (2)
H160.37500.22090.10350.022*
C170.17711 (14)0.23325 (9)0.07308 (8)0.0190 (2)
H170.19100.28030.03570.023*
C180.04303 (13)0.19955 (10)0.08841 (8)0.0179 (2)
C190.03170 (14)0.12759 (10)0.14505 (7)0.0180 (2)
H19−0.05490.10340.15810.022*
C200.14907 (14)0.09318 (9)0.18106 (7)0.0175 (2)
H200.13950.04420.21710.021*
Cu20.926147 (17)0.588239 (11)0.265503 (9)0.01796 (4)
N91.07098 (11)0.53919 (8)0.18340 (6)0.01519 (19)
N101.36478 (12)0.42921 (8)0.01531 (6)0.0183 (2)
H10A1.44010.39750.02830.022*
H10B1.34900.4372−0.03240.022*
N110.91724 (11)0.45781 (8)0.31403 (6)0.01547 (19)
N120.91541 (14)0.18712 (8)0.41402 (7)0.0248 (3)
H12A0.90610.18010.46310.030*
H12B0.92510.13820.38550.030*
N130.77568 (12)0.64322 (8)0.34276 (6)0.0170 (2)
N140.45970 (14)0.77011 (10)0.49076 (7)0.0262 (3)
H14A0.48120.80300.52840.031*
H14B0.37280.76330.48350.031*
N150.91270 (11)0.71282 (8)0.20637 (6)0.01664 (19)
N160.89456 (13)0.95381 (8)0.06323 (7)0.0204 (2)
H16A0.81730.97180.04280.024*
H16B0.96800.98500.05370.024*
C211.05091 (13)0.55075 (9)0.10788 (7)0.0157 (2)
H210.96800.58320.09390.019*
C221.14589 (13)0.51732 (9)0.05055 (7)0.0156 (2)
H221.12730.5283−0.00060.019*
C231.27166 (12)0.46630 (9)0.06954 (7)0.0141 (2)
C241.29340 (13)0.45489 (9)0.14834 (7)0.0164 (2)
H241.37530.42280.16420.020*
C251.19284 (14)0.49147 (9)0.20156 (7)0.0167 (2)
H251.20940.48300.25320.020*
C260.92843 (13)0.37962 (9)0.27115 (7)0.0165 (2)
H260.93610.38730.21800.020*
C270.92913 (14)0.28925 (9)0.30160 (7)0.0171 (2)
H270.93890.23770.26930.021*
C280.91497 (13)0.27475 (9)0.38181 (7)0.0164 (2)
C290.89945 (13)0.35662 (9)0.42649 (7)0.0164 (2)
H290.88730.35150.47970.020*
C300.90246 (13)0.44415 (9)0.39074 (7)0.0164 (2)
H300.89380.49730.42140.020*
C310.63836 (14)0.63335 (10)0.33431 (8)0.0185 (2)
H310.61500.59650.29440.022*
C320.53041 (14)0.67467 (10)0.38134 (7)0.0182 (2)
H320.43720.66660.37230.022*
C330.56243 (14)0.72915 (9)0.44304 (7)0.0177 (2)
C340.70551 (15)0.73799 (10)0.45233 (8)0.0210 (2)
H340.73230.77230.49290.025*
C350.80628 (14)0.69599 (10)0.40169 (8)0.0196 (2)
H350.90040.70440.40840.024*
C360.79327 (13)0.74421 (9)0.17431 (8)0.0180 (2)
H360.71380.71050.18450.022*
C370.78247 (13)0.82367 (9)0.12713 (8)0.0174 (2)
H370.69750.84260.10630.021*
C380.90066 (13)0.87553 (9)0.11090 (7)0.0160 (2)
C391.02509 (14)0.84304 (9)0.14474 (8)0.0181 (2)
H391.10610.87550.13590.022*
C401.02618 (13)0.76286 (9)0.19099 (8)0.0179 (2)
H401.10960.74220.21270.021*
Cl10.20362 (3)0.01980 (2)0.361362 (18)0.01910 (6)
Cl20.64240 (3)0.12291 (2)0.122477 (17)0.01617 (5)
Cl30.69715 (4)0.51337 (2)0.161801 (18)0.02111 (6)
Cl41.14798 (3)0.62545 (2)0.353735 (19)0.01962 (6)
O1W0.82107 (13)0.18216 (8)0.57474 (6)0.0285 (2)
O2W1.62468 (11)0.33858 (7)0.07154 (6)0.02102 (19)
H1W10.810 (2)0.1333 (8)0.6007 (10)0.037 (6)*
H2W10.834 (2)0.2276 (9)0.6020 (10)0.039 (6)*
H1W21.628 (3)0.2884 (9)0.0979 (11)0.052 (7)*
H2W21.648 (2)0.3826 (10)0.0992 (11)0.048 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01684 (7)0.01299 (7)0.01708 (7)0.00168 (5)−0.00697 (5)−0.00320 (5)
N10.0164 (5)0.0146 (5)0.0136 (4)0.0001 (4)−0.0033 (3)−0.0015 (3)
N20.0330 (6)0.0165 (5)0.0193 (5)−0.0048 (5)−0.0016 (5)−0.0046 (4)
N30.0160 (4)0.0138 (4)0.0141 (4)0.0008 (4)−0.0033 (3)−0.0021 (3)
N40.0158 (5)0.0302 (6)0.0149 (5)0.0041 (4)−0.0036 (4)−0.0019 (4)
N50.0137 (4)0.0139 (5)0.0170 (5)0.0003 (4)−0.0035 (3)−0.0029 (3)
N60.0220 (6)0.0183 (6)0.0442 (8)−0.0008 (5)−0.0034 (5)−0.0124 (5)
N70.0162 (5)0.0144 (5)0.0177 (5)−0.0003 (4)−0.0053 (4)−0.0017 (3)
N80.0167 (5)0.0331 (7)0.0325 (7)0.0028 (5)−0.0063 (5)0.0052 (5)
C10.0161 (5)0.0158 (5)0.0147 (5)−0.0011 (4)−0.0026 (4)−0.0002 (4)
C20.0153 (5)0.0182 (5)0.0128 (5)−0.0008 (4)−0.0019 (4)−0.0026 (4)
C30.0152 (5)0.0155 (5)0.0174 (5)−0.0013 (4)−0.0004 (4)−0.0027 (4)
C40.0210 (6)0.0149 (5)0.0156 (5)−0.0019 (4)−0.0006 (4)0.0003 (4)
C50.0178 (5)0.0168 (5)0.0140 (5)−0.0011 (4)−0.0024 (4)−0.0006 (4)
C60.0202 (6)0.0185 (6)0.0126 (5)0.0040 (4)−0.0020 (4)−0.0032 (4)
C70.0173 (5)0.0215 (6)0.0146 (5)0.0044 (5)−0.0013 (4)−0.0035 (4)
C80.0145 (5)0.0150 (5)0.0139 (5)−0.0009 (4)−0.0027 (4)−0.0010 (4)
C90.0151 (5)0.0194 (6)0.0129 (5)−0.0009 (4)−0.0004 (4)−0.0016 (4)
C100.0142 (5)0.0170 (5)0.0164 (5)0.0001 (4)−0.0014 (4)−0.0017 (4)
C110.0137 (5)0.0180 (6)0.0208 (6)0.0003 (4)−0.0023 (4)−0.0026 (4)
C120.0149 (5)0.0165 (6)0.0262 (6)−0.0019 (4)−0.0033 (4)−0.0036 (4)
C130.0188 (5)0.0138 (5)0.0202 (6)0.0003 (4)−0.0030 (4)−0.0021 (4)
C140.0146 (5)0.0153 (5)0.0203 (6)0.0006 (4)−0.0007 (4)−0.0012 (4)
C150.0140 (5)0.0150 (5)0.0191 (6)−0.0007 (4)−0.0032 (4)−0.0013 (4)
C160.0153 (5)0.0155 (5)0.0238 (6)−0.0032 (4)−0.0044 (4)0.0006 (4)
C170.0177 (5)0.0158 (6)0.0239 (6)−0.0009 (4)−0.0051 (5)0.0024 (4)
C180.0144 (5)0.0191 (6)0.0201 (6)0.0029 (4)−0.0045 (4)−0.0034 (4)
C190.0156 (5)0.0224 (6)0.0163 (6)−0.0037 (4)−0.0010 (4)−0.0027 (4)
C200.0193 (6)0.0189 (6)0.0149 (5)−0.0032 (4)−0.0023 (4)−0.0010 (4)
Cu20.01974 (8)0.01387 (7)0.01829 (8)0.00360 (6)0.00663 (6)0.00303 (5)
N90.0154 (4)0.0139 (4)0.0155 (5)0.0015 (4)0.0009 (3)0.0007 (3)
N100.0168 (5)0.0225 (5)0.0146 (5)0.0031 (4)0.0012 (4)−0.0009 (4)
N110.0175 (5)0.0137 (4)0.0149 (5)−0.0004 (4)0.0000 (4)0.0007 (3)
N120.0378 (7)0.0138 (5)0.0215 (6)0.0015 (5)0.0031 (5)0.0021 (4)
N130.0177 (5)0.0149 (5)0.0174 (5)0.0012 (4)0.0034 (4)0.0004 (4)
N140.0234 (6)0.0300 (7)0.0239 (6)0.0050 (5)0.0040 (5)−0.0088 (5)
N150.0157 (5)0.0145 (5)0.0186 (5)0.0015 (4)0.0030 (4)0.0015 (4)
N160.0218 (5)0.0163 (5)0.0226 (6)−0.0012 (4)0.0002 (4)0.0039 (4)
C210.0144 (5)0.0153 (5)0.0172 (5)0.0003 (4)−0.0006 (4)0.0002 (4)
C220.0155 (5)0.0172 (5)0.0144 (5)−0.0011 (4)−0.0020 (4)−0.0008 (4)
C230.0137 (5)0.0129 (5)0.0156 (5)−0.0017 (4)0.0002 (4)−0.0013 (4)
C240.0161 (5)0.0157 (5)0.0169 (5)0.0027 (4)−0.0018 (4)−0.0002 (4)
C250.0192 (5)0.0156 (5)0.0147 (5)0.0021 (4)0.0000 (4)0.0006 (4)
C260.0176 (5)0.0172 (5)0.0144 (5)−0.0005 (4)0.0001 (4)−0.0015 (4)
C270.0185 (5)0.0143 (5)0.0184 (6)−0.0003 (4)0.0003 (4)−0.0030 (4)
C280.0153 (5)0.0150 (5)0.0186 (6)−0.0003 (4)−0.0005 (4)0.0009 (4)
C290.0185 (5)0.0159 (5)0.0143 (5)0.0004 (4)0.0000 (4)0.0005 (4)
C300.0189 (5)0.0148 (5)0.0153 (5)0.0002 (4)−0.0003 (4)−0.0013 (4)
C310.0201 (6)0.0193 (6)0.0156 (6)−0.0007 (5)0.0018 (4)−0.0017 (4)
C320.0173 (5)0.0207 (6)0.0159 (6)0.0006 (5)0.0007 (4)−0.0008 (4)
C330.0207 (6)0.0152 (5)0.0161 (5)0.0018 (4)0.0029 (4)−0.0001 (4)
C340.0226 (6)0.0208 (6)0.0199 (6)−0.0021 (5)−0.0011 (5)−0.0051 (5)
C350.0180 (6)0.0182 (6)0.0226 (6)−0.0016 (5)0.0003 (5)−0.0008 (4)
C360.0145 (5)0.0154 (5)0.0237 (6)−0.0011 (4)0.0011 (4)0.0000 (4)
C370.0146 (5)0.0154 (5)0.0219 (6)0.0000 (4)−0.0011 (4)0.0011 (4)
C380.0179 (5)0.0138 (5)0.0156 (5)0.0003 (4)0.0017 (4)−0.0004 (4)
C390.0160 (5)0.0172 (6)0.0210 (6)−0.0026 (4)0.0010 (4)0.0003 (4)
C400.0143 (5)0.0174 (6)0.0215 (6)0.0008 (4)0.0000 (4)0.0006 (4)
Cl10.02220 (14)0.01924 (14)0.01585 (13)−0.00149 (11)−0.00145 (10)0.00041 (10)
Cl20.01525 (12)0.01728 (13)0.01575 (13)−0.00059 (10)−0.00079 (9)0.00145 (9)
Cl30.02782 (16)0.02046 (14)0.01555 (13)−0.00381 (12)−0.00212 (11)−0.00224 (10)
Cl40.01772 (13)0.02048 (14)0.02104 (14)−0.00009 (11)−0.00386 (10)−0.00442 (11)
O1W0.0419 (6)0.0194 (5)0.0242 (5)−0.0066 (5)0.0045 (5)−0.0017 (4)
O2W0.0255 (5)0.0154 (4)0.0226 (5)0.0002 (4)−0.0064 (4)−0.0015 (4)
Geometric parameters (Å, °) top
Cu1—N12.0140 (11)Cu2—N92.0224 (10)
Cu1—N32.0177 (10)Cu2—N132.0286 (11)
Cu1—N52.0190 (11)Cu2—Cl42.7907 (4)
Cu1—N72.0258 (11)Cu2—Cl33.1884 (4)
Cu1—Cl22.7199 (3)N9—C211.3498 (16)
Cu1—Cl13.2185 (4)N9—C251.3539 (16)
N1—C51.3494 (16)N10—C231.3435 (16)
N1—C11.3536 (16)N10—H10A0.86
N2—C31.3431 (17)N10—H10B0.86
N2—H2A0.86N11—C261.3469 (17)
N2—H2B0.86N11—C301.3478 (16)
N3—C101.3466 (16)N12—C281.3485 (17)
N3—C61.3506 (16)N12—H12A0.86
N4—C81.3431 (16)N12—H12B0.86
N4—H4A0.86N13—C311.3465 (18)
N4—H4B0.86N13—C351.3482 (18)
N5—C111.3468 (17)N14—C331.3502 (17)
N5—C151.3496 (16)N14—H14A0.86
N6—C131.3564 (18)N14—H14B0.86
N6—H6A0.86N15—C361.3451 (17)
N6—H6B0.86N15—C401.3453 (17)
N7—C161.3466 (17)N16—C381.3685 (17)
N7—C201.3477 (17)N16—H16A0.86
N8—C181.3455 (17)N16—H16B0.86
N8—H8A0.86C21—C221.3735 (17)
N8—H8B0.86C21—H210.93
C1—C21.3716 (18)C22—C231.4095 (17)
C1—H10.93C22—H220.93
C2—C31.4073 (18)C23—C241.4092 (18)
C2—H20.93C24—C251.3726 (17)
C3—C41.4104 (18)C24—H240.93
C4—C51.3757 (18)C25—H250.93
C4—H40.93C26—C271.3723 (18)
C5—H50.93C26—H260.93
C6—C71.3695 (18)C27—C281.4091 (18)
C6—H60.93C27—H270.93
C7—C81.4080 (17)C28—C291.4080 (18)
C7—H70.93C29—C301.3742 (18)
C8—C91.4098 (17)C29—H290.93
C9—C101.3765 (18)C30—H300.93
C9—H90.93C31—C321.3783 (18)
C10—H100.93C31—H310.93
C11—C121.3721 (19)C32—C331.4050 (19)
C11—H110.93C32—H320.93
C12—C131.4071 (18)C33—C341.401 (2)
C12—H120.93C34—C351.3742 (19)
C13—C141.4025 (18)C34—H340.93
C14—C151.3770 (18)C35—H350.93
C14—H140.93C36—C371.3786 (18)
C15—H150.93C36—H360.93
C16—C171.3762 (18)C37—C381.3996 (18)
C16—H160.93C37—H370.93
C17—C181.4044 (19)C38—C391.4043 (19)
C17—H170.93C39—C401.3755 (18)
C18—C191.4057 (19)C39—H390.93
C19—C201.3738 (19)C40—H400.93
C19—H190.93O1W—H1W10.827 (9)
C20—H200.93O1W—H2W10.833 (9)
Cu2—N112.0165 (11)O2W—H1W20.835 (9)
Cu2—N152.0206 (11)O2W—H2W20.849 (9)
N1—Cu1—N391.10 (4)N11—Cu2—N991.26 (4)
N1—Cu1—N5173.52 (4)N15—Cu2—N988.17 (4)
N3—Cu1—N589.52 (4)N11—Cu2—N1391.71 (4)
N1—Cu1—N789.32 (4)N15—Cu2—N1388.57 (4)
N3—Cu1—N7173.70 (4)N9—Cu2—N13176.35 (4)
N5—Cu1—N789.35 (4)N11—Cu2—Cl490.90 (3)
N1—Cu1—Cl292.32 (3)N15—Cu2—Cl497.84 (3)
N3—Cu1—Cl291.83 (3)N9—Cu2—Cl488.13 (3)
N5—Cu1—Cl294.11 (3)N13—Cu2—Cl493.94 (3)
N7—Cu1—Cl294.43 (3)N11—Cu2—Cl382.30 (3)
N1—Cu1—Cl186.84 (3)N15—Cu2—Cl388.92 (3)
N3—Cu1—Cl186.48 (3)N9—Cu2—Cl386.13 (3)
N5—Cu1—Cl186.76 (3)N13—Cu2—Cl392.17 (3)
N7—Cu1—Cl187.27 (3)Cl4—Cu2—Cl3170.991 (11)
Cl2—Cu1—Cl1178.098 (10)C21—N9—C25116.39 (11)
C5—N1—C1116.35 (11)C21—N9—Cu2122.13 (8)
C5—N1—Cu1122.70 (9)C25—N9—Cu2121.47 (9)
C1—N1—Cu1120.80 (9)C23—N10—H10A120.0
C3—N2—H2A120.0C23—N10—H10B120.0
C3—N2—H2B120.0H10A—N10—H10B120.0
H2A—N2—H2B120.0C26—N11—C30116.62 (11)
C10—N3—C6116.61 (11)C26—N11—Cu2121.42 (9)
C10—N3—Cu1120.95 (8)C30—N11—Cu2121.96 (9)
C6—N3—Cu1122.37 (9)C28—N12—H12A120.0
C8—N4—H4A120.0C28—N12—H12B120.0
C8—N4—H4B120.0H12A—N12—H12B120.0
H4A—N4—H4B120.0C31—N13—C35116.72 (11)
C11—N5—C15116.96 (11)C31—N13—Cu2120.80 (9)
C11—N5—Cu1122.09 (8)C35—N13—Cu2122.35 (9)
C15—N5—Cu1120.91 (9)C33—N14—H14A120.0
C13—N6—H6A120.0C33—N14—H14B120.0
C13—N6—H6B120.0H14A—N14—H14B120.0
H6A—N6—H6B120.0C36—N15—C40117.21 (11)
C16—N7—C20116.54 (11)C36—N15—Cu2121.08 (9)
C16—N7—Cu1123.33 (9)C40—N15—Cu2121.39 (9)
C20—N7—Cu1119.96 (9)C38—N16—H16A120.0
C18—N8—H8A120.0C38—N16—H16B120.0
C18—N8—H8B120.0H16A—N16—H16B120.0
H8A—N8—H8B120.0N9—C21—C22123.79 (11)
N1—C1—C2124.04 (12)N9—C21—H21118.1
N1—C1—H1118.0C22—C21—H21118.1
C2—C1—H1118.0C21—C22—C23119.77 (11)
C1—C2—C3119.61 (11)C21—C22—H22120.1
C1—C2—H2120.2C23—C22—H22120.1
C3—C2—H2120.2N10—C23—C24121.81 (11)
N2—C3—C2121.70 (12)N10—C23—C22121.67 (11)
N2—C3—C4121.76 (12)C24—C23—C22116.51 (11)
C2—C3—C4116.53 (11)C25—C24—C23119.55 (11)
C5—C4—C3119.69 (12)C25—C24—H24120.2
C5—C4—H4120.2C23—C24—H24120.2
C3—C4—H4120.2N9—C25—C24123.97 (12)
N1—C5—C4123.77 (12)N9—C25—H25118.0
N1—C5—H5118.1C24—C25—H25118.0
C4—C5—H5118.1N11—C26—C27123.57 (12)
N3—C6—C7123.97 (12)N11—C26—H26118.2
N3—C6—H6118.0C27—C26—H26118.2
C7—C6—H6118.0C26—C27—C28119.91 (12)
C6—C7—C8119.66 (12)C26—C27—H27120.0
C6—C7—H7120.2C28—C27—H27120.0
C8—C7—H7120.2N12—C28—C29121.79 (12)
N4—C8—C7122.44 (11)N12—C28—C27121.76 (12)
N4—C8—C9121.15 (11)C29—C28—C27116.45 (11)
C7—C8—C9116.41 (11)C30—C29—C28119.36 (12)
C10—C9—C8119.74 (11)C30—C29—H29120.3
C10—C9—H9120.1C28—C29—H29120.3
C8—C9—H9120.1N11—C30—C29124.06 (12)
N3—C10—C9123.60 (11)N11—C30—H30118.0
N3—C10—H10118.2C29—C30—H30118.0
C9—C10—H10118.2N13—C31—C32123.80 (13)
N5—C11—C12123.69 (12)N13—C31—H31118.1
N5—C11—H11118.2C32—C31—H31118.1
C12—C11—H11118.2C31—C32—C33119.43 (13)
C11—C12—C13119.42 (12)C31—C32—H32120.3
C11—C12—H12120.3C33—C32—H32120.3
C13—C12—H12120.3N14—C33—C34122.24 (13)
N6—C13—C14121.09 (12)N14—C33—C32121.20 (13)
N6—C13—C12121.88 (12)C34—C33—C32116.56 (12)
C14—C13—C12117.02 (12)C35—C34—C33120.14 (13)
C15—C14—C13119.50 (11)C35—C34—H34119.9
C15—C14—H14120.2C33—C34—H34119.9
C13—C14—H14120.2N13—C35—C34123.33 (13)
N5—C15—C14123.41 (12)N13—C35—H35118.3
N5—C15—H15118.3C34—C35—H35118.3
C14—C15—H15118.3N15—C36—C37123.47 (12)
N7—C16—C17123.80 (12)N15—C36—H36118.3
N7—C16—H16118.1C37—C36—H36118.3
C17—C16—H16118.1C36—C37—C38119.33 (12)
C16—C17—C18119.65 (12)C36—C37—H37120.3
C16—C17—H17120.2C38—C37—H37120.3
C18—C17—H17120.2N16—C38—C37120.96 (12)
N8—C18—C17122.71 (13)N16—C38—C39121.87 (12)
N8—C18—C19120.80 (13)C37—C38—C39117.17 (11)
C17—C18—C19116.49 (12)C40—C39—C38119.49 (12)
C20—C19—C18119.76 (12)C40—C39—H39120.3
C20—C19—H19120.1C38—C39—H39120.3
C18—C19—H19120.1N15—C40—C39123.33 (12)
N7—C20—C19123.73 (12)N15—C40—H40118.3
N7—C20—H20118.1C39—C40—H40118.3
C19—C20—H20118.1H1W1—O1W—H2W1111.7 (14)
N11—Cu2—N15171.22 (5)H1W2—O2W—H2W2107.8 (13)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl2i0.932.683.5955 (13)167
C6—H6···Cl20.932.803.3665 (13)121
C10—H10···Cl10.932.783.4430 (13)129
C20—H20···Cl10.932.643.3522 (13)134
C25—H25···Cl40.932.713.2928 (13)121
C26—H26···N90.932.623.0473 (17)108
C35—H35···Cl40.932.673.3947 (14)136
N4—H4A···O1Wii0.862.383.2094 (17)163
N4—H4B···Cl1iii0.862.433.2893 (13)175
N6—H6A···Cl4iv0.862.823.4066 (13)127
N8—H8B···Cl2iv0.862.563.4021 (13)166
N10—H10B···Cl3v0.862.413.2596 (11)171
N12—H12A···O1W0.862.062.8908 (16)162
N14—H14B···O1Wvi0.862.253.0103 (18)147
N16—H16B···N16vii0.862.523.2036 (17)137
O1W—H1W1···Cl1iii0.83 (1)2.26 (1)3.0614 (12)163 (2)
O1W—H2W1···Cl4viii0.83 (1)2.26 (1)3.0694 (12)164 (2)
C37—H37···Cg1ix0.932.813.5492 (14)137
C39—H39···Cg1x0.932.953.7306 (14)142
N2—H2B···Cg2xi0.862.753.3359 (13)126
C12—H12···Cg30.932.793.6488 (14)154
C14—H14···Cg3iv0.932.833.6193 (13)144
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y, −z+1; (iii) −x+1, −y, −z+1; (iv) x−1, y, z; (v) −x+2, −y+1, −z; (vi) −x+1, −y+1, −z+1; (vii) −x+2, −y+2, −z; (viii) −x+2, −y+1, −z+1; (ix) x, y+1, z; (x) x+1, y+1, z; (xi) x−1, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl2i0.932.683.5955 (13)167
C6—H6···Cl20.932.803.3665 (13)121
C10—H10···Cl10.932.783.4430 (13)129
C20—H20···Cl10.932.643.3522 (13)134
C25—H25···Cl40.932.713.2928 (13)121
C26—H26···N90.932.623.0473 (17)108
C35—H35···Cl40.932.673.3947 (14)136
N4—H4A···O1Wii0.862.383.2094 (17)163
N4—H4B···Cl1iii0.862.433.2893 (13)175
N6—H6A···Cl4iv0.862.823.4066 (13)127
N8—H8B···Cl2iv0.862.563.4021 (13)166
N10—H10B···Cl3v0.862.413.2596 (11)171
N12—H12A···O1W0.862.062.8908 (16)162
N14—H14B···O1Wvi0.862.253.0103 (18)147
N16—H16B···N16vii0.862.523.2036 (17)137
O1W—H1W1···Cl1iii0.83 (1)2.26 (1)3.0614 (12)163 (2)
O1W—H2W1···Cl4viii0.83 (1)2.26 (1)3.0694 (12)164 (2)
C37—H37···Cg1ix0.932.813.5492 (14)137
C39—H39···Cg1x0.932.953.7306 (14)142
N2—H2B···Cg2xi0.862.753.3359 (13)126
C12—H12···Cg30.932.793.6488 (14)154
C14—H14···Cg3iv0.932.833.6193 (13)144
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+2, −y, −z+1; (iii) −x+1, −y, −z+1; (iv) x−1, y, z; (v) −x+2, −y+1, −z; (vi) −x+1, −y+1, −z+1; (vii) −x+2, −y+2, −z; (viii) −x+2, −y+1, −z+1; (ix) x, y+1, z; (x) x+1, y+1, z; (xi) x−1, y−1, z.
Acknowledgements top

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for Science Fund Grant No. 305/PFIZIK/613312. SRJ thanks the Universiti Sains Malaysia for a post-doctoral research fellowship.

references
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