supplementary materials


vm2181 scheme

Acta Cryst. (2012). E68, o3354-o3355    [ doi:10.1107/S1600536812046193 ]

(1R*,2S*)-N,N'-Bis[(E)-1H-pyrrol-2-ylmethylidene]cyclohexane-1,2-diamine monohydrate

K. J. Akerman

Abstract top

The title compound, C16H20N4·H2O, was synthesized from cis-1,2-diaminocyclohexane (a racemic mixture of the (1R,2S) and (1S,2R) enantiomers). The compound crystallized with two molecules (A and B) in the asymmetric unit with a single water solvent molecule per Schiff base molecule. Molecules A and B have similar conformations as illustrated by the least-squares-fit with an r.m.s. deviation of 0.242 Å. The molecules within the asymmetric unit are bridged by hydrogen bonds to the two water molecules, resulting in a heterotetramer. The water molecule acts as both a hydrogen-bond donor and acceptor. The pyrrole-imine units are not co-planar, making an angle of 73.9 (3)° and 76.9 (3)° in molecules A and B, respectively.

Comment top

The R,R and S,S enantiomers of the title compound have been extensively studied both as the metal chelate (Zn(II), Cu(II), Ni(II), Pd(II), Pt(II) and Ti(IV)) and the free ligand (Bacchi et al., 2003; Shan et al., 2008; van den Ancker et al., 2006; Wang et al., 2007 and Zhang et al., 2008) while the mixed R,S enantiomer has received little attention. This is possibly owing to the fact that upon metal chelation the mean plane of the cyclohexyl ring is co-planar with the pyrrole-imine Schiff base moiety for the R,R and S,S enantiomers while in the case of the R,S enantiomer the mean plane of the cyclohexyl ring would be perpendicular to the pyrrole-imine Schiff base moiety; an unusual coordination geometry.

The asymmetric unit of the title compound comprises two molecules, A and B, and two water solvent molecules. The structure of molecule A showing the atom numbering scheme is shown in Figure 1. The geometry of molecules A and B are very similar, this is illustrated by a least squares fit (Figure 2) (Mercury, Macrae et al., 2006). The RMSD for the fit is 0.242 Å. The fit shows that the biggest difference between the two structures is the torsion angle of the pyrrole rings relative to the cyclohexane linkage. The C6—N2—C4—N1 torsion angle is 179.7 (2) and 167.0 (2)° for molecules A and B, respectively. The C11—N3—C16—N4 torsion angle measures 173.5 (2) and 178.9 (2)° for molecules A and B, respectively. The mean imine C=N bond lengths are 1.270 (4) and 1.269 (3) Å for molecules A and B, respectively. These bond lengths highlight the double bond character of the imine bond. The pyrrole-imine moieties of both molecules A and B in the asymmetric unit are not co-planar. The angle subtended by the two seven atom mean planes comprising the pyrrole ring and imine carbon and nitrogen atoms is 73.9 (3)° and 76.9 (3)° for molecules A and B, respectively. This angle allows for hydrogen bonding to two water molecules. Both the imine nitrogen atoms and the pyrrole NH groups are involved in the hydrogen bonding, giving a total of eight hydrogen bonds. The hydrogen bonds result in a water-bridged dimer structure (Figure 3). The hydrogen bonds are considerably shorter than the sum of the van der Waals radii and the bond angles are approaching ideality, suggesting that they are likely to be relatively strong interactions. The hydrogen bond lengths and bond angles are summarized in Table 1.

Related literature top

For a study of the helical structures formed by both the S,S and R,R bis(pyrrolide-imine) ligands as well as the ZnII, CuII and NiII chelates in the solid state, see: Wang et al. (2007). For the solid-state synthesis and X-ray structure of the anhydrous trans racemate of the ligand, see: van den Ancker et al. (2006). For the TiIV chelate of the trans racemic complex, see: Zhang et al. (2008). For the intermolecular interaction-controlled self-assembly and a study of the photophysics of the PtII chelate of the R,R and S,S enantiomers as well as the trans racemic complex, see: Shan et al. (2008). For the X-ray structure and applications of the trans racemate of the PdII chelate as a hydrogenation catalyst, see: Bacchi et al. (2003).

Experimental top

The enatiomerically pure diamine, (1R,2S)-diaminocyclohexane, (0.303 g, 2.65 mmol) was ground in an agate pestle and mortar with pyrrole-2-carboxaldehyde (0.500 g, 5.30 mmol) for 10 minutes. The resulting brown oil was dissolved in dichloromethane and dried over magnesium sulfate to remove the water, a by-product from the condensation reaction. The dichloromethane solution was then concentrated and layered with hexane to re-crystallize the ligand by liquid-liquid difussion (0.512 g, 72% yield). Crystals suitable for single-crystal X-ray crystallography, were obtained from the crystallization process.

Refinement top

The positions of all C-bonded hydrogen atoms were calculated using the standard riding model of SHELXL97 (Sheldrick, 2008) with C—H(aromatic) distances of 0.95 Å and Uiso = 1.2 Ueq, CH(methylene) distances of 0.99 Å and Uiso = 1.2 Ueq and a C—H(methine) distance of 1.00 Å and Uiso = 1.2 Ueq. The pyrrole NH atoms and the hydrogen atoms of the water molecules were located in the difference density map and allowed to refine isotropically.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of molecule A of (1), rendered at 30% probability. Hydrogen atoms are shown as spheres of arbitrary radius. The solvent molecules and the second molecule of the asymmetric unit have been omitted for clarity.
[Figure 2] Fig. 2. Least squares fit of molecules A and B, highlighting their similar geometries. Molecule A is shown in yellow and molecule B is shown in blue. RMSD = 0.242 Å.
[Figure 3] Fig. 3. Contents of the asymmetric unit showing the water-bridged hydrogen-bonded dimer structure. Hydrogen bonds are shown as dashed, purple tubes. The atoms involved in hydrogen bonding have been labelled.
(1R*,2S*)-N,N'-Bis[(E)-1H-pyrrol-2- ylmethylidene]cyclohexane-1,2-diamine monohydrate top
Crystal data top
C16H20N4·H2OF(000) = 1232
Mr = 286.38Dx = 1.166 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3290 reflections
a = 9.7207 (7) Åθ = 3.0–26.0°
b = 18.4183 (13) ŵ = 0.08 mm1
c = 18.2460 (12) ÅT = 296 K
β = 92.721 (7)°Needle, colourless
V = 3263.1 (4) Å30.60 × 0.30 × 0.15 mm
Z = 8
Data collection top
Oxford Diffraction Xcalibur 2 CCD
diffractometer
6428 independent reflections
Radiation source: fine-focus sealed tube3290 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.067
ω scans at fixed θ anglesθmax = 26.1°, θmin = 3.1°
Absorption correction: multi-scan
(Blessing, 1995)
h = 912
Tmin = 0.956, Tmax = 0.989k = 2222
23848 measured reflectionsl = 2222
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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 0.85 w = 1/[σ2(Fo2) + (0.0682P)2]
where P = (Fo2 + 2Fc2)/3
6428 reflections(Δ/σ)max = 0.001
414 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C16H20N4·H2OV = 3263.1 (4) Å3
Mr = 286.38Z = 8
Monoclinic, P21/nMo Kα radiation
a = 9.7207 (7) ŵ = 0.08 mm1
b = 18.4183 (13) ÅT = 296 K
c = 18.2460 (12) Å0.60 × 0.30 × 0.15 mm
β = 92.721 (7)°
Data collection top
Oxford Diffraction Xcalibur 2 CCD
diffractometer
6428 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
3290 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.989Rint = 0.067
23848 measured reflectionsθmax = 26.1°
Refinement top
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.131Δρmax = 0.15 e Å3
S = 0.85Δρmin = 0.19 e Å3
6428 reflectionsAbsolute structure: ?
414 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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
C1A0.1913 (3)0.02963 (13)0.54953 (14)0.0834 (7)
H1A0.11230.05810.54570.100*
C1B0.1477 (4)0.14986 (14)0.40497 (14)0.0960 (8)
H1B0.22690.16800.42910.115*
C2A0.2955 (3)0.03661 (17)0.60134 (15)0.1018 (9)
H2A0.30060.07040.63930.122*
C2B0.0173 (4)0.17302 (14)0.41394 (14)0.0997 (9)
H2B0.00880.21000.44510.120*
C3A0.3926 (3)0.01569 (18)0.58726 (14)0.1030 (9)
H3A0.47500.02330.61410.124*
C3B0.0705 (3)0.13179 (13)0.36854 (12)0.0845 (7)
H3B0.16590.13600.36400.101*
C4A0.3457 (2)0.05500 (14)0.52605 (12)0.0730 (6)
C4B0.0090 (3)0.08341 (11)0.33145 (11)0.0615 (6)
C5A0.4118 (2)0.11473 (14)0.49148 (12)0.0766 (7)
H5A0.49980.12660.50980.092*
C5B0.0379 (2)0.03242 (10)0.27595 (10)0.0549 (5)
H5B0.13230.03070.26480.066*
C6A0.4517 (2)0.21372 (13)0.41631 (11)0.0730 (7)
H6A0.546 (2)0.2008 (3)0.4273 (3)0.088*
C6B0.0344 (2)0.05047 (10)0.17992 (9)0.0503 (5)
H6B0.1358 (19)0.04579 (13)0.18469 (13)0.060*
C7A0.4180 (3)0.28228 (16)0.45948 (14)0.1059 (10)
H7A10.42370.27120.51150.127*
H7A20.48630.31920.45050.127*
C7B0.0038 (2)0.01703 (11)0.10669 (10)0.0626 (6)
H7B10.01590.03460.10730.075*
H7B20.05270.03870.06730.075*
C8A0.2756 (4)0.31233 (15)0.43906 (16)0.1124 (11)
H8A10.26080.35630.46690.135*
H8A20.20640.27720.45180.135*
C8B0.1533 (2)0.02822 (11)0.09196 (11)0.0633 (6)
H8B10.17250.00720.04480.076*
H8B20.21010.00340.12930.076*
C9A0.2600 (3)0.32906 (13)0.35746 (16)0.0992 (9)
H9A10.16640.34460.34520.119*
H9A20.32160.36830.34560.119*
C9B0.1900 (2)0.10788 (11)0.09191 (10)0.0636 (6)
H9B10.14150.13160.05090.076*
H9B20.28810.11320.08580.076*
C10A0.2932 (2)0.26221 (11)0.31272 (12)0.0688 (6)
H10C0.22280.22570.31910.083*
H10D0.29130.27520.26120.083*
C10B0.1521 (2)0.14446 (10)0.16339 (10)0.0546 (5)
H10A0.21160.12610.20340.065*
H10B0.16750.19630.15960.065*
C11B0.0035 (2)0.13095 (10)0.18041 (10)0.0504 (5)
H11B0.0552 (12)0.1553 (5)0.1421 (8)0.060*
C12A0.5241 (2)0.17287 (11)0.23370 (11)0.0575 (5)
H12A0.56080.21870.22570.069*
C12B0.0978 (2)0.22135 (11)0.25033 (11)0.0580 (5)
H12B0.12860.23900.20470.070*
C13A0.6098 (2)0.12312 (12)0.11422 (11)0.0651 (6)
H13A0.64930.16470.09540.078*
C13B0.1349 (2)0.26176 (10)0.31397 (11)0.0568 (5)
C14A0.6021 (2)0.05552 (14)0.08030 (13)0.0747 (7)
H14A0.63590.04370.03500.090*
C14B0.2075 (2)0.32555 (12)0.31707 (14)0.0760 (7)
H14B0.24460.35140.27700.091*
C15A0.5365 (2)0.01026 (13)0.12521 (14)0.0750 (7)
H15A0.51630.03830.11580.090*
C15B0.2160 (2)0.34479 (12)0.39040 (14)0.0760 (7)
H15B0.25920.38570.40840.091*
C16A0.54886 (19)0.11759 (11)0.18053 (10)0.0542 (5)
C16B0.1498 (2)0.29299 (13)0.43048 (13)0.0773 (7)
H16B0.13950.29200.48140.093*
C11A0.4329 (2)0.23015 (11)0.33462 (11)0.0641 (6)
H11A0.50290.26590.32250.077*
N1A0.2222 (2)0.02607 (10)0.50414 (10)0.0681 (5)
N1B0.1010 (2)0.24262 (10)0.38442 (10)0.0657 (5)
N2A0.36308 (17)0.15331 (10)0.43840 (9)0.0634 (5)
N2B0.02667 (16)0.16364 (8)0.25133 (8)0.0515 (4)
N3A0.45633 (16)0.16439 (8)0.29072 (8)0.0564 (4)
N3B0.03694 (15)0.01051 (8)0.24065 (8)0.0490 (4)
N4A0.50504 (19)0.04740 (10)0.18633 (10)0.0622 (5)
N4B0.1423 (3)0.09489 (11)0.35398 (10)0.0752 (6)
O1W0.31430 (19)0.01940 (10)0.29915 (9)0.0662 (4)
O2W0.08724 (17)0.12068 (8)0.39628 (9)0.0597 (4)
H01A0.163 (2)0.0437 (12)0.4667 (13)0.084 (7)*
H01B0.045 (2)0.2011 (13)0.3941 (12)0.088 (8)*
H1W0.344 (3)0.0587 (18)0.3136 (18)0.143 (15)*
H2W0.227 (3)0.0243 (14)0.2780 (15)0.111 (10)*
H3W0.067 (3)0.1230 (13)0.3531 (15)0.097 (10)*
H04A0.452 (2)0.0314 (10)0.2203 (11)0.060 (6)*
H04B0.213 (3)0.0690 (14)0.3444 (14)0.093 (9)*
H4W0.181 (3)0.1399 (14)0.4011 (14)0.116 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.1007 (19)0.0744 (16)0.0764 (17)0.0119 (14)0.0177 (16)0.0254 (14)
C1B0.135 (3)0.0733 (17)0.0773 (18)0.0007 (17)0.0223 (17)0.0273 (14)
C2A0.116 (2)0.119 (2)0.0715 (19)0.0344 (19)0.0133 (18)0.0394 (16)
C2B0.159 (3)0.0757 (18)0.0619 (17)0.0357 (19)0.0142 (18)0.0187 (13)
C3A0.0846 (18)0.164 (3)0.0595 (16)0.0235 (19)0.0083 (14)0.0293 (17)
C3B0.115 (2)0.0806 (17)0.0571 (14)0.0313 (15)0.0029 (14)0.0140 (13)
C4A0.0652 (14)0.1068 (19)0.0467 (13)0.0077 (14)0.0012 (11)0.0139 (13)
C4B0.0913 (17)0.0508 (13)0.0424 (12)0.0126 (11)0.0028 (12)0.0006 (10)
C5A0.0606 (13)0.123 (2)0.0460 (13)0.0104 (14)0.0041 (11)0.0040 (14)
C5B0.0678 (13)0.0512 (12)0.0453 (11)0.0057 (10)0.0019 (10)0.0054 (10)
C6A0.0754 (14)0.0983 (18)0.0458 (12)0.0344 (13)0.0070 (11)0.0200 (12)
C6B0.0536 (11)0.0563 (13)0.0399 (11)0.0028 (9)0.0095 (9)0.0005 (9)
C7A0.150 (3)0.115 (2)0.0548 (15)0.068 (2)0.0248 (17)0.0360 (15)
C7B0.0786 (15)0.0648 (14)0.0428 (12)0.0001 (11)0.0125 (10)0.0110 (10)
C8A0.161 (3)0.0830 (19)0.098 (2)0.038 (2)0.059 (2)0.0525 (16)
C8B0.0810 (15)0.0716 (15)0.0368 (11)0.0136 (11)0.0026 (10)0.0119 (10)
C9A0.139 (2)0.0598 (15)0.102 (2)0.0112 (15)0.0414 (19)0.0284 (14)
C9B0.0746 (14)0.0794 (16)0.0368 (11)0.0086 (11)0.0044 (10)0.0102 (10)
C10A0.0991 (18)0.0484 (12)0.0598 (14)0.0084 (12)0.0138 (12)0.0085 (10)
C10B0.0754 (13)0.0478 (11)0.0401 (11)0.0042 (10)0.0012 (10)0.0064 (9)
C11B0.0691 (13)0.0499 (12)0.0312 (10)0.0088 (10)0.0072 (9)0.0047 (8)
C12A0.0641 (12)0.0622 (13)0.0465 (12)0.0104 (10)0.0053 (10)0.0036 (10)
C12B0.0776 (14)0.0500 (12)0.0454 (12)0.0067 (11)0.0061 (10)0.0032 (9)
C13A0.0718 (14)0.0757 (15)0.0491 (12)0.0018 (11)0.0163 (11)0.0016 (11)
C13B0.0666 (13)0.0474 (12)0.0562 (13)0.0080 (10)0.0004 (10)0.0043 (10)
C14A0.0742 (15)0.0912 (18)0.0603 (15)0.0071 (13)0.0209 (12)0.0173 (13)
C14B0.0962 (17)0.0586 (14)0.0720 (16)0.0218 (12)0.0082 (13)0.0002 (12)
C15A0.0776 (15)0.0657 (15)0.0831 (17)0.0064 (12)0.0172 (13)0.0204 (13)
C15B0.0831 (16)0.0575 (14)0.0882 (19)0.0126 (12)0.0123 (14)0.0159 (13)
C16A0.0593 (12)0.0586 (13)0.0449 (12)0.0013 (10)0.0046 (10)0.0016 (10)
C16B0.0989 (17)0.0711 (16)0.0631 (15)0.0170 (14)0.0171 (13)0.0071 (13)
C11A0.0831 (15)0.0620 (13)0.0484 (12)0.0293 (12)0.0154 (11)0.0167 (10)
N1A0.0729 (13)0.0778 (13)0.0533 (11)0.0068 (11)0.0006 (10)0.0151 (10)
N1B0.0864 (13)0.0570 (11)0.0545 (12)0.0201 (10)0.0112 (10)0.0006 (9)
N2A0.0669 (11)0.0879 (13)0.0353 (9)0.0162 (9)0.0004 (8)0.0047 (9)
N2B0.0695 (10)0.0470 (9)0.0377 (9)0.0084 (8)0.0005 (8)0.0002 (7)
N3A0.0692 (11)0.0614 (11)0.0394 (9)0.0114 (8)0.0113 (8)0.0074 (8)
N3B0.0602 (10)0.0465 (9)0.0399 (9)0.0024 (8)0.0024 (8)0.0005 (7)
N4A0.0702 (11)0.0622 (12)0.0555 (11)0.0013 (9)0.0150 (10)0.0001 (9)
N4B0.0966 (17)0.0629 (13)0.0653 (13)0.0041 (12)0.0064 (12)0.0177 (10)
O1W0.0643 (10)0.0714 (12)0.0625 (10)0.0013 (9)0.0032 (8)0.0150 (8)
O2W0.0682 (10)0.0679 (10)0.0427 (9)0.0000 (7)0.0019 (8)0.0094 (7)
Geometric parameters (Å, º) top
C1A—C2A1.358 (3)C9A—H9A20.9700
C1A—N1A1.361 (3)C9B—C10B1.528 (3)
C1A—H1A0.9300C9B—H9B10.9700
C1B—C2B1.355 (4)C9B—H9B20.9700
C1B—N4B1.374 (3)C10A—C11A1.517 (3)
C1B—H1B0.9300C10A—H10C0.9700
C2A—C3A1.381 (4)C10A—H10D0.9700
C2A—H2A0.9300C10B—C11B1.512 (3)
C2B—C3B1.387 (3)C10B—H10A0.9700
C2B—H2B0.9300C10B—H10B0.9700
C3A—C4A1.390 (3)C11B—N2B1.469 (2)
C3A—H3A0.9300C11B—H11B0.9894
C3B—C4B1.378 (3)C12A—N3A1.267 (2)
C3B—H3B0.9300C12A—C16A1.435 (3)
C4A—N1A1.356 (3)C12A—H12A0.9300
C4A—C5A1.435 (3)C12B—N2B1.268 (2)
C4B—N4B1.357 (3)C12B—C13B1.439 (3)
C4B—C5B1.439 (3)C12B—H12B0.9300
C5A—N2A1.274 (3)C13A—C16A1.376 (3)
C5A—H5A0.9300C13A—C14A1.391 (3)
C5B—N3B1.271 (2)C13A—H13A0.9300
C5B—H5B0.9300C13B—N1B1.358 (2)
C6A—N2A1.475 (3)C13B—C14B1.373 (3)
C6A—C11A1.523 (3)C14A—C15A1.350 (3)
C6A—C7A1.532 (3)C14A—H14A0.9300
C6A—H6A0.9609C14B—C15B1.390 (3)
C6B—N3B1.476 (2)C14B—H14B0.9300
C6B—C11B1.527 (3)C15A—N4A1.356 (3)
C6B—C7B1.533 (3)C15A—H15A0.9300
C6B—H6B0.9975C15B—C16B1.347 (3)
C7A—C8A1.520 (4)C15B—H15B0.9300
C7A—H7A10.9700C16A—N4A1.367 (3)
C7A—H7A20.9700C16B—N1B1.353 (3)
C7B—C8B1.505 (3)C16B—H16B0.9300
C7B—H7B10.9700C11A—N3A1.476 (2)
C7B—H7B20.9700C11A—H11A0.9800
C8A—C9A1.521 (4)N1A—H01A0.93 (2)
C8A—H8A10.9700N1B—H01B0.95 (2)
C8A—H8A20.9700N4A—H04A0.88 (2)
C8B—C9B1.510 (3)N4B—H04B0.86 (2)
C8B—H8B10.9700O1W—H1W0.82 (3)
C8B—H8B20.9700O1W—H2W0.92 (3)
C9A—C10A1.520 (3)O2W—H3W0.81 (3)
C9A—H9A10.9700O2W—H4W0.98 (3)
C2A—C1A—N1A108.4 (3)C8B—C9B—H9B2109.4
C2A—C1A—H1A125.8C10B—C9B—H9B2109.4
N1A—C1A—H1A125.8H9B1—C9B—H9B2108.0
C2B—C1B—N4B107.9 (3)C11A—C10A—C9A112.6 (2)
C2B—C1B—H1B126.0C11A—C10A—H10C109.1
N4B—C1B—H1B126.0C9A—C10A—H10C109.1
C1A—C2A—C3A107.3 (2)C11A—C10A—H10D109.1
C1A—C2A—H2A126.3C9A—C10A—H10D109.1
C3A—C2A—H2A126.3H10C—C10A—H10D107.8
C1B—C2B—C3B107.9 (2)C11B—C10B—C9B111.97 (16)
C1B—C2B—H2B126.0C11B—C10B—H10A109.2
C3B—C2B—H2B126.0C9B—C10B—H10A109.2
C2A—C3A—C4A108.2 (2)C11B—C10B—H10B109.2
C2A—C3A—H3A125.9C9B—C10B—H10B109.2
C4A—C3A—H3A125.9H10A—C10B—H10B107.9
C4B—C3B—C2B107.7 (2)N2B—C11B—C10B110.24 (15)
C4B—C3B—H3B126.2N2B—C11B—C6B110.17 (14)
C2B—C3B—H3B126.2C10B—C11B—C6B113.02 (15)
N1A—C4A—C3A106.5 (2)N2B—C11B—H11B107.7
N1A—C4A—C5A125.5 (2)C10B—C11B—H11B107.7
C3A—C4A—C5A128.0 (3)C6B—C11B—H11B107.7
N4B—C4B—C3B107.5 (2)N3A—C12A—C16A125.31 (19)
N4B—C4B—C5B125.49 (19)N3A—C12A—H12A117.3
C3B—C4B—C5B127.0 (2)C16A—C12A—H12A117.3
N2A—C5A—C4A127.1 (2)N2B—C12B—C13B125.39 (18)
N2A—C5A—H5A116.4N2B—C12B—H12B117.3
C4A—C5A—H5A116.4C13B—C12B—H12B117.3
N3B—C5B—C4B126.36 (19)C16A—C13A—C14A108.0 (2)
N3B—C5B—H5B116.8C16A—C13A—H13A126.0
C4B—C5B—H5B116.8C14A—C13A—H13A126.0
N2A—C6A—C11A111.87 (16)N1B—C13B—C14B106.57 (18)
N2A—C6A—C7A109.82 (18)N1B—C13B—C12B124.79 (18)
C11A—C6A—C7A108.7 (2)C14B—C13B—C12B128.6 (2)
N2A—C6A—H6A108.8C15A—C14A—C13A107.43 (19)
C11A—C6A—H6A108.8C15A—C14A—H14A126.3
C7A—C6A—H6A108.8C13A—C14A—H14A126.3
N3B—C6B—C11B112.01 (14)C13B—C14B—C15B108.2 (2)
N3B—C6B—C7B109.23 (15)C13B—C14B—H14B125.9
C11B—C6B—C7B109.08 (15)C15B—C14B—H14B125.9
N3B—C6B—H6B108.8C14A—C15A—N4A108.6 (2)
C11B—C6B—H6B108.8C14A—C15A—H15A125.7
C7B—C6B—H6B108.8N4A—C15A—H15A125.7
C8A—C7A—C6A112.9 (2)C16B—C15B—C14B107.0 (2)
C8A—C7A—H7A1109.0C16B—C15B—H15B126.5
C6A—C7A—H7A1109.0C14B—C15B—H15B126.5
C8A—C7A—H7A2109.0N4A—C16A—C13A106.68 (18)
C6A—C7A—H7A2109.0N4A—C16A—C12A123.78 (18)
H7A1—C7A—H7A2107.8C13A—C16A—C12A129.4 (2)
C8B—C7B—C6B112.12 (16)C15B—C16B—N1B108.7 (2)
C8B—C7B—H7B1109.2C15B—C16B—H16B125.6
C6B—C7B—H7B1109.2N1B—C16B—H16B125.6
C8B—C7B—H7B2109.2N3A—C11A—C10A109.62 (16)
C6B—C7B—H7B2109.2N3A—C11A—C6A110.71 (18)
H7B1—C7B—H7B2107.9C10A—C11A—C6A113.55 (18)
C7A—C8A—C9A111.2 (2)N3A—C11A—H11A107.6
C7A—C8A—H8A1109.4C10A—C11A—H11A107.6
C9A—C8A—H8A1109.4C6A—C11A—H11A107.6
C7A—C8A—H8A2109.4C4A—N1A—C1A109.6 (2)
C9A—C8A—H8A2109.4C4A—N1A—H01A126.1 (14)
H8A1—C8A—H8A2108.0C1A—N1A—H01A124.1 (14)
C7B—C8B—C9B111.30 (17)C16B—N1B—C13B109.48 (19)
C7B—C8B—H8B1109.4C16B—N1B—H01B130.6 (14)
C9B—C8B—H8B1109.4C13B—N1B—H01B119.7 (14)
C7B—C8B—H8B2109.4C5A—N2A—C6A115.31 (19)
C9B—C8B—H8B2109.4C12B—N2B—C11B117.55 (15)
H8B1—C8B—H8B2108.0C12A—N3A—C11A116.37 (16)
C10A—C9A—C8A110.3 (2)C5B—N3B—C6B115.52 (16)
C10A—C9A—H9A1109.6C15A—N4A—C16A109.28 (19)
C8A—C9A—H9A1109.6C15A—N4A—H04A125.2 (13)
C10A—C9A—H9A2109.6C16A—N4A—H04A124.7 (13)
C8A—C9A—H9A2109.6C4B—N4B—C1B109.0 (2)
H9A1—C9A—H9A2108.1C4B—N4B—H04B127.7 (17)
C8B—C9B—C10B111.18 (15)C1B—N4B—H04B122.7 (18)
C8B—C9B—H9B1109.4H1W—O1W—H2W110 (3)
C10B—C9B—H9B1109.4H3W—O2W—H4W105 (2)
N1A—C1A—C2A—C3A0.2 (3)C14A—C13A—C16A—N4A0.0 (2)
N4B—C1B—C2B—C3B0.4 (3)C14A—C13A—C16A—C12A176.2 (2)
C1A—C2A—C3A—C4A0.2 (3)N3A—C12A—C16A—N4A2.1 (3)
C1B—C2B—C3B—C4B0.3 (3)N3A—C12A—C16A—C13A173.5 (2)
C2A—C3A—C4A—N1A0.1 (3)C14B—C15B—C16B—N1B0.0 (3)
C2A—C3A—C4A—C5A179.8 (2)C9A—C10A—C11A—N3A178.26 (18)
C2B—C3B—C4B—N4B0.1 (3)C9A—C10A—C11A—C6A53.9 (2)
C2B—C3B—C4B—C5B176.8 (2)N2A—C6A—C11A—N3A55.2 (2)
N1A—C4A—C5A—N2A5.0 (4)C7A—C6A—C11A—N3A176.66 (18)
C3A—C4A—C5A—N2A174.8 (3)N2A—C6A—C11A—C10A68.6 (2)
N4B—C4B—C5B—N3B1.5 (3)C7A—C6A—C11A—C10A52.9 (2)
C3B—C4B—C5B—N3B177.9 (2)C3A—C4A—N1A—C1A0.0 (3)
N2A—C6A—C7A—C8A67.8 (3)C5A—C4A—N1A—C1A179.9 (2)
C11A—C6A—C7A—C8A54.9 (3)C2A—C1A—N1A—C4A0.2 (3)
N3B—C6B—C7B—C8B66.8 (2)C15B—C16B—N1B—C13B0.3 (3)
C11B—C6B—C7B—C8B56.0 (2)C14B—C13B—N1B—C16B0.4 (2)
C6A—C7A—C8A—C9A57.4 (3)C12B—C13B—N1B—C16B179.0 (2)
C6B—C7B—C8B—C9B57.8 (2)C4A—C5A—N2A—C6A177.1 (2)
C7A—C8A—C9A—C10A54.9 (3)C11A—C6A—N2A—C5A148.9 (2)
C7B—C8B—C9B—C10B55.1 (2)C7A—C6A—N2A—C5A90.3 (3)
C8A—C9A—C10A—C11A53.4 (3)C13B—C12B—N2B—C11B178.54 (18)
C8B—C9B—C10B—C11B52.8 (2)C10B—C11B—N2B—C12B105.68 (19)
C9B—C10B—C11B—N2B176.98 (15)C6B—C11B—N2B—C12B128.92 (18)
C9B—C10B—C11B—C6B53.2 (2)C16A—C12A—N3A—C11A174.75 (18)
N3B—C6B—C11B—N2B56.5 (2)C10A—C11A—N3A—C12A95.5 (2)
C7B—C6B—C11B—N2B177.59 (15)C6A—C11A—N3A—C12A138.48 (19)
N3B—C6B—C11B—C10B67.27 (19)C4B—C5B—N3B—C6B172.32 (17)
C7B—C6B—C11B—C10B53.8 (2)C11B—C6B—N3B—C5B134.21 (17)
N2B—C12B—C13B—N1B1.5 (3)C7B—C6B—N3B—C5B104.84 (19)
N2B—C12B—C13B—C14B177.8 (2)C14A—C15A—N4A—C16A0.9 (3)
C16A—C13A—C14A—C15A0.5 (3)C13A—C16A—N4A—C15A0.5 (2)
N1B—C13B—C14B—C15B0.4 (3)C12A—C16A—N4A—C15A175.93 (18)
C12B—C13B—C14B—C15B179.0 (2)C3B—C4B—N4B—C1B0.1 (3)
C13A—C14A—C15A—N4A0.8 (3)C5B—C4B—N4B—C1B177.1 (2)
C13B—C14B—C15B—C16B0.3 (3)C2B—C1B—N4B—C4B0.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···N3A0.82 (3)2.28 (3)3.014 (2)149 (3)
O1W—H2W···N3B0.92 (3)1.96 (3)2.857 (2)166 (3)
O2W—H3W···N2B0.80 (3)2.16 (3)2.927 (2)159 (3)
O2W—H4W···N2A0.98 (3)1.88 (3)2.819 (2)159 (2)
N1A—H01A···O2W0.93 (2)2.03 (2)2.896 (2)154 (2)
N1B—H01B···O2W0.95 (2)1.96 (2)2.899 (2)169 (2)
N4A—H04A···O1W0.88 (2)2.02 (2)2.882 (3)166 (2)
N4B—H04B···O1W0.86 (3)2.09 (3)2.896 (3)155 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···N3A0.82 (3)2.28 (3)3.014 (2)149 (3)
O1W—H2W···N3B0.92 (3)1.96 (3)2.857 (2)166 (3)
O2W—H3W···N2B0.80 (3)2.16 (3)2.927 (2)159 (3)
O2W—H4W···N2A0.98 (3)1.88 (3)2.819 (2)159 (2)
N1A—H01A···O2W0.93 (2)2.03 (2)2.896 (2)154 (2)
N1B—H01B···O2W0.95 (2)1.96 (2)2.899 (2)169 (2)
N4A—H04A···O1W0.88 (2)2.02 (2)2.882 (3)166 (2)
N4B—H04B···O1W0.86 (3)2.09 (3)2.896 (3)155 (2)
Acknowledgements top

I would like to thank the University of KwaZulu-Natal for the use of their facilities and the National Research Foundation (South Africa) for funding.

references
References top

Ancker, T. R. van den, Cave, G. W. V. & Raston, C. L. (2006). Green Chem. 8, 50–53.

Bacchi, A., Carcelli, M., Gabba, L., Ianelli, S., Pelagatti, P., Pelizzi, G. & Rogolino, D. (2003). Inorg. Chim. Acta, 342, 229–235.

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.

Shan, X.-F., Wang, D.-H., Tung, C.-H. & Wu, L.-Z. (2008). Tetrahedron, 64, 5577–5582.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, Y., Fu, H., Shen, F., Sheng, X., Peng, A., Gu, Z., Ma, H., Ma, J. S. & Yao, J. (2007). Inorg. Chem. 46, 3548–3556.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Zhang, X.-Q., Xu, B., Li, Y.-H. & Li, W. (2008). Acta Cryst. E64, m437–?.