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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 1| January 2014| Pages o83-o84

1-(2,3-Di­hy­droxy­prop­yl)-4-{2-[4-(di­methyl­amino)­phen­yl]vin­yl}pyridinium chloride

aCallaghan Innovation, PO Box 31-310, Lower Hutt, New Zealand
*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 28 November 2013; accepted 8 December 2013; online 21 December 2013)

The title compound, C18H23N2O2+·Cl, crystallizes with two independent cations and anions per cell. Each cation has twofold rotational disorder about the linking vinyl groups but with unequal occupancies [0.963 (5):0.037 (5) and 0.860 (8):0.140 (8)]. The two independent cations are close to being related by an inversion centre but the data does not support the expected centrosymmetric space-group assignment. The conclusion is that the differing rotational disorder has lead to an overall non-centrosymmetric lattice. In the crystal, the mol­ecules pack in layers parallel to (133) and (-13-3), chain-linked with motif C12(7) by the di­hydroxy­propyl O–H⋯Cl⋯H–O hydrogen bonds. Other lattice binding is provided by O—H⋯Cl, C—H⋯Cl and C—H⋯N inter­actions.

Related literature

For applications of organic push–pull chromophores, see: Kay et al. (2004[Kay, A. J., Woolhouse, A. D., Zhao, Y. & Clays, K. (2004). J. Mater. Chem. 14, 1321-1330.]); Bass et al. (2001[Bass, M., Enoch, J. M., Stryland, E. W. V. & Wolfe, W. L. (2001). In Handbook of Optics IV: Fibre Optics and Nonlinear Optics. New York: Academic Press.]); Prasad et al. (1988[Prasad, P. N. & Ulrich, D. R. (1988). In Nonlinear Optical and Electro active Polymers. New York: Plenum.]). For a related example of rotational disorder, see: Moreno-Fuquen et al. (2009[Moreno-Fuquen, R., Dvries, R., Theodoro, J. & Ellena, J. (2009). Acta Cryst. E65, o1371.]). For details of the synthesis, see: Kay et al. (2001[Kay, A. J., Woolhouse, A. D., Gainsford, G. J., Haskell, T. G., Barnes, T. H., McKinnie, I. T. & Wyss, C. P. (2001). J. Mater. Chem. 11, 996-1002.]). For hydrogen-bond motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C18H23N2O2+·Cl

  • Mr = 334.83

  • Monoclinic, P 21

  • a = 8.4452 (3) Å

  • b = 13.2433 (5) Å

  • c = 15.3649 (6) Å

  • β = 100.077 (3)°

  • V = 1691.94 (11) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.24 mm−1

  • T = 123 K

  • 0.55 × 0.10 × 0.09 mm

Data collection
  • Bruker–Nonius APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.651, Tmax = 0.746

  • 38193 measured reflections

  • 7581 independent reflections

  • 5545 reflections with I > 2σ(I)

  • Rint = 0.063

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.096

  • S = 1.02

  • 7581 reflections

  • 474 parameters

  • 13 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.20 e Å−3

  • Absolute structure: Flack parameter determined using 2152 quotients [(I+)−(I)]/[(I+)+(I)] (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])

  • Absolute structure parameter: 0.07 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1O⋯Cl1 0.83 (3) 2.20 (3) 3.024 (3) 174 (4)
O2—H2O⋯Cl1i 0.83 (3) 2.27 (3) 3.086 (3) 169 (4)
C2—H2⋯O2′i 0.95 2.40 3.222 (5) 145
C5A—H5A⋯Cl2ii 0.95 2.78 3.687 (5) 159
C8—H8A⋯N2ii 0.99 2.65 3.637 (5) 176
O1′—H1O′⋯Cl2 0.84 (3) 2.25 (3) 3.083 (3) 171 (4)
O2′—H2O′⋯Cl2iii 0.83 (3) 2.29 (3) 3.104 (3) 169 (4)
C6′—H6′⋯O2iii 0.95 2.40 3.236 (6) 147
Symmetry codes: (i) x+1, y, z; (ii) [-x+1, y-{\script{1\over 2}}, -z+1]; (iii) x-1, y, z.

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and Mercury.

Supporting information


Comment top

Organic push–pull chromophores with large second-order nonlinear optical (NLO) properties are in demand due to their potential applications in photonic devices and optical information processing (Kay et al., 2004; Bass et al., 2001; Prasad et al., 1988). A significant number of organic compounds available in the literature with large molecular NLO responses contain N,N-disubstituted anilines as this nucleus is an excellent electron donor. Due to the lack of tethering functionality of these chromophores, the possibility of synthesizing polymer containing chromophores is restricted. In this work, we have synthesized a new NLO chromophore containing an N,N-dimethyl aniline donor and an acceptor based on the dihydroxypropyl pyridinium chloride. The dihydroxypropyl substituent on the acceptor pyridinium nucleus will allow for covalent attachment of the molecule to a polymer backbone.

The asymmetric unit of the title compound (I) contains two independent 1-(2,3-dihydroxy-propyl)-4-[2-(4-dimethylamino-phenyl)-vinyl]-pyridinium cations (with primed and unprimed labels) and chloride anions almost related by an inversion centre (Fig. 1) in space group P21. The screw axis and the c glide defining data number, average intensities and ratio of intensity/standard deviations were 61, 1/5, 0.4 and 906, 1.9, 3.1 respectively. The corresponding centosymmetric, and more usual, space group found for these compounds, P21/c was rejected through the small but significant presence of the required glide plane absences; this was confirmed in attempted least squares refinements. At the conclusion of both space group refinements, the difference Fourier maps show the presence of two partially occupied rotational conformers about the alkene atoms (C9C10, C9' C10') apparently confined to the vinyl linking atoms, also related by the same inversion centre (Fig. 2). Inclusion of the carbon atoms located on the Fourier difference map (see experimental) improved the agreement factors by about ~0.7% and results in a featureless difference map. Such rotational disorder is not uncommon amongst compounds containing CC and CN linkages: for example see Moreno-Fuquen et al. (2009).

The two cations (Fig 1) are very similar with RMS fits of 0.020 Å and 1.28° (PLATON, Spek, 2009); excluding the dihydroxy end groups, they are approximately planar (maximum deviations from the 18 atom planes are 0.055 (4) & 0.057 (5) Å for atoms C16 & C16') corresponding to the angle between the phenyl and pyridinium rings of 1.6 (2) & 2.8 (2)° for the unprimed and primed cations respectively.

The molecules pack in layers parallel to (133) and (133 planes), chain-linked by dihydroxypropyl O—H···Cl···H—O hydrogen bonds with motif C12(7) (Bernstein et al., 1995). Other lattice binding is provided by O—H···Cl and C—H···Cl, C—H···N interactions (Table 1).

Related literature top

For applications of organic push–pull chromophores, see: Kay et al. (2004); Bass et al. (2001); Prasad et al. (1988). For a related example of rotational disorder, see: Moreno-Fuquen et al. (2009). For details of the synthesis, see: Kay et al. (2001). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

We synthesized the title compound by following the procedure in Kay et al. (2001). Single crystals were grown by slow ethyl acetate diffusion into a methanol solution of the compound.

Refinement top

Indications from the final solution were that the structure could be refined in the centrosymmetric space group P21/c (viz. 95% in agreeement according to a PLATON analysis (Spek, 2009), with each molecule except atoms O1 & O1' related by inversion symmetry). The dataset does not support this with 984 glide plane systematic absences found to be weakly but significantly present out of the total set of 38305. Our experience with these planar NLO molecules is that they frequently form crystals with centrosymmetrically related molecules. In addition at the R1 value of 0.049, residual peaks in the same plane as the target molecules formed recognizable partial occupancy two fold rotational cation atoms, about the C9C10 & C9'C10' linkages (Figure 2).

The defined atoms were paired with the corresponding two major conformer cation atoms (a & b labels) and corresponding H atoms added in calculated positions where observed on the difference maps. H atoms on the located phenyl pyridinium C atoms were not resolved and so were fixed in calculated positions. All non-hydrogen atoms in the partially occupied minor rotamers were given a single group isotropic thermal parameter, which refined to 0.005 (3) A2. It was possible to model a chemically reasonable model using the SHELXL SAME controlling parameters (but only) with the pyridinium and phenyl rings treated independently & occupancies fixed. We elected to remain with the linked group occupancy refinement model presented here. Using SADI, the bond lengths C9C10, C4–C9, C10–C11,C11—C12 and O–H were restrained to the same lengths. The final occupancies for major(A): minor(B) rotamers were 0.963 (5):0.037 (5)(unprimed a:b) and 0.860 (8):0.140 (8) (primed a:b).

Six reflections with Fo<<Fc at low angle were omitted on the basis of background scatter and 2 were OMITted as outliers with Δ|(Fo2-Fc2)|/σ(Fo2) > 4.5. A l l carbon-bound H atoms were constrained to their expected geometries [C—H 0.95,0.98, 0.99 Å] and refined with Uiso 1.2 times the Ueq of their parent atom except for the minor rotamer(b) H atoms with Uiso=1.5Ueq of their parent atom. All other non-hydrogen atoms were refined with anisotropic thermal parameters.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Figures top
[Figure 1] Fig. 1. Labelling of the major(a) conformer cations and anions of the title compound, with 50% thermal ellipsoids (Farrugia, 2012).
[Figure 2] Fig. 2. The total contents of the asymmetric unit, as for Fig. 1, with the minor cation rotamer (labelled b atoms) shown with filled bonds and major rotamer atoms (labelled a) connected with dotted bonds. The centre of the rotation is shown by inclusion of the C9 & C10 (a & b)labels.
[Figure 3] Fig. 3. Packing diagram of (I) without H atoms for clarity. Hydrogen bonds shown as dashed blue lines (Mercury; Macrae et al., 2006). Symmetry codes: (i) 1 + x, y, z (ii) -1 + x, y, z (iii) 1 - x, 1/2 + y, 1 - z (iv) 2 - x, 1/2 + y, 1 - z.
1-(2,3-Dihydroxypropyl)-4-{2-[4-(dimethylamino)phenyl]vinyl}pyridinium chloride top
Crystal data top
C18H23N2O2+·ClF(000) = 712
Mr = 334.83Dx = 1.314 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 8.4452 (3) ÅCell parameters from 4999 reflections
b = 13.2433 (5) Åθ = 2.7–23.4°
c = 15.3649 (6) ŵ = 0.24 mm1
β = 100.077 (3)°T = 123 K
V = 1691.94 (11) Å3Needle, red
Z = 40.55 × 0.10 × 0.09 mm
Data collection top
Bruker–Nonius APEXII CCD area-detector
diffractometer
7581 independent reflections
Radiation source: fine-focus sealed tube5545 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
Detector resolution: 8.333 pixels mm-1θmax = 27.3°, θmin = 2.6°
ϕ and ω scansh = 1010
Absorption correction: multi-scan
(Blessing, 1995)
k = 1717
Tmin = 0.651, Tmax = 0.746l = 1919
38193 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.042 w = 1/[σ2(Fo2) + (0.0362P)2 + 0.2405P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.096(Δ/σ)max = 0.001
S = 1.02Δρmax = 0.18 e Å3
7581 reflectionsΔρmin = 0.20 e Å3
474 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
13 restraintsExtinction coefficient: 0.0039 (10)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack parameter determined using 2152 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.07 (4)
Crystal data top
C18H23N2O2+·ClV = 1691.94 (11) Å3
Mr = 334.83Z = 4
Monoclinic, P21Mo Kα radiation
a = 8.4452 (3) ŵ = 0.24 mm1
b = 13.2433 (5) ÅT = 123 K
c = 15.3649 (6) Å0.55 × 0.10 × 0.09 mm
β = 100.077 (3)°
Data collection top
Bruker–Nonius APEXII CCD area-detector
diffractometer
7581 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
5545 reflections with I > 2σ(I)
Tmin = 0.651, Tmax = 0.746Rint = 0.063
38193 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096Δρmax = 0.18 e Å3
S = 1.02Δρmin = 0.20 e Å3
7581 reflectionsAbsolute structure: Flack parameter determined using 2152 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
474 parametersAbsolute structure parameter: 0.07 (4)
13 restraints
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl10.46974 (12)0.13741 (8)0.18879 (7)0.0391 (3)
O10.8050 (3)0.2226 (2)0.20024 (17)0.0340 (6)
H1O0.716 (4)0.196 (3)0.200 (3)0.041*
O21.1625 (3)0.2328 (2)0.2362 (2)0.0367 (8)
H2O1.241 (4)0.211 (4)0.216 (3)0.044*
N10.8014 (4)0.2692 (2)0.3860 (2)0.0238 (8)
N20.2944 (4)0.4615 (3)0.6126 (2)0.0267 (8)
C10.9463 (5)0.2493 (3)0.3480 (3)0.0283 (10)
H1A1.03120.22100.39420.034*
H1B0.98660.31350.32720.034*
C20.6990 (6)0.3426 (3)0.3522 (3)0.0291 (10)
H20.72220.38260.30460.035*
C3A0.5613 (6)0.3606 (4)0.3857 (3)0.0273 (11)0.963 (5)
H3A0.48950.41220.36060.033*0.963 (5)
C4A0.5256 (6)0.3031 (4)0.4569 (3)0.0224 (10)0.963 (5)
C5A0.6362 (6)0.2279 (4)0.4900 (3)0.0272 (12)0.963 (5)
H5A0.61770.18730.53820.033*0.963 (5)
C60.7688 (5)0.2128 (3)0.4541 (3)0.0306 (10)
H60.84170.16080.47730.037*
C70.9110 (4)0.1751 (3)0.2706 (2)0.0257 (9)
H70.85840.11330.28980.031*
C81.0658 (5)0.1459 (3)0.2410 (3)0.0298 (10)
H8A1.12510.09690.28330.036*
H8B1.04160.11320.18220.036*
C9A0.3844 (5)0.3174 (3)0.4975 (3)0.0274 (11)0.963 (5)
H9A0.37030.27330.54440.033*0.963 (5)
C10A0.2722 (5)0.3887 (3)0.4733 (3)0.0243 (11)0.963 (5)
H10A0.28720.43190.42610.029*0.963 (5)
C11A0.1307 (5)0.4060 (4)0.5123 (3)0.0221 (10)0.963 (5)
C12A0.0194 (6)0.4797 (4)0.4758 (3)0.0262 (11)0.963 (5)
H12A0.03980.51750.42640.031*0.963 (5)
C130.1171 (5)0.4989 (3)0.5090 (3)0.0257 (10)
H130.18780.55060.48290.031*
C140.1560 (5)0.4442 (3)0.5807 (3)0.0239 (9)
C150.0453 (5)0.3693 (3)0.6177 (3)0.0287 (10)
H150.06660.33080.66650.034*
C160.0916 (5)0.3513 (3)0.5845 (3)0.0288 (10)
H160.16320.30020.61090.035*
C170.3366 (5)0.4042 (3)0.6852 (3)0.0317 (10)
H17A0.39280.34230.66240.038*
H17B0.40700.44470.71570.038*
H17C0.23870.38650.72660.038*
C180.3998 (5)0.5442 (3)0.5770 (3)0.0305 (10)
H18A0.34360.60850.59030.037*
H18B0.49680.54320.60380.037*
H18C0.43000.53630.51280.037*
Cl20.52229 (11)0.62109 (8)0.32090 (6)0.0353 (3)
O1'0.1812 (3)0.67503 (19)0.22476 (18)0.0358 (6)
H1O'0.276 (3)0.668 (3)0.251 (2)0.043*
O2'0.1666 (4)0.5388 (2)0.2646 (2)0.0375 (8)
H2O'0.256 (4)0.558 (3)0.273 (3)0.045*
N1'0.1959 (4)0.5059 (2)0.1129 (2)0.0265 (8)
N2'1.2916 (4)0.3085 (3)0.1111 (2)0.0301 (9)
C1'0.0508 (5)0.5298 (4)0.1502 (3)0.0315 (10)
H1C0.00470.46630.16060.038*
H1D0.02370.57050.10700.038*
C2'0.2335 (5)0.5609 (3)0.0466 (3)0.0299 (10)
H2'0.16420.61530.02500.036*
C3'A0.3618 (6)0.5448 (5)0.0084 (4)0.0272 (14)0.860 (8)
H3'A0.37820.58430.04090.033*0.860 (8)
C4'A0.4716 (6)0.4694 (5)0.0416 (4)0.0255 (13)0.860 (8)
C5'A0.4347 (7)0.4125 (5)0.1115 (4)0.0289 (13)0.860 (8)
H5'A0.50610.36030.13590.035*0.860 (8)
C6'0.2939 (5)0.4303 (3)0.1473 (3)0.0344 (11)
H6'0.26910.39000.19430.041*
C7'0.0910 (5)0.5876 (3)0.2360 (3)0.0240 (9)
H7'0.15300.54350.28280.029*
C8'0.0630 (5)0.6221 (3)0.2639 (2)0.0292 (9)
H8C0.03900.65250.32360.035*
H8D0.11580.67400.22230.035*
C9'A0.6120 (6)0.4533 (4)0.0014 (3)0.0262 (13)0.860 (8)
H9'A0.62340.49490.04750.031*0.860 (8)
C0'A0.7267 (6)0.3854 (4)0.0271 (3)0.0277 (14)0.860 (8)
H0'A0.71350.34420.07590.033*0.860 (8)
C1A'0.8693 (7)0.3668 (5)0.0108 (4)0.0274 (16)0.860 (8)
C12'0.9755 (5)0.2958 (4)0.0236 (3)0.0329 (11)
H12'0.95350.25800.07270.040*
C13'1.1137 (5)0.2746 (3)0.0080 (3)0.0300 (10)
H13'1.18350.22300.01920.036*
C14'1.1537 (5)0.3282 (3)0.0805 (3)0.0237 (9)
C15'1.0459 (5)0.4038 (3)0.1190 (3)0.0294 (10)
H15'1.06930.44190.16750.035*
C16'0.9064 (5)0.4225 (4)0.0862 (3)0.0333 (11)
H16'0.83360.47260.11340.040*
C17'1.3372 (5)0.3656 (4)0.1837 (3)0.0383 (12)
H17D1.26000.35240.23800.046*
H17E1.44500.34510.19210.046*
H17F1.33720.43790.17000.046*
C18'1.3947 (5)0.2250 (4)0.0766 (3)0.0368 (11)
H18D1.44190.23830.01480.044*
H18E1.48070.21740.11150.044*
H18F1.33110.16270.08030.044*
C3'B0.410 (4)0.524 (2)0.0343 (17)0.006 (3)*0.140 (8)
H3'B0.46880.56170.00240.008*0.140 (8)
C4'B0.479 (3)0.439 (3)0.077 (2)0.006 (3)*0.140 (8)
C5'B0.413 (3)0.3892 (19)0.1394 (17)0.006 (3)*0.140 (8)
H5'B0.45450.32920.17250.008*0.140 (8)
C9'B0.628 (2)0.3994 (16)0.0562 (14)0.006 (3)*0.140 (8)
H9'B0.67530.34430.09120.008*0.140 (8)
C0'B0.709 (3)0.4332 (18)0.0095 (16)0.006 (3)*0.140 (8)
H0'B0.66340.48980.04260.008*0.140 (8)
C1B'0.863 (4)0.391 (2)0.035 (2)0.006 (3)*0.140 (8)
C3B0.597 (12)0.347 (7)0.348 (6)0.006 (3)*0.037 (5)
H3B0.54090.36270.29110.008*0.037 (5)
C4B0.505 (9)0.332 (8)0.418 (8)0.006 (3)*0.037 (5)
C5B0.600 (15)0.265 (9)0.478 (7)0.006 (3)*0.037 (5)
H5B0.56420.24600.52970.008*0.037 (5)
C9B0.351 (8)0.361 (6)0.440 (4)0.006 (3)*0.037 (5)
H9B0.27870.38870.39210.008*0.037 (5)
C10B0.290 (9)0.355 (6)0.515 (5)0.006 (3)*0.037 (5)
H10B0.37000.34280.56580.008*0.037 (5)
C11B0.130 (8)0.364 (7)0.537 (7)0.006 (3)*0.037 (5)
C12B0.072 (12)0.456 (7)0.501 (6)0.006 (3)*0.037 (5)
H12B0.13790.49730.47070.008*0.037 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0256 (6)0.0416 (7)0.0534 (7)0.0007 (5)0.0158 (5)0.0082 (6)
O10.0258 (14)0.0429 (15)0.0330 (15)0.0025 (12)0.0042 (11)0.0092 (12)
O20.0278 (17)0.0325 (17)0.055 (2)0.0010 (15)0.0217 (15)0.0060 (16)
N10.0173 (18)0.0271 (19)0.029 (2)0.0026 (15)0.0086 (14)0.0003 (16)
N20.0214 (19)0.0282 (19)0.031 (2)0.0049 (16)0.0057 (15)0.0031 (17)
C10.021 (2)0.036 (2)0.030 (2)0.0027 (18)0.0100 (18)0.0025 (19)
C20.031 (3)0.022 (2)0.034 (3)0.0003 (19)0.008 (2)0.0018 (19)
C3A0.024 (3)0.027 (3)0.031 (3)0.003 (2)0.005 (2)0.003 (2)
C4A0.017 (2)0.024 (3)0.026 (3)0.001 (2)0.0025 (19)0.003 (2)
C5A0.026 (3)0.024 (3)0.033 (3)0.000 (2)0.008 (2)0.002 (2)
C60.028 (2)0.029 (2)0.036 (3)0.0018 (19)0.0085 (19)0.001 (2)
C70.022 (2)0.027 (2)0.027 (2)0.0044 (18)0.0031 (16)0.0017 (18)
C80.029 (2)0.029 (2)0.033 (2)0.0012 (19)0.0091 (17)0.002 (2)
C9A0.028 (3)0.026 (3)0.029 (3)0.006 (2)0.009 (2)0.004 (2)
C10A0.027 (3)0.023 (2)0.022 (2)0.0025 (19)0.0033 (19)0.001 (2)
C11A0.018 (2)0.021 (3)0.028 (3)0.0019 (19)0.0045 (19)0.003 (2)
C12A0.023 (2)0.029 (3)0.024 (3)0.0009 (19)0.0015 (19)0.004 (2)
C130.023 (2)0.027 (2)0.025 (2)0.0041 (18)0.0002 (18)0.0015 (19)
C140.022 (2)0.022 (2)0.027 (2)0.0022 (17)0.0044 (18)0.0050 (18)
C150.030 (2)0.028 (2)0.028 (2)0.0022 (19)0.0061 (19)0.002 (2)
C160.028 (2)0.031 (2)0.028 (2)0.0039 (19)0.006 (2)0.003 (2)
C170.029 (2)0.032 (2)0.037 (3)0.004 (2)0.011 (2)0.005 (2)
C180.026 (2)0.032 (2)0.034 (3)0.006 (2)0.0063 (19)0.001 (2)
Cl20.0285 (5)0.0390 (6)0.0390 (6)0.0064 (5)0.0072 (4)0.0030 (5)
O1'0.0276 (14)0.0284 (14)0.0486 (17)0.0042 (11)0.0008 (12)0.0010 (12)
O2'0.0325 (18)0.0292 (17)0.057 (2)0.0004 (15)0.0247 (16)0.0018 (16)
N1'0.0205 (18)0.0269 (19)0.033 (2)0.0015 (15)0.0066 (15)0.0085 (17)
N2'0.028 (2)0.029 (2)0.037 (2)0.0055 (17)0.0158 (17)0.0049 (17)
C1'0.018 (2)0.042 (3)0.036 (3)0.0042 (19)0.0101 (18)0.009 (2)
C2'0.032 (2)0.027 (2)0.031 (2)0.0012 (19)0.0052 (19)0.000 (2)
C3'A0.019 (3)0.031 (3)0.030 (3)0.001 (2)0.001 (2)0.000 (2)
C4'A0.022 (3)0.025 (3)0.030 (3)0.010 (2)0.004 (2)0.006 (2)
C5'A0.034 (3)0.024 (3)0.030 (4)0.003 (2)0.010 (3)0.003 (2)
C6'0.040 (3)0.027 (2)0.035 (3)0.001 (2)0.002 (2)0.002 (2)
C7'0.028 (2)0.020 (2)0.025 (2)0.0014 (17)0.0051 (17)0.0024 (16)
C8'0.033 (2)0.025 (2)0.030 (2)0.001 (2)0.0088 (17)0.002 (2)
C9'A0.022 (3)0.030 (3)0.026 (3)0.002 (2)0.002 (2)0.001 (2)
C0'A0.026 (3)0.032 (3)0.025 (3)0.004 (2)0.002 (2)0.003 (3)
C1A'0.028 (3)0.036 (4)0.018 (3)0.007 (3)0.004 (3)0.005 (3)
C12'0.031 (3)0.043 (3)0.027 (2)0.012 (2)0.012 (2)0.010 (2)
C13'0.032 (3)0.029 (2)0.029 (2)0.007 (2)0.005 (2)0.002 (2)
C14'0.020 (2)0.026 (2)0.026 (2)0.0038 (17)0.0037 (18)0.0053 (18)
C15'0.027 (2)0.033 (2)0.029 (2)0.0047 (19)0.0053 (19)0.000 (2)
C16'0.022 (2)0.034 (3)0.041 (3)0.0056 (19)0.004 (2)0.006 (2)
C17'0.034 (3)0.048 (3)0.037 (3)0.000 (2)0.017 (2)0.000 (2)
C18'0.028 (2)0.034 (3)0.049 (3)0.008 (2)0.007 (2)0.001 (2)
Geometric parameters (Å, º) top
O1—C71.424 (4)C1'—C7'1.511 (5)
O1—H1O0.83 (3)C1'—H1C0.9900
O2—C81.420 (5)C1'—H1D0.9900
O2—H2O0.83 (3)C2'—C3'A1.336 (6)
N1—C21.344 (5)C2'—H2'0.9500
N1—C61.352 (5)C3'A—C4'A1.397 (8)
N1—C11.469 (5)C3'A—H3'A0.9500
N2—C141.365 (5)C4'A—C5'A1.392 (7)
N2—C171.444 (5)C4'A—C9'A1.444 (7)
N2—C181.456 (5)C5'A—C6'1.414 (7)
C1—C71.531 (6)C5'A—H5'A0.9500
C1—H1A0.9900C6'—H6'0.9500
C1—H1B0.9900C7'—C8'1.510 (5)
C2—C3A1.372 (6)C7'—H7'1.0000
C2—H20.9500C8'—H8C0.9900
C3A—C4A1.409 (6)C8'—H8D0.9900
C3A—H3A0.9500C9'A—C0'A1.331 (7)
C4A—C5A1.398 (6)C9'A—H9'A0.9500
C4A—C9A1.452 (6)C0'A—C1A'1.447 (8)
C5A—C61.348 (6)C0'A—H0'A0.9500
C5A—H5A0.9500C1A'—C12'1.343 (8)
C6—H60.9500C1A'—C16'1.454 (7)
C7—C81.507 (5)C12'—C13'1.369 (6)
C7—H71.0000C12'—H12'0.9500
C8—H8A0.9900C13'—C14'1.410 (6)
C8—H8B0.9900C13'—H13'0.9500
C9A—C10A1.344 (6)C14'—C15'1.411 (6)
C9A—H9A0.9500C15'—C16'1.382 (6)
C10A—C11A1.445 (6)C15'—H15'0.9500
C10A—H10A0.9500C16'—H16'0.9500
C11A—C12A1.402 (6)C17'—H17D0.9800
C11A—C161.412 (6)C17'—H17E0.9800
C12A—C131.363 (6)C17'—H17F0.9800
C12A—H12A0.9500C18'—H18D0.9800
C13—C141.405 (5)C18'—H18E0.9800
C13—H130.9500C18'—H18F0.9800
C14—C151.412 (5)C3'B—C4'B1.38 (4)
C15—C161.364 (6)C3'B—H3'B0.95 (3)
C15—H150.9500C4'B—C5'B1.36 (4)
C16—H160.9500C4'B—C9'B1.45 (2)
C17—H17A0.9800C5'B—H5'B0.98 (2)
C17—H17B0.9800C9'B—C0'B1.39 (3)
C17—H17C0.9800C9'B—H9'B0.9500
C18—H18A0.9800C0'B—C1B'1.53 (4)
C18—H18B0.9800C0'B—H0'B0.9500
C18—H18C0.9800C3B—C4B1.44 (12)
O1'—C7'1.413 (5)C3B—H3B0.94 (9)
O1'—H1O'0.84 (3)C4B—C5B1.42 (14)
O2'—C8'1.409 (5)C4B—C9B1.45 (3)
O2'—H2O'0.83 (3)C5B—H5B0.93 (10)
N1'—C2'1.336 (5)C9B—C10B1.35 (3)
N1'—C6'1.347 (5)C9B—H9B0.9500
N1'—C1'1.475 (5)C10B—C11B1.45 (3)
N2'—C14'1.356 (5)C10B—H10B0.9500
N2'—C18'1.449 (5)C11B—C12B1.39 (3)
N2'—C17'1.455 (5)C12B—H12B0.95 (9)
C7—O1—H1O105 (3)C7'—C1'—H1D109.2
C8—O2—H2O104 (3)H1C—C1'—H1D107.9
C2—N1—C6119.6 (4)N1'—C2'—C3'A124.6 (5)
C2—N1—C1120.0 (3)N1'—C2'—H2'117.7
C6—N1—C1120.3 (4)C3'A—C2'—H2'117.7
C14—N2—C17122.1 (3)C2'—C3'A—C4'A119.5 (5)
C14—N2—C18119.8 (3)C2'—C3'A—H3'A120.3
C17—N2—C18118.0 (3)C4'A—C3'A—H3'A120.3
N1—C1—C7111.2 (3)C5'A—C4'A—C3'A116.4 (5)
N1—C1—H1A109.4C5'A—C4'A—C9'A124.2 (6)
C7—C1—H1A109.4C3'A—C4'A—C9'A119.4 (5)
N1—C1—H1B109.4C4'A—C5'A—C6'121.8 (5)
C7—C1—H1B109.4C4'A—C5'A—H5'A119.1
H1A—C1—H1B108.0C6'—C5'A—H5'A119.1
N1—C2—C3A120.7 (4)N1'—C6'—C5'A118.2 (5)
N1—C2—H2119.6N1'—C6'—H6'120.9
C3A—C2—H2119.6C5'A—C6'—H6'120.9
C2—C3A—C4A120.6 (4)O1'—C7'—C8'107.3 (3)
C2—C3A—H3A119.7O1'—C7'—C1'110.6 (3)
C4A—C3A—H3A119.7C8'—C7'—C1'109.1 (3)
C5A—C4A—C3A116.6 (4)O1'—C7'—H7'109.9
C5A—C4A—C9A118.9 (5)C8'—C7'—H7'109.9
C3A—C4A—C9A124.5 (5)C1'—C7'—H7'109.9
C6—C5A—C4A120.4 (4)O2'—C8'—C7'109.4 (3)
C6—C5A—H5A119.8O2'—C8'—H8C109.8
C4A—C5A—H5A119.8C7'—C8'—H8C109.8
C5A—C6—N1122.1 (4)O2'—C8'—H8D109.8
C5A—C6—H6119.0C7'—C8'—H8D109.8
N1—C6—H6119.0H8C—C8'—H8D108.2
O1—C7—C8110.3 (3)C0'A—C9'A—C4'A125.6 (5)
O1—C7—C1108.5 (3)C0'A—C9'A—H9'A117.2
C8—C7—C1109.7 (3)C4'A—C9'A—H9'A117.2
O1—C7—H7109.4C9'A—C0'A—C1A'127.6 (6)
C8—C7—H7109.4C9'A—C0'A—H0'A116.2
C1—C7—H7109.4C1A'—C0'A—H0'A116.2
O2—C8—C7110.2 (3)C12'—C1A'—C0'A120.5 (5)
O2—C8—H8A109.6C12'—C1A'—C16'116.5 (5)
C7—C8—H8A109.6C0'A—C1A'—C16'123.0 (6)
O2—C8—H8B109.6C1A'—C12'—C13'123.8 (5)
C7—C8—H8B109.6C1A'—C12'—H12'118.1
H8A—C8—H8B108.1C13'—C12'—H12'118.1
C10A—C9A—C4A124.4 (5)C12'—C13'—C14'120.9 (4)
C10A—C9A—H9A117.8C12'—C13'—H13'119.6
C4A—C9A—H9A117.8C14'—C13'—H13'119.6
C9A—C10A—C11A126.2 (5)N2'—C14'—C15'121.4 (4)
C9A—C10A—H10A116.9N2'—C14'—C13'121.1 (4)
C11A—C10A—H10A116.9C15'—C14'—C13'117.5 (4)
C12A—C11A—C16116.0 (4)C16'—C15'—C14'120.2 (4)
C12A—C11A—C10A119.3 (5)C16'—C15'—H15'119.9
C16—C11A—C10A124.6 (5)C14'—C15'—H15'119.9
C13—C12A—C11A122.1 (4)C15'—C16'—C1A'121.0 (4)
C13—C12A—H12A118.9C15'—C16'—H16'119.5
C11A—C12A—H12A118.9C1A'—C16'—H16'119.5
C12A—C13—C14121.7 (4)N2'—C17'—H17D109.5
C12A—C13—H13119.1N2'—C17'—H17E109.5
C14—C13—H13119.1H17D—C17'—H17E109.5
N2—C14—C13121.9 (4)N2'—C17'—H17F109.5
N2—C14—C15121.4 (4)H17D—C17'—H17F109.5
C13—C14—C15116.7 (4)H17E—C17'—H17F109.5
C16—C15—C14121.1 (4)N2'—C18'—H18D109.5
C16—C15—H15119.5N2'—C18'—H18E109.5
C14—C15—H15119.5H18D—C18'—H18E109.5
C15—C16—C11A122.3 (4)N2'—C18'—H18F109.5
C15—C16—H16118.8H18D—C18'—H18F109.5
C11A—C16—H16118.8H18E—C18'—H18F109.5
N2—C17—H17A109.5C4'B—C3'B—H3'B119 (3)
N2—C17—H17B109.5C5'B—C4'B—C3'B123 (2)
H17A—C17—H17B109.5C5'B—C4'B—C9'B117 (3)
N2—C17—H17C109.5C3'B—C4'B—C9'B120 (3)
H17A—C17—H17C109.5C4'B—C5'B—H5'B127 (3)
H17B—C17—H17C109.5C0'B—C9'B—C4'B127 (2)
N2—C18—H18A109.5C0'B—C9'B—H9'B116.5
N2—C18—H18B109.5C4'B—C9'B—H9'B116.5
H18A—C18—H18B109.5C9'B—C0'B—C1B'128 (2)
N2—C18—H18C109.5C9'B—C0'B—H0'B115.8
H18A—C18—H18C109.5C1B'—C0'B—H0'B115.8
H18B—C18—H18C109.5C4B—C3B—H3B118 (10)
C7'—O1'—H1O'110 (3)C5B—C4B—C3B105 (7)
C8'—O2'—H2O'111 (3)C5B—C4B—C9B116 (10)
C2'—N1'—C6'119.5 (4)C3B—C4B—C9B139 (10)
C2'—N1'—C1'120.3 (4)C4B—C5B—H5B119 (10)
C6'—N1'—C1'120.2 (4)C10B—C9B—C4B133 (8)
C14'—N2'—C18'121.2 (4)C10B—C9B—H9B113.4
C14'—N2'—C17'121.6 (4)C4B—C9B—H9B113.4
C18'—N2'—C17'117.1 (3)C9B—C10B—C11B135 (8)
N1'—C1'—C7'111.9 (3)C9B—C10B—H10B112.6
N1'—C1'—H1C109.2C11B—C10B—H10B112.6
C7'—C1'—H1C109.2C12B—C11B—C10B105 (8)
N1'—C1'—H1D109.2C11B—C12B—H12B120 (10)
C2—N1—C1—C787.1 (4)N1'—C2'—C3'A—C4'A3.7 (8)
C6—N1—C1—C791.8 (4)C2'—C3'A—C4'A—C5'A2.5 (7)
C6—N1—C2—C3A0.4 (6)C2'—C3'A—C4'A—C9'A178.7 (4)
C1—N1—C2—C3A178.4 (4)C3'A—C4'A—C5'A—C6'0.2 (7)
N1—C2—C3A—C4A0.8 (7)C9'A—C4'A—C5'A—C6'178.8 (5)
C2—C3A—C4A—C5A0.4 (6)C2'—N1'—C6'—C5'A0.4 (6)
C2—C3A—C4A—C9A179.1 (4)C1'—N1'—C6'—C5'A177.7 (4)
C3A—C4A—C5A—C60.3 (7)C4'A—C5'A—C6'—N1'1.3 (7)
C9A—C4A—C5A—C6179.8 (4)N1'—C1'—C7'—O1'54.5 (5)
C4A—C5A—C6—N10.6 (7)N1'—C1'—C7'—C8'172.2 (3)
C2—N1—C6—C5A0.3 (6)O1'—C7'—C8'—O2'172.2 (3)
C1—N1—C6—C5A179.2 (4)C1'—C7'—C8'—O2'52.4 (4)
N1—C1—C7—O166.8 (4)C5'A—C4'A—C9'A—C0'A2.3 (8)
N1—C1—C7—C8172.6 (3)C3'A—C4'A—C9'A—C0'A179.0 (5)
O1—C7—C8—O275.1 (4)C4'A—C9'A—C0'A—C1A'179.8 (5)
C1—C7—C8—O244.4 (5)C9'A—C0'A—C1A'—C12'179.2 (5)
C5A—C4A—C9A—C10A178.0 (4)C9'A—C0'A—C1A'—C16'0.6 (9)
C3A—C4A—C9A—C10A1.5 (7)C0'A—C1A'—C12'—C13'179.4 (5)
C4A—C9A—C10A—C11A179.5 (4)C16'—C1A'—C12'—C13'0.4 (8)
C9A—C10A—C11A—C12A176.0 (4)C1A'—C12'—C13'—C14'0.3 (7)
C9A—C10A—C11A—C162.0 (7)C18'—N2'—C14'—C15'174.4 (4)
C16—C11A—C12A—C131.2 (7)C17'—N2'—C14'—C15'1.3 (6)
C10A—C11A—C12A—C13179.3 (4)C18'—N2'—C14'—C13'6.4 (6)
C11A—C12A—C13—C141.4 (7)C17'—N2'—C14'—C13'177.8 (4)
C17—N2—C14—C13178.7 (4)C12'—C13'—C14'—N2'178.9 (4)
C18—N2—C14—C135.1 (6)C12'—C13'—C14'—C15'0.2 (6)
C17—N2—C14—C150.6 (6)N2'—C14'—C15'—C16'179.7 (4)
C18—N2—C14—C15175.6 (3)C13'—C14'—C15'—C16'0.6 (6)
C12A—C13—C14—N2178.4 (4)C14'—C15'—C16'—C1A'1.3 (7)
C12A—C13—C14—C150.9 (6)C12'—C1A'—C16'—C15'1.2 (7)
N2—C14—C15—C16178.9 (4)C0'A—C1A'—C16'—C15'178.5 (5)
C13—C14—C15—C160.4 (6)C5'B—C4'B—C9'B—C0'B175 (2)
C14—C15—C16—C11A0.2 (6)C3'B—C4'B—C9'B—C0'B5 (4)
C12A—C11A—C16—C150.6 (6)C4'B—C9'B—C0'B—C1B'178 (3)
C10A—C11A—C16—C15178.6 (4)C5B—C4B—C9B—C10B17 (15)
C2'—N1'—C1'—C7'101.2 (5)C3B—C4B—C9B—C10B167 (10)
C6'—N1'—C1'—C7'76.9 (5)C4B—C9B—C10B—C11B166 (10)
C6'—N1'—C2'—C3'A2.2 (7)C9B—C10B—C11B—C12B53 (13)
C1'—N1'—C2'—C3'A179.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···Cl10.83 (3)2.20 (3)3.024 (3)174 (4)
O2—H2O···Cl1i0.83 (3)2.27 (3)3.086 (3)169 (4)
C2—H2···O2i0.952.403.222 (5)145
C5A—H5A···Cl2ii0.952.783.687 (5)159
C8—H8A···N2ii0.992.653.637 (5)176
O1—H1O···Cl20.84 (3)2.25 (3)3.083 (3)171 (4)
O2—H2O···Cl2iii0.83 (3)2.29 (3)3.104 (3)169 (4)
C6—H6···O2iii0.952.403.236 (6)147
Symmetry codes: (i) x+1, y, z; (ii) x+1, y1/2, z+1; (iii) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···Cl10.83 (3)2.20 (3)3.024 (3)174 (4)
O2—H2O···Cl1i0.83 (3)2.27 (3)3.086 (3)169 (4)
C2—H2···O2'i0.952.403.222 (5)145.2
C5A—H5A···Cl2ii0.952.783.687 (5)159.1
C8—H8A···N2ii0.992.653.637 (5)176.0
O1'—H1O'···Cl20.84 (3)2.25 (3)3.083 (3)171 (4)
O2'—H2O'···Cl2iii0.83 (3)2.29 (3)3.104 (3)169 (4)
C6'—H6'···O2iii0.952.403.236 (6)146.5
Symmetry codes: (i) x+1, y, z; (ii) x+1, y1/2, z+1; (iii) x1, y, z.
 

Acknowledgements

This work was supported by the New Zealand Foundation for Science and Innovation grant (contract C08X0704). We thank Dr C. Fitchett of the University of Canterbury, New Zealand, for the data collection.

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Volume 70| Part 1| January 2014| Pages o83-o84
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