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The structures of three compounds with potential anti­malarial activity are reported. In N,N-diethyl-N′-(7-iodo­quinolin-4-yl)ethane-1,2-diamine, C15H20IN3, (I), the mol­ecules are linked into ribbons by N—H...N and C—H...N hydrogen bonds. In N-(7-bromo­quinolin-4-yl)-N′,N′-diethyl­ethane-1,2-diamine dihydrate, C15H20BrN3·2H2O, (II), two amino­quino­line mol­ecules and four water mol­ecules form an R54(13) hydrogen-bonded ring which links to its neighbours to form a T5(2) one-dimensional infinite tape with pendant hydrogen bonds to the amino­quinolines. The phosphate salt 7-chloro-4-[2-(diethyl­ammonio)ethyl­amino]quinolinium bis­(dihydrogen­phosphate) phospho­ric acid, C15H22ClN32+·2H2PO4·H3PO4, (III), was prepared in order to establish the protonation sites of these compounds. The phosphate ions form a two-dimensional hydrogen-bonded sheet, while the amino­quino­line cations are linked to the phosphates by N—H...O hydrogen bonds from each of their three N atoms. While the conformation of the quinoline region hardly varies between (I), (II) and (III), the amino side chain is much more flexible and adopts a significantly different conformation in each case. Aromatic π–π stacking inter­actions are the only supramolecular inter­actions seen in all three structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105041235/hj1079sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105041235/hj1079Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105041235/hj1079IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105041235/hj1079IIIsup4.hkl
Contains datablock III

CCDC references: 299647; 299648; 299649

Comment top

Quinoline antimalarial drugs, such as chloroquine, quinine, amodiaquine and mefloquine, have been used as effective treatments for malaria (Tilley et al., 2001). Until the onset of parasite resistance, chloroquine was especially valuable, owing to its affordability, limited toxicity and potency. It is believed to accumulate in its diprotonated state in the acidic environment of the Plasmodium food vacuole in an infected red blood cell, unable to re-cross the lipid membrane. The drug activity is understood to arise from complex formation between the 4-aminoquinoline drug and its target, haematin, thus preventing the haematin from aggregating to crystalline haemozoin (Egan et al., 1994). The structure–activity relationships for a series of aminoquinolines have been investigated in order to determine which molecular constituents confer antimalarial activity (Kaschula et al., 2002). A 4-aminoquinoline nucleus provides a planar electron-rich conjugated system able to associate with the porphyrin dimer. A moderately electron-withdrawing and strongly lipophilic group at position 7 is needed to maximize the drug activity, while the terminal amino group is basic and helps to ensure that the drug accumulates in the acidic food vacuole.

Molecular modelling provides a useful probe for investigating these complexes and crystallographic studies can provide complementary information about the structure of 4-aminoquinoline compounds. As part of an ongoing study into the mechanism of antimalarial drug activity, we have elucidated the crystal structures of three short-chain 4-aminoquinolines, viz. N,N-diethyl-N'-(7-iodoquinolin-4-yl)ethane-1,2-diamine, (I), N-(7-bromoquinolin-4-yl)-N',N'-diethylethane-1,2-diamine dihydrate, (II), and 7-chloro-4-[2-(diethylammonio)ethylamino]quinolinium bis(dihydrogenphosphate) phosphoric acid, (III) (see scheme). This class of compounds has been shown to inhibit the formation of synthetic β-haematin and to exhibit antiplasmodial activity in vitro (Kaschula et al., 2002), and they are therefore potential antimalarials. While this class of compounds forms complexes with haematin and prevents its aggregation to crystalline haemozoin, complexes between the drug molecule and haematin are notoriously difficult to crystallize. Molecular modelling using computational methods may provide a means of studying such interactions in solution.

The crystal structures obtained in this study are valuable for comparison with the structures generated using molecular modelling. The intermolecular parameters determined from the crystal structures were compared with those of related compounds generated using molecular modelling. The results of these computational investigations will be reported separately.

The iodo-compound, (I), is shown in Fig. 1. The bromoquinoline derivative crystallizes with two water molecules to form (II) (Fig. 2). The asymmetric unit of (III) consists of two crystallographically independent quinoline molecules (labelled A and B), and six phosphate ions (Fig. 3); structural refinement confirmed that the diprotic salt of N'-(7-chloroquinolin-4-yl)-N,N-diethyl-1,2-ethanediamine had crystallized.

The molecular conformations of compounds (I)-(III) can be defined in terms of six torsion angles, which are given in Table 1. The quinoline rings are planar in each case. Thus, the only conformational differences arise within the diamine side chain. The N11—C12 bond is nearly coplanar with the ring system in each case, with the greatest deviation being in molecule A of (III). The torsion angles C4—N11—C12—C13 (τ2) and N11—C12—C13—N14 (τ3) show that for (I), the side chain is in the more extended conformation induced by the gauche and anti conformations in τ2 and τ3, respectively. In (II), these torsion angles are anti and gauche, while in (III) they are both gauche, in each case resulting in the side chain folding back to a greater degree. The three different side chain conformations are shown in Fig. 4. NMR-constrained molecular mechanics and molecular dynamics/simulated annealing studies (Leed et al., 2002) have found that, on complexation with haematin, the aliphatic side chains of chloroquine, quinine and quinidine fold back to interact with the tetrapyrrole. It should be noted that the more extended conformation observed in this study may therefore change significantly on complexation.

In the supramolecular structure of (I), quinoline atom N1 of the molecule at (x, y, z) acts as a hydrogen-bond acceptor to the 4-amino group (atom N11) and quinoline atom C6 of the molecule at (1/2 + x, y, 1/2 − z), generating an R21(7) ring (Table 2) (Bernstein et al., 1995). Propagation by a twofold screw axis generates a ribbon of molecules parallel to [100] (Fig. 5). Perpendicular to the ribbons, molecules stack in parallel orientations to allow ππ interactions between adjacent quinoline rings (centroid separations are between 3.82 and 4.53 Å)

Intermolecular hydrogen bonds are prominent in the crystal structure of (II) (Table 3). Two aminoquinoline molecules and four water molecules form an R54(13) hydrogen-bonded ring. These rings then form a linked network with shared O1—H···O2 edges. This network is illustrated in Fig. 6 as green dotted lines. O2—H···N1(quinoline) hydrogen-bonded chains (shown as red dotted lines in Fig. 6) are pendant to these rings. It is worth noting that this arrangement allows each aminoquinoline N atom to act as either a hydrogen-bond acceptor (N1 and N14) or donor (N11). Water is potentially capable of participating in four hydrogen bonds but frequently shows a three-coordinate configuration (Jeffrey & Maluszynska, 1990). This is illustrated in the case of (II), where atom O1 donates two hydrogen bonds but accepts one, while atom O2 participates in a full quota of four hydrogen bonds. Infantes et al. (2002, 2003) have investigated the role of water molecules in stabilizing hydrated crystal structures of organic compounds. The hydrogen-bonded rings in (II) form the relatively common one-dimensional infinite tapes denoted by Infantes as T5(2). Aromatic stacking is again significant in this structure (centroid separations 3.57 and 3.58 Å). In addition, a Br···Br interaction [distance 3.6967 (5) Å; sum of radii 3.70 Å (Reference?)] is also evident.

The phosphate salt of (III) was prepared in order to confirm that protonation of these compounds occurs at the terminal amine and quinoline N atoms. The conformations of aminoquinoline molecules A and B are essentially identical but there are six crystallographically independent phosphate ions in the asymmetric unit. As in (I) and (II), there is an extended network of hydrogen bonds stabilizing the structure. A list of `strong' hydrogen bonds is given in Table 4; there are also a large number of C—H···O interactions, but these have not been detailed. Aromatic stacking also plays a role in the crystal packing, which takes the form of stacks of aminoquinoline and phosphate ions. The phosphate ions form a two-dimensional hydrogen-bonded sheet parallel to [111], similar to those reported for anilinium phosphate salts (Paxão et al., 2000; Mahmoudkhani & Langer, 2002). We note that all hydrogen bonds within this sheet are of the form P—O—H···OP, with correspondingly short O···O distances (2.48–2.67 Å). This phenomenon has been noted previously: shorter bonds (ca 2.5 Å) connect P—O—H and PO groups, while longer distances (ca 2.8 Å) link P—O—H moieties on adjacent molecules (Greenwood & Earnshaw, 1984; Dega-Szafran et al., 2000). In addition, P—O bond lengths corroborate the assignment of P—O—H (between 1.53 and 1.58 Å) and P O bonds (between 1.49 and 1.52 Å) within the phosphates. Aminoquinoline cations are linked to the phosphate anions via N—H···O—P hydrogen bonds. The aromatic ends of the quinolines point towards the phosphate layer and stack with their Cl atoms in alternating directions (centroid separations are in the range 3.65–3.95 Å). These features are illustrated in Fig. 7.

In conclusion, the molecular constituents of (I)–(III) potentially allow four different types of direction-specific intermolecular interactions. These are N—H···N and C—H···N hydrogen bonds, halogen interactions and aromatic ππ stacking interactions. In fact, the only interaction observed in all three structures is the last of these. In (I), N—H···N and C—H···N hydrogen bonds govern the supramolecular network, while in (II) and (III) the stronger hydrogen-bonding capability of O atoms (in water molecules or phosphate ions) dominates. The molecular conformation of the quinoline nucleus hardly varies between the three structures, while the amino side-chain is found to be much more flexible. The conformations of these three related 7-haloaminoquinolines and the patterns in their supramolecular networks suggest there is a subtle interplay between the weak direction-specific interactions between molecules. Weak forces of the type seen here, which depend on molecular polarizability, are not easy to model computationally, especially in the prediction of supramolecular structures. The variation in the supramolecular aggregation observed in these compounds suggests that experimental results of the type reported here are likely to be of prime importance for some time to come.

The observation of the two protonation sites in (III) is important. The terminal amine N atom has been previously recognized as a site of protonation but some uncertainty existed as to whether the second protonation site is the 4-amino or the quinoline N atom. This study provides evidence that the second protonation site is indeed the latter.

Experimental top

Compounds (I)–(III) were synthesized for an earlier study by reaction of N,N-diethylethanediamine with the corresponding 7-substituted 4-chloroquinolines (Kaschula et al., 2002). Single crystals of the free base forms of (I) and (II) were obtained by dissolving the respective compounds (ca 12 mg) in a minimum volume of diethyl ether and allowing slow evaporation of the solvent in the refrigerator (283 K). Compound (III) (ca 10 mg) was dissolved in a dilute solution of phosphoric acid to facilitate the formation of the diprotic species. An aliquot of n-hexane was added to the solution and the vial placed in the refrigerator (283 K) to allow slow mixing of the solvent layers. Needle-like crystals formed in the aqueous layer within one week.

Refinement top

H atoms attached to N or O atoms were located in difference maps and included in the refinements with independent displacement parameters. All other H atoms were placed in geometrically calculated positions and refined as riding atoms, with C—H = 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl groups. [Please check added text] Since there are only four protonation sites on the two quinoline molecules in (III), it seems reasonable to surmise that four of the six phosphates exist as H2PO4, each having donated one proton. In dilute aqueous solution, phosphoric acid behaves as a strong acid but only one of its H atoms is readily ionisable. The pKa values are 2.15, 7.20 and 12.37 for the successive loss of protons (Weast, 1974). The remaining two phosphates are most likely in the form H3PO4, and the location of the H atoms in the difference Fourier map seemed to confirm this.

Computing details top

For all compounds, data collection: COLLECT (Nonius, 1997); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: POV-RAY (Cason, 2003); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The asymmetric unit of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. The asymmetric unit of (III), showing the atom-labelling scheme for molecule A; molecule B is similarly numbered. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. The conformations of the diamine side chain in compounds (I), (II) and (II). For (III), molecule A is illustrated; the side chain of molecule B has an almost identical conformation.
[Figure 5] Fig. 5. Part of the crystal structure of (I), showing the formation of a ribbon of R21(7) rings along [100].
[Figure 6] Fig. 6. A packing diagram for compound (II), indicating the linked R54(13) rings (green) and appended O2···N1 chains (red). H atoms not involved in the hydrogen bonding have been omitted for clarity.
[Figure 7] Fig. 7. Part of the crystal structure of (III), showing the formation of a two-dimensional hydrogen-bonded sheet of phosphate ions and aminoquinoline stacks. H atoms not involved in the hydrogen bonding have been omitted for clarity.
(I) N,N-diethyl-N'-(7-iodoquinolin-4-yl)ethane-1,2-diamine top
Crystal data top
C15H20IN3Dx = 1.597 Mg m3
Mr = 369.24Melting point = 359–360 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 9238 reflections
a = 13.2379 (7) Åθ = 3.1–27.2°
b = 7.8883 (4) ŵ = 2.08 mm1
c = 29.4118 (17) ÅT = 114 K
V = 3071.3 (3) Å3Plate, pale yellow
Z = 80.10 × 0.10 × 0.02 mm
F(000) = 1472
Data collection top
Nonius KappaCCD area-detector
diffractometer
3328 independent reflections
Radiation source: fine-focus sealed tube2401 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ω and ϕ scansθmax = 27.2°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 1616
Tmin = 0.820, Tmax = 0.961k = 910
34000 measured reflectionsl = 3737
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0361P)2 + 3.0942P]
where P = (Fo2 + 2Fc2)/3
3328 reflections(Δ/σ)max = 0.001
178 parametersΔρmax = 1.14 e Å3
0 restraintsΔρmin = 1.02 e Å3
Crystal data top
C15H20IN3V = 3071.3 (3) Å3
Mr = 369.24Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 13.2379 (7) ŵ = 2.08 mm1
b = 7.8883 (4) ÅT = 114 K
c = 29.4118 (17) Å0.10 × 0.10 × 0.02 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3328 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
2401 reflections with I > 2σ(I)
Tmin = 0.820, Tmax = 0.961Rint = 0.053
34000 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 1.14 e Å3
3328 reflectionsΔρmin = 1.02 e Å3
178 parameters
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. The structure was solved by direct methods and refined on F2 using SHELX97 (Sheldrick, 1997) within the X-SEED interface (Barbour, 2003). A weighting scheme based on P = (Fo2 + 2Fc2)/3 was employed in order to reduce statistical bias (Wilson, 1976). Molecular geometry and supramolecular interactions were analysed with the aid of PLATON (Spek, 2003). Diagrams were prepared using POV-RAY (Cason, 2003) within the X-SEED interface. Bond lengths and angles are in agreement with typical literature values. 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. [Wilson, A. J. C. (1976). Acta Cryst. A32, 994–996.]

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.834275 (18)0.19709 (3)0.407928 (7)0.03463 (10)
N10.93606 (18)0.4940 (4)0.24943 (9)0.0256 (6)
N110.6361 (2)0.5477 (4)0.20344 (9)0.0231 (6)
N140.60814 (18)0.6236 (4)0.07778 (8)0.0228 (6)
C20.9124 (2)0.5623 (4)0.20984 (11)0.0262 (8)
H20.96690.60020.19150.031*
C30.8157 (2)0.5843 (4)0.19239 (11)0.0231 (7)
H30.80620.63710.16370.028*
C40.7327 (2)0.5282 (4)0.21748 (10)0.0195 (7)
C50.7535 (2)0.4482 (4)0.26032 (9)0.0193 (7)
C60.6775 (2)0.3821 (4)0.28907 (10)0.0221 (7)
H60.60900.38640.27950.027*
C70.7005 (2)0.3124 (4)0.33017 (11)0.0249 (7)
H70.64830.26910.34910.030*
C80.8010 (2)0.3049 (4)0.34443 (10)0.0230 (7)
C90.8777 (2)0.3648 (4)0.31738 (10)0.0230 (7)
H90.94580.35750.32740.028*
C100.8552 (2)0.4370 (4)0.27475 (11)0.0199 (7)
C120.6089 (2)0.6359 (4)0.16168 (10)0.0226 (7)
H12A0.65210.73770.15850.027*
H12B0.53790.67440.16390.027*
C130.6207 (2)0.5256 (4)0.11947 (10)0.0235 (7)
H13A0.68850.47280.11960.028*
H13B0.56990.43370.12020.028*
C150.5007 (2)0.6630 (5)0.07024 (12)0.0332 (9)
H15A0.46880.69050.09980.040*
H15B0.46650.56120.05790.040*
C160.4846 (3)0.8095 (5)0.03789 (12)0.0374 (9)
H16A0.51990.90990.04940.056*
H16B0.41230.83380.03540.056*
H16C0.51140.77970.00790.056*
C170.6496 (2)0.5320 (5)0.03847 (11)0.0304 (8)
H17A0.62770.59020.01030.036*
H17B0.62080.41620.03800.036*
C180.7630 (3)0.5194 (5)0.03847 (13)0.0394 (9)
H18A0.79220.63240.04270.059*
H18B0.78590.47250.00940.059*
H18C0.78480.44490.06330.059*
H110.590 (3)0.521 (5)0.2212 (12)0.034 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.04390 (16)0.03291 (17)0.02708 (14)0.00529 (12)0.01132 (10)0.00636 (10)
N10.0170 (14)0.0312 (17)0.0286 (15)0.0018 (13)0.0007 (12)0.0003 (13)
N110.0142 (13)0.0335 (18)0.0216 (14)0.0001 (13)0.0005 (11)0.0019 (12)
N140.0193 (14)0.0294 (17)0.0196 (13)0.0025 (12)0.0016 (11)0.0025 (12)
C20.0198 (16)0.027 (2)0.0321 (19)0.0035 (15)0.0066 (14)0.0016 (15)
C30.0208 (17)0.0249 (19)0.0238 (16)0.0030 (14)0.0008 (13)0.0002 (14)
C40.0160 (16)0.0193 (18)0.0232 (15)0.0002 (14)0.0001 (12)0.0049 (13)
C50.0167 (15)0.0205 (17)0.0208 (15)0.0003 (13)0.0006 (13)0.0058 (13)
C60.0160 (15)0.027 (2)0.0231 (16)0.0005 (14)0.0008 (12)0.0037 (14)
C70.0235 (16)0.029 (2)0.0222 (16)0.0039 (15)0.0020 (13)0.0003 (15)
C80.0296 (16)0.0232 (18)0.0161 (15)0.0003 (15)0.0053 (12)0.0042 (14)
C90.0184 (15)0.0230 (19)0.0276 (17)0.0004 (14)0.0049 (13)0.0017 (14)
C100.0154 (15)0.0175 (18)0.0269 (16)0.0004 (13)0.0007 (12)0.0046 (14)
C120.0190 (16)0.0266 (19)0.0221 (16)0.0019 (14)0.0027 (12)0.0008 (14)
C130.0184 (16)0.029 (2)0.0231 (17)0.0014 (15)0.0004 (13)0.0009 (14)
C150.0177 (16)0.046 (2)0.0357 (19)0.0019 (17)0.0042 (15)0.0115 (17)
C160.0309 (19)0.042 (2)0.039 (2)0.0103 (18)0.0082 (16)0.0008 (18)
C170.035 (2)0.034 (2)0.0219 (17)0.0040 (16)0.0004 (14)0.0026 (15)
C180.041 (2)0.032 (2)0.045 (2)0.0079 (18)0.0196 (18)0.0042 (18)
Geometric parameters (Å, º) top
I1—C82.099 (3)C8—C91.373 (4)
N1—C21.321 (4)C9—C101.409 (4)
N1—C101.379 (4)C9—H90.9500
N11—C41.353 (4)C12—C131.524 (4)
N11—C121.457 (4)C12—H12A0.9900
N11—H110.83 (3)C12—H12B0.9900
N14—C131.459 (4)C13—H13A0.9900
N14—C171.470 (4)C13—H13B0.9900
N14—C151.473 (4)C15—C161.512 (5)
C2—C31.390 (4)C15—H15A0.9900
C2—H20.9500C15—H15B0.9900
C3—C41.396 (4)C16—H16A0.9800
C3—H30.9500C16—H16B0.9800
C4—C51.436 (4)C16—H16C0.9800
C5—C61.413 (4)C17—C181.505 (4)
C5—C101.415 (4)C17—H17A0.9900
C6—C71.362 (4)C17—H17B0.9900
C6—H60.9500C18—H18A0.9800
C7—C81.397 (4)C18—H18B0.9800
C7—H70.9500C18—H18C0.9800
C2—N1—C10115.2 (3)N11—C12—H12A109.0
C4—N11—C12123.0 (3)C13—C12—H12A109.0
C4—N11—H11119 (2)N11—C12—H12B109.0
C12—N11—H11118 (2)C13—C12—H12B109.0
C13—N14—C17111.0 (3)H12A—C12—H12B107.8
C13—N14—C15110.4 (2)N14—C13—C12111.8 (3)
C17—N14—C15110.2 (3)N14—C13—H13A109.3
N1—C2—C3126.5 (3)C12—C13—H13A109.3
N1—C2—H2116.7N14—C13—H13B109.3
C3—C2—H2116.7C12—C13—H13B109.3
C2—C3—C4119.3 (3)H13A—C13—H13B107.9
C2—C3—H3120.3N14—C15—C16113.0 (3)
C4—C3—H3120.3N14—C15—H15A109.0
N11—C4—C3123.1 (3)C16—C15—H15A109.0
N11—C4—C5119.9 (3)N14—C15—H15B109.0
C3—C4—C5116.9 (3)C16—C15—H15B109.0
C6—C5—C10118.4 (3)H15A—C15—H15B107.8
C6—C5—C4123.4 (3)C15—C16—H16A109.5
C10—C5—C4118.2 (3)C15—C16—H16B109.5
C7—C6—C5121.4 (3)H16A—C16—H16B109.5
C7—C6—H6119.3C15—C16—H16C109.5
C5—C6—H6119.3H16A—C16—H16C109.5
C6—C7—C8119.8 (3)H16B—C16—H16C109.5
C6—C7—H7120.1N14—C17—C18113.9 (3)
C8—C7—H7120.1N14—C17—H17A108.8
C9—C8—C7121.0 (3)C18—C17—H17A108.8
C9—C8—I1120.0 (2)N14—C17—H17B108.8
C7—C8—I1119.0 (2)C18—C17—H17B108.8
C8—C9—C10119.9 (3)H17A—C17—H17B107.7
C8—C9—H9120.0C17—C18—H18A109.5
C10—C9—H9120.0C17—C18—H18B109.5
N1—C10—C9116.7 (3)H18A—C18—H18B109.5
N1—C10—C5123.8 (3)C17—C18—H18C109.5
C9—C10—C5119.5 (3)H18A—C18—H18C109.5
N11—C12—C13112.9 (3)H18B—C18—H18C109.5
C10—N1—C2—C31.4 (5)C2—N1—C10—C9179.4 (3)
N1—C2—C3—C41.2 (5)C2—N1—C10—C50.3 (4)
C12—N11—C4—C32.8 (5)C8—C9—C10—N1179.9 (3)
C12—N11—C4—C5176.5 (3)C8—C9—C10—C50.4 (5)
C2—C3—C4—N11178.6 (3)C6—C5—C10—N1178.8 (3)
C2—C3—C4—C50.6 (4)C4—C5—C10—N12.0 (4)
N11—C4—C5—C61.9 (4)C6—C5—C10—C91.5 (4)
C3—C4—C5—C6178.8 (3)C4—C5—C10—C9177.7 (3)
N11—C4—C5—C10177.2 (3)C4—N11—C12—C1380.7 (4)
C3—C4—C5—C102.1 (4)C17—N14—C13—C12162.5 (3)
C10—C5—C6—C71.4 (5)C15—N14—C13—C1275.0 (3)
C4—C5—C6—C7177.7 (3)N11—C12—C13—N14171.2 (2)
C5—C6—C7—C80.3 (5)C13—N14—C15—C16160.6 (3)
C6—C7—C8—C90.9 (5)C17—N14—C15—C1676.5 (4)
C6—C7—C8—I1179.9 (2)C13—N14—C17—C1869.9 (4)
C7—C8—C9—C100.8 (5)C15—N14—C17—C18167.5 (3)
I1—C8—C9—C10180.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···N1i0.83 (3)2.22 (3)3.019 (4)161 (3)
C6—H6···N1i0.952.593.504 (4)163
Symmetry code: (i) x1/2, y, z+1/2.
(II) N-(7-bromoquinolin-4-yl)-N',N'-diethylethane-1,2-diamine dihydrate top
Crystal data top
C15H20BrN3·2H2OF(000) = 1488
Mr = 358.28Dx = 1.435 Mg m3
Monoclinic, C2/cMelting point = 340–341 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 28.0177 (4) ÅCell parameters from 8774 reflections
b = 6.8221 (9) Åθ = 1.6–26.4°
c = 18.9339 (4) ŵ = 2.49 mm1
β = 113.61 (3)°T = 113 K
V = 3316.1 (9) Å3Plate, colourless
Z = 80.13 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
3403 independent reflections
Radiation source: fine-focus sealed tube2470 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
ω and ϕ scansθmax = 26.4°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 3434
Tmin = 0.738, Tmax = 0.789k = 88
26586 measured reflectionsl = 2323
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) = 0.080H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0305P)2 + 3.5408P]
where P = (Fo2 + 2Fc2)/3
3403 reflections(Δ/σ)max = 0.002
212 parametersΔρmax = 0.38 e Å3
5 restraintsΔρmin = 0.51 e Å3
Crystal data top
C15H20BrN3·2H2OV = 3316.1 (9) Å3
Mr = 358.28Z = 8
Monoclinic, C2/cMo Kα radiation
a = 28.0177 (4) ŵ = 2.49 mm1
b = 6.8221 (9) ÅT = 113 K
c = 18.9339 (4) Å0.13 × 0.10 × 0.10 mm
β = 113.61 (3)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
3403 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
2470 reflections with I > 2σ(I)
Tmin = 0.738, Tmax = 0.789Rint = 0.074
26586 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0375 restraints
wR(F2) = 0.080H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.38 e Å3
3403 reflectionsΔρmin = 0.51 e Å3
212 parameters
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. The structure was solved by direct methods and refined on F2 using SHELX97 (Sheldrick, 1997) within the X-SEED interface (Barbour, 2003). A weighting scheme based on P = (Fo2 + 2Fc2)/3 was employed in order to reduce statistical bias (Wilson, 1976). Molecular geometry and supramolecular interactions were analysed with the aid of PLATON (Spek, 2003). Diagrams were prepared using POV-RAY (Cason, 2003) within the X-SEED interface. Bond lengths and angles are in agreement with typical literature values. 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. [Wilson, A. J. C. (1976). Acta Cryst. A32, 994–996.]

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.059437 (10)0.97961 (4)0.340318 (17)0.03556 (11)
O10.29418 (8)1.2080 (3)0.29291 (12)0.0275 (4)
N10.23553 (8)0.9821 (3)0.57984 (11)0.0219 (5)
O20.19338 (7)1.1306 (3)0.18035 (11)0.0258 (4)
C20.28697 (10)0.9862 (3)0.61193 (14)0.0221 (5)
H20.30320.97890.66660.027*
C30.31936 (10)1.0004 (3)0.57244 (14)0.0211 (5)
H30.35611.00400.60010.025*
C40.29786 (9)1.0094 (3)0.49231 (14)0.0188 (5)
C50.24186 (9)1.0027 (3)0.45438 (13)0.0180 (5)
C60.21440 (9)1.0026 (3)0.37340 (14)0.0203 (5)
H60.23341.00870.34160.024*
C70.16129 (10)0.9940 (3)0.33976 (14)0.0221 (5)
H70.14340.99180.28520.027*
C80.13353 (9)0.9883 (3)0.38726 (14)0.0223 (5)
C90.15807 (9)0.9859 (3)0.46556 (14)0.0211 (5)
H90.13830.98090.49620.025*
C100.21297 (9)0.9908 (3)0.50103 (14)0.0183 (5)
N110.32747 (8)1.0191 (3)0.45075 (12)0.0207 (5)
H110.3144 (10)1.055 (4)0.4047 (15)0.025 (8)*
C120.38398 (9)1.0288 (4)0.48757 (15)0.0221 (5)
H12A0.39760.90870.51840.026*
H12B0.39451.14260.52290.026*
C130.40721 (10)1.0483 (3)0.42820 (15)0.0221 (6)
H13A0.38951.15710.39280.027*
H13B0.44441.08410.45500.027*
N140.40334 (8)0.8709 (3)0.38220 (11)0.0199 (5)
C150.40570 (11)0.9224 (4)0.30768 (15)0.0277 (6)
H15A0.37851.02160.28200.033*
H15B0.39680.80390.27470.033*
C160.45759 (12)1.0017 (4)0.31104 (19)0.0387 (7)
H16C0.46841.11350.34640.058*
H16A0.45351.04390.25950.058*
H16B0.48410.89850.32940.058*
C170.44336 (10)0.7282 (4)0.42671 (15)0.0256 (6)
H17A0.44000.70180.47600.031*
H17B0.47820.78650.43910.031*
C180.44002 (11)0.5357 (4)0.38517 (18)0.0322 (6)
H18A0.40460.48290.36820.048*
H17C0.46480.44220.42020.048*
H18B0.44840.55740.34030.048*
H11W0.3026 (11)1.338 (4)0.3064 (17)0.047 (9)*
H12W0.2655 (11)1.192 (4)0.2616 (17)0.040 (10)*
H21W0.1678 (11)1.207 (4)0.1614 (17)0.045 (10)*
H22W0.2038 (12)1.109 (5)0.1430 (17)0.049 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01681 (15)0.0525 (2)0.03318 (17)0.00043 (13)0.00561 (12)0.00042 (15)
O10.0272 (12)0.0288 (12)0.0230 (11)0.0006 (9)0.0063 (10)0.0012 (9)
N10.0254 (12)0.0208 (11)0.0190 (11)0.0015 (9)0.0083 (10)0.0007 (9)
O20.0218 (11)0.0341 (11)0.0215 (11)0.0064 (9)0.0087 (9)0.0024 (8)
C20.0236 (14)0.0236 (13)0.0159 (12)0.0007 (11)0.0044 (11)0.0002 (11)
C30.0191 (13)0.0209 (13)0.0196 (13)0.0012 (10)0.0040 (11)0.0000 (11)
C40.0230 (13)0.0133 (12)0.0213 (12)0.0015 (10)0.0101 (11)0.0007 (10)
C50.0185 (12)0.0149 (12)0.0185 (12)0.0008 (10)0.0051 (10)0.0008 (10)
C60.0218 (13)0.0189 (13)0.0199 (13)0.0008 (11)0.0082 (11)0.0001 (10)
C70.0237 (14)0.0227 (14)0.0185 (13)0.0011 (11)0.0068 (11)0.0001 (11)
C80.0175 (13)0.0192 (13)0.0259 (14)0.0018 (10)0.0043 (11)0.0000 (11)
C90.0217 (13)0.0192 (13)0.0250 (14)0.0012 (10)0.0121 (12)0.0004 (11)
C100.0226 (13)0.0130 (12)0.0210 (13)0.0010 (10)0.0105 (11)0.0017 (10)
N110.0175 (11)0.0273 (12)0.0157 (11)0.0001 (9)0.0049 (9)0.0008 (10)
C120.0168 (13)0.0235 (13)0.0240 (13)0.0000 (10)0.0062 (11)0.0025 (11)
C130.0161 (13)0.0211 (13)0.0272 (14)0.0015 (10)0.0065 (12)0.0012 (11)
N140.0171 (11)0.0210 (11)0.0206 (12)0.0002 (9)0.0064 (10)0.0010 (9)
C150.0293 (16)0.0304 (15)0.0241 (15)0.0018 (12)0.0116 (13)0.0013 (12)
C160.0435 (18)0.0345 (17)0.0511 (19)0.0024 (14)0.0326 (16)0.0005 (14)
C170.0213 (15)0.0254 (14)0.0270 (15)0.0004 (11)0.0063 (13)0.0013 (11)
C180.0254 (15)0.0264 (15)0.0419 (17)0.0015 (12)0.0103 (14)0.0012 (13)
Geometric parameters (Å, º) top
Br1—C81.904 (3)N11—C121.454 (3)
O1—H11W0.93 (3)N11—H110.84 (2)
O1—H12W0.79 (3)C12—C131.514 (3)
N1—C21.321 (3)C12—H12A0.9900
N1—C101.369 (3)C12—H12B0.9900
O2—H21W0.84 (3)C13—N141.470 (3)
O2—H22W0.88 (3)C13—H13A0.9900
C2—C31.391 (3)C13—H13B0.9900
C2—H20.9500N14—C171.469 (3)
C3—C41.392 (3)N14—C151.481 (3)
C3—H30.9500C15—C161.529 (4)
C4—N111.354 (3)C15—H15A0.9900
C4—C51.441 (3)C15—H15B0.9900
C5—C61.413 (3)C16—H16C0.9800
C5—C101.419 (3)C16—H16A0.9800
C6—C71.366 (3)C16—H16B0.9800
C6—H60.9500C17—C181.514 (4)
C7—C81.405 (3)C17—H17A0.9900
C7—H70.9500C17—H17B0.9900
C8—C91.362 (4)C18—H18A0.9800
C9—C101.411 (3)C18—H17C0.9800
C9—H90.9500C18—H18B0.9800
H11W—O1—H12W114 (3)N11—C12—H12B109.4
C2—N1—C10116.3 (2)C13—C12—H12B109.4
H21W—O2—H22W105 (3)H12A—C12—H12B108.0
N1—C2—C3125.5 (2)N14—C13—C12114.6 (2)
N1—C2—H2117.3N14—C13—H13A108.6
C3—C2—H2117.3C12—C13—H13A108.6
C2—C3—C4119.9 (2)N14—C13—H13B108.6
C2—C3—H3120.1C12—C13—H13B108.6
C4—C3—H3120.1H13A—C13—H13B107.6
N11—C4—C3122.5 (2)C17—N14—C13110.35 (19)
N11—C4—C5120.7 (2)C17—N14—C15112.87 (19)
C3—C4—C5116.8 (2)C13—N14—C15110.40 (19)
C6—C5—C10118.5 (2)N14—C15—C16116.7 (2)
C6—C5—C4123.5 (2)N14—C15—H15A108.1
C10—C5—C4118.0 (2)C16—C15—H15A108.1
C7—C6—C5121.6 (2)N14—C15—H15B108.1
C7—C6—H6119.2C16—C15—H15B108.1
C5—C6—H6119.2H15A—C15—H15B107.3
C6—C7—C8118.8 (2)C15—C16—H16C109.5
C6—C7—H7120.6C15—C16—H16A109.5
C8—C7—H7120.6H16C—C16—H16A109.5
C9—C8—C7122.0 (2)C15—C16—H16B109.5
C9—C8—Br1119.25 (19)H16C—C16—H16B109.5
C7—C8—Br1118.78 (19)H16A—C16—H16B109.5
C8—C9—C10119.8 (2)N14—C17—C18113.7 (2)
C8—C9—H9120.1N14—C17—H17A108.8
C10—C9—H9120.1C18—C17—H17A108.8
N1—C10—C9117.2 (2)N14—C17—H17B108.8
N1—C10—C5123.5 (2)C18—C17—H17B108.8
C9—C10—C5119.3 (2)H17A—C17—H17B107.7
C4—N11—C12121.8 (2)C17—C18—H18A109.5
C4—N11—H11120.4 (19)C17—C18—H17C109.5
C12—N11—H11115.1 (19)H18A—C18—H17C109.5
N11—C12—C13110.9 (2)C17—C18—H18B109.5
N11—C12—H12A109.4H18A—C18—H18B109.5
C13—C12—H12A109.4H17C—C18—H18B109.5
C10—N1—C2—C30.6 (3)C8—C9—C10—N1178.1 (2)
N1—C2—C3—C40.7 (4)C8—C9—C10—C51.4 (3)
C2—C3—C4—N11178.6 (2)C6—C5—C10—N1177.4 (2)
C2—C3—C4—C50.2 (3)C4—C5—C10—N11.2 (3)
N11—C4—C5—C61.0 (3)C6—C5—C10—C92.1 (3)
C3—C4—C5—C6177.4 (2)C4—C5—C10—C9179.4 (2)
N11—C4—C5—C10179.4 (2)C3—C4—N11—C122.6 (3)
C3—C4—C5—C101.0 (3)C5—C4—N11—C12179.1 (2)
C10—C5—C6—C70.8 (3)C4—N11—C12—C13177.3 (2)
C4—C5—C6—C7179.3 (2)N11—C12—C13—N1470.9 (3)
C5—C6—C7—C81.1 (3)C12—C13—N14—C1778.3 (3)
C6—C7—C8—C91.8 (4)C12—C13—N14—C15156.2 (2)
C6—C7—C8—Br1179.21 (18)C17—N14—C15—C1656.2 (3)
C7—C8—C9—C100.5 (4)C13—N14—C15—C1667.9 (3)
Br1—C8—C9—C10179.55 (16)C13—N14—C17—C18176.5 (2)
C2—N1—C10—C9179.8 (2)C15—N14—C17—C1859.5 (3)
C2—N1—C10—C50.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O10.84 (2)2.22 (3)3.038 (3)166 (3)
O1—H11W···O2i0.93 (3)2.01 (3)2.924 (3)169 (3)
O1—H12W···O20.79 (3)2.03 (3)2.824 (3)176 (3)
O2—H22W···N1ii0.88 (3)1.86 (3)2.722 (3)166 (3)
O2—H21W···N14i0.84 (3)2.14 (3)2.977 (3)172 (3)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x, y+2, z1/2.
(III) 7-chloro-4-[2-(diethylammonio)ethylamino]quinolinium bis(dihydrogenphosphate) phosphoric acid top
Crystal data top
C15H22ClN32+·2H2O4P·H3O4PZ = 4
Mr = 571.77F(000) = 1192
Triclinic, P1Dx = 1.643 Mg m3
Hall symbol: -P 1Melting point = 466–468 K
a = 11.0960 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 14.6481 (3) ÅCell parameters from 9976 reflections
c = 15.1797 (4) Åθ = 1.5–26.8°
α = 79.552 (1)°µ = 0.44 mm1
β = 88.019 (1)°T = 113 K
γ = 72.336 (1)°Plate, colourless
V = 2311.38 (9) Å30.25 × 0.15 × 0.04 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
9766 independent reflections
Radiation source: fine-focus sealed tube6450 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.128
ω and ϕ scansθmax = 26.8°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 1413
Tmin = 0.898, Tmax = 0.984k = 1818
42956 measured reflectionsl = 1919
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0549P)2]
where P = (Fo2 + 2Fc2)/3
9766 reflections(Δ/σ)max = 0.001
697 parametersΔρmax = 0.54 e Å3
14 restraintsΔρmin = 0.75 e Å3
Crystal data top
C15H22ClN32+·2H2O4P·H3O4Pγ = 72.336 (1)°
Mr = 571.77V = 2311.38 (9) Å3
Triclinic, P1Z = 4
a = 11.0960 (2) ÅMo Kα radiation
b = 14.6481 (3) ŵ = 0.44 mm1
c = 15.1797 (4) ÅT = 113 K
α = 79.552 (1)°0.25 × 0.15 × 0.04 mm
β = 88.019 (1)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
9766 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
6450 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 0.984Rint = 0.128
42956 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05414 restraints
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.54 e Å3
9766 reflectionsΔρmin = 0.75 e Å3
697 parameters
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. The structure was solved by direct methods and refined on F2 using SHELX97 (Sheldrick, 1997) within the X-SEED interface (Barbour, 2003). A weighting scheme based on P = (Fo2 + 2Fc2)/3 was employed in order to reduce statistical bias (Wilson, 1976). Molecular geometry and supramolecular interactions were analysed with the aid of PLATON (Spek, 2003). Diagrams were prepared using POV-RAY (Cason, 2003) within the X-SEED interface. Bond lengths and angles are in agreement with typical literature values. 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. [Wilson, A. J. C. (1976). Acta Cryst. A32, 994–996.]

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl1A1.03866 (7)0.65341 (6)0.23778 (5)0.0239 (2)
N1A1.1493 (2)0.54579 (19)0.57057 (18)0.0201 (6)
H1A1.235 (3)0.511 (2)0.554 (2)0.026 (9)*
C2A1.1225 (3)0.5429 (2)0.6573 (2)0.0208 (7)
H2A1.18670.50640.70070.025*
C3A1.0065 (3)0.5904 (2)0.6858 (2)0.0201 (7)
H3A0.99250.58870.74810.024*
C4A0.9065 (3)0.6423 (2)0.6233 (2)0.0166 (7)
C5A0.9349 (3)0.6455 (2)0.5296 (2)0.0172 (7)
C6A0.8446 (3)0.6958 (2)0.4590 (2)0.0186 (7)
H6A0.76050.72900.47320.022*
C7A0.8771 (3)0.6970 (2)0.3721 (2)0.0216 (7)
H7A0.81560.73090.32600.026*
C8A1.0003 (3)0.6487 (2)0.3496 (2)0.0195 (7)
C9A1.0918 (3)0.5993 (2)0.4147 (2)0.0201 (7)
H9A1.17560.56740.39890.024*
C10A1.0584 (3)0.5972 (2)0.5051 (2)0.0171 (7)
N11A0.7903 (2)0.68560 (19)0.65015 (17)0.0179 (6)
H11A0.717 (4)0.224 (3)0.616 (3)0.052 (12)*
C12A0.7586 (3)0.6956 (2)0.7431 (2)0.0182 (7)
H12A0.68120.75160.74260.022*
H12B0.82790.71180.77000.022*
C13A0.7368 (3)0.6076 (2)0.8039 (2)0.0183 (7)
H13A0.78970.54790.78340.022*
H13B0.76550.60540.86550.022*
N14A0.6013 (2)0.6068 (2)0.80656 (17)0.0174 (6)
H14A0.557 (3)0.661 (2)0.822 (2)0.017 (9)*
C15A0.5531 (3)0.6001 (2)0.7172 (2)0.0203 (7)
H15A0.60410.53820.69950.024*
H15B0.56440.65430.67150.024*
C16A0.4156 (3)0.6045 (2)0.7183 (2)0.0278 (8)
H16A0.40630.54410.75350.042*
H16B0.38480.61240.65680.042*
H16C0.36630.65990.74520.042*
C17A0.5809 (3)0.5299 (2)0.8822 (2)0.0229 (7)
H17A0.62030.53520.93790.028*
H17B0.48890.54350.89200.028*
C18A0.6348 (3)0.4266 (2)0.8652 (2)0.0260 (8)
H18A0.59480.42000.81110.039*
H18B0.61810.38110.91660.039*
H18C0.72630.41170.85710.039*
Cl1B1.03743 (8)0.13997 (6)0.26036 (5)0.0260 (2)
N1B1.1423 (2)0.05115 (19)0.59475 (17)0.0185 (6)
H1B1.223 (3)0.023 (2)0.580 (2)0.025 (9)*
C2B1.1139 (3)0.0530 (2)0.6806 (2)0.0189 (7)
H2B1.17810.02020.72510.023*
C3B0.9960 (3)0.1003 (2)0.7070 (2)0.0191 (7)
H3B0.98020.10180.76870.023*
C4B0.8974 (3)0.1469 (2)0.6426 (2)0.0165 (7)
C5B0.9287 (3)0.1463 (2)0.5495 (2)0.0173 (7)
C6B0.8393 (3)0.1916 (2)0.4777 (2)0.0214 (7)
H6B0.75440.22420.49070.026*
C7B0.8727 (3)0.1893 (2)0.3911 (2)0.0214 (7)
H7B0.81170.22010.34410.026*
C8B0.9981 (3)0.1409 (2)0.3715 (2)0.0199 (7)
C9B1.0885 (3)0.0953 (2)0.4381 (2)0.0196 (7)
H9B1.17290.06300.42380.024*
C10B1.0532 (3)0.0977 (2)0.5278 (2)0.0167 (7)
N11B0.7792 (2)0.18997 (18)0.66548 (17)0.0176 (6)
H11B0.728 (4)0.715 (3)0.609 (3)0.049 (12)*
C12B0.7424 (3)0.1960 (2)0.7584 (2)0.0190 (7)
H12C0.66170.24900.75800.023*
H12D0.80730.21420.78830.023*
C13B0.7260 (3)0.1029 (2)0.8138 (2)0.0183 (7)
H13C0.78440.04640.79160.022*
H13D0.75090.09870.87680.022*
N14B0.5940 (2)0.09551 (19)0.81179 (17)0.0171 (6)
H14B0.546 (3)0.155 (2)0.828 (2)0.019 (9)*
C15B0.5517 (3)0.0942 (2)0.7189 (2)0.0192 (7)
H17C0.60990.03750.69670.023*
H17D0.55660.15390.67820.023*
C16B0.4181 (3)0.0885 (2)0.7166 (2)0.0243 (8)
H18D0.41770.02200.74170.036*
H18E0.38610.10580.65450.036*
H18F0.36390.13390.75220.036*
C17B0.5781 (3)0.0122 (2)0.8809 (2)0.0221 (7)
H15C0.48680.01900.88670.026*
H15D0.61030.01640.93950.026*
C18B0.6462 (3)0.0869 (2)0.8584 (2)0.0258 (8)
H16D0.61280.09250.80140.039*
H16E0.63290.13770.90600.039*
H16F0.73690.09460.85340.039*
P1C0.04913 (7)0.11808 (6)0.97748 (5)0.0168 (2)
O2C0.11285 (19)0.04409 (15)0.92098 (14)0.0192 (5)
O3C0.11599 (19)0.19243 (15)0.98368 (14)0.0202 (5)
O4C0.08912 (19)0.16847 (15)0.93799 (14)0.0204 (5)
H4C0.154 (3)0.197 (3)0.981 (3)0.059 (13)*
O5C0.0351 (2)0.07007 (15)1.07751 (14)0.0202 (5)
H5C0.024 (4)0.031 (3)1.085 (3)0.074 (15)*
P1D0.47262 (7)0.37797 (6)0.58040 (5)0.0171 (2)
O2D0.5658 (2)0.42734 (16)0.61219 (14)0.0237 (5)
H2D0.574 (5)0.482 (3)0.562 (3)0.11 (2)*
O3D0.54951 (19)0.28257 (15)0.55642 (15)0.0234 (5)
O4D0.3870 (2)0.36299 (18)0.66206 (16)0.0284 (6)
H4D0.416 (6)0.339 (5)0.720 (3)0.16 (3)*
O5D0.38181 (19)0.44600 (15)0.50729 (14)0.0195 (5)
P1E0.08354 (8)0.59654 (6)0.93870 (5)0.0182 (2)
O2E0.2019 (2)0.62296 (17)0.90365 (15)0.0284 (6)
H2E0.226 (4)0.679 (3)0.918 (3)0.097 (18)*
O3E0.0982 (2)0.57117 (15)1.04258 (14)0.0215 (5)
H3E0.032 (3)0.549 (3)1.065 (3)0.061 (14)*
O4E0.07182 (19)0.51287 (15)0.89873 (14)0.0194 (5)
O5E0.0384 (2)0.68249 (16)0.91437 (15)0.0237 (5)
H5E0.071 (4)0.727 (3)0.948 (3)0.050 (13)*
P1F0.33922 (7)0.81462 (6)0.89529 (5)0.0164 (2)
O2F0.47519 (18)0.75201 (14)0.90124 (13)0.0183 (5)
O3F0.24895 (19)0.76555 (15)0.94554 (14)0.0218 (5)
O4F0.2932 (2)0.84771 (16)0.79549 (14)0.0234 (5)
H4F0.364 (3)0.847 (3)0.749 (2)0.039 (10)*
O5F0.3323 (2)0.90787 (16)0.93465 (15)0.0227 (5)
H5F0.259 (3)0.955 (3)0.931 (3)0.067 (15)*
P1G0.48709 (7)0.88015 (6)0.59041 (5)0.0174 (2)
O2G0.59085 (19)0.92980 (16)0.60234 (14)0.0202 (5)
H2G0.605 (4)0.968 (3)0.549 (3)0.079 (16)*
O3G0.55876 (19)0.80070 (16)0.53399 (15)0.0206 (5)
H3G0.516 (3)0.772 (3)0.504 (3)0.063 (14)*
O4G0.4602 (2)0.83212 (16)0.68111 (14)0.0274 (6)
O5G0.37415 (18)0.95214 (15)0.53753 (14)0.0202 (5)
P1H0.34869 (7)0.29833 (6)0.88708 (5)0.0175 (2)
O2H0.2345 (2)0.37879 (17)0.83702 (14)0.0254 (5)
H2H0.177 (4)0.432 (3)0.862 (3)0.067 (14)*
O3H0.3185 (2)0.20034 (16)0.90912 (16)0.0281 (6)
H3H0.237 (3)0.194 (3)0.941 (3)0.068 (14)*
O4H0.46035 (18)0.28290 (15)0.82823 (14)0.0190 (5)
O5H0.3664 (2)0.33338 (16)0.97447 (15)0.0248 (5)
H5H0.428 (5)0.300 (4)1.019 (3)0.13 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl1A0.0266 (4)0.0299 (5)0.0146 (4)0.0084 (4)0.0017 (3)0.0018 (3)
N1A0.0165 (14)0.0196 (15)0.0187 (15)0.0001 (12)0.0058 (12)0.0019 (12)
C2A0.0201 (17)0.0228 (18)0.0164 (17)0.0052 (14)0.0067 (14)0.0035 (14)
C3A0.0220 (17)0.0221 (18)0.0147 (16)0.0067 (14)0.0071 (14)0.0022 (13)
C4A0.0190 (16)0.0148 (16)0.0153 (16)0.0064 (13)0.0049 (14)0.0024 (13)
C5A0.0189 (16)0.0136 (16)0.0172 (16)0.0039 (13)0.0047 (14)0.0017 (13)
C6A0.0162 (16)0.0203 (17)0.0167 (17)0.0031 (13)0.0017 (14)0.0010 (13)
C7A0.0199 (17)0.0237 (18)0.0176 (18)0.0041 (14)0.0100 (14)0.0032 (14)
C8A0.0249 (17)0.0186 (17)0.0146 (16)0.0068 (14)0.0029 (14)0.0006 (13)
C9A0.0173 (16)0.0177 (17)0.0236 (18)0.0031 (13)0.0027 (15)0.0022 (14)
C10A0.0177 (16)0.0144 (16)0.0172 (17)0.0040 (13)0.0056 (14)0.0017 (13)
N11A0.0178 (14)0.0210 (15)0.0126 (14)0.0043 (12)0.0038 (12)0.0010 (11)
C12A0.0194 (16)0.0181 (17)0.0160 (16)0.0033 (13)0.0045 (14)0.0035 (13)
C13A0.0161 (16)0.0217 (17)0.0160 (16)0.0043 (13)0.0046 (13)0.0017 (13)
N14A0.0195 (14)0.0184 (15)0.0123 (14)0.0032 (12)0.0054 (12)0.0014 (11)
C15A0.0245 (17)0.0204 (17)0.0135 (16)0.0048 (14)0.0083 (14)0.0012 (13)
C16A0.0247 (18)0.0253 (19)0.032 (2)0.0047 (15)0.0119 (16)0.0043 (16)
C17A0.0243 (17)0.0227 (18)0.0219 (18)0.0105 (15)0.0013 (15)0.0017 (14)
C18A0.0302 (18)0.0221 (18)0.0256 (19)0.0088 (15)0.0066 (16)0.0010 (15)
Cl1B0.0310 (5)0.0310 (5)0.0154 (4)0.0093 (4)0.0003 (4)0.0032 (3)
N1B0.0144 (14)0.0190 (15)0.0188 (15)0.0012 (12)0.0049 (12)0.0010 (11)
C2B0.0190 (16)0.0190 (17)0.0167 (17)0.0053 (14)0.0083 (14)0.0028 (13)
C3B0.0206 (17)0.0210 (17)0.0145 (16)0.0066 (14)0.0046 (14)0.0017 (13)
C4B0.0182 (16)0.0141 (16)0.0156 (16)0.0055 (13)0.0039 (14)0.0031 (13)
C5B0.0207 (16)0.0154 (16)0.0147 (16)0.0051 (13)0.0047 (14)0.0009 (13)
C6B0.0150 (16)0.0244 (18)0.0212 (18)0.0022 (14)0.0063 (14)0.0006 (14)
C7B0.0228 (17)0.0214 (18)0.0157 (17)0.0016 (14)0.0070 (14)0.0004 (14)
C8B0.0257 (17)0.0205 (17)0.0137 (16)0.0082 (14)0.0004 (14)0.0015 (13)
C9B0.0160 (16)0.0198 (17)0.0217 (18)0.0044 (13)0.0011 (14)0.0016 (14)
C10B0.0178 (16)0.0152 (16)0.0149 (16)0.0040 (13)0.0085 (14)0.0026 (13)
N11B0.0177 (14)0.0215 (15)0.0107 (13)0.0031 (12)0.0040 (12)0.0003 (11)
C12B0.0203 (16)0.0201 (17)0.0156 (16)0.0038 (14)0.0034 (14)0.0037 (13)
C13B0.0157 (15)0.0237 (18)0.0140 (16)0.0052 (13)0.0079 (13)0.0003 (13)
N14B0.0168 (13)0.0180 (15)0.0148 (14)0.0031 (12)0.0058 (11)0.0012 (11)
C15B0.0216 (17)0.0225 (17)0.0126 (16)0.0054 (14)0.0070 (14)0.0015 (13)
C16B0.0206 (17)0.0266 (19)0.0244 (19)0.0048 (15)0.0085 (15)0.0036 (15)
C17B0.0262 (17)0.0260 (19)0.0150 (17)0.0117 (15)0.0026 (14)0.0009 (14)
C18B0.0286 (18)0.0224 (18)0.0246 (19)0.0088 (15)0.0103 (16)0.0042 (15)
P1C0.0180 (4)0.0173 (4)0.0136 (4)0.0044 (3)0.0046 (3)0.0000 (3)
O2C0.0213 (11)0.0179 (12)0.0166 (11)0.0040 (9)0.0030 (10)0.0014 (9)
O3C0.0203 (11)0.0209 (12)0.0197 (12)0.0067 (10)0.0020 (10)0.0030 (10)
O4C0.0165 (11)0.0237 (12)0.0164 (12)0.0004 (10)0.0068 (10)0.0017 (10)
O5C0.0247 (12)0.0189 (12)0.0140 (11)0.0042 (10)0.0072 (10)0.0017 (9)
P1D0.0170 (4)0.0179 (4)0.0136 (4)0.0024 (3)0.0045 (3)0.0002 (3)
O2D0.0299 (13)0.0239 (13)0.0179 (12)0.0107 (10)0.0119 (10)0.0017 (10)
O3D0.0219 (11)0.0222 (12)0.0240 (12)0.0017 (10)0.0082 (10)0.0057 (10)
O4D0.0213 (12)0.0409 (15)0.0171 (13)0.0049 (11)0.0008 (11)0.0021 (11)
O5D0.0178 (11)0.0201 (12)0.0150 (11)0.0003 (9)0.0065 (9)0.0031 (9)
P1E0.0218 (4)0.0168 (4)0.0150 (4)0.0052 (3)0.0038 (4)0.0005 (3)
O2E0.0332 (13)0.0276 (14)0.0290 (14)0.0138 (11)0.0076 (11)0.0096 (11)
O3E0.0260 (13)0.0217 (12)0.0157 (12)0.0068 (10)0.0082 (10)0.0000 (9)
O4E0.0220 (11)0.0176 (12)0.0174 (12)0.0031 (9)0.0042 (9)0.0039 (9)
O5E0.0300 (13)0.0179 (12)0.0178 (12)0.0017 (10)0.0091 (11)0.0025 (10)
P1F0.0174 (4)0.0163 (4)0.0139 (4)0.0029 (3)0.0041 (3)0.0012 (3)
O2F0.0174 (11)0.0200 (12)0.0144 (11)0.0004 (9)0.0051 (9)0.0034 (9)
O3F0.0238 (12)0.0222 (12)0.0191 (12)0.0071 (10)0.0003 (10)0.0026 (10)
O4F0.0223 (12)0.0305 (13)0.0127 (12)0.0030 (10)0.0056 (10)0.0006 (10)
O5F0.0196 (12)0.0197 (12)0.0271 (13)0.0021 (10)0.0046 (11)0.0059 (10)
P1G0.0175 (4)0.0180 (4)0.0137 (4)0.0017 (3)0.0040 (3)0.0005 (3)
O2G0.0209 (11)0.0226 (12)0.0160 (12)0.0050 (10)0.0072 (10)0.0015 (10)
O3G0.0169 (11)0.0226 (12)0.0207 (12)0.0014 (10)0.0063 (10)0.0064 (10)
O4G0.0320 (13)0.0277 (13)0.0171 (12)0.0050 (11)0.0002 (11)0.0031 (10)
O5G0.0167 (11)0.0191 (12)0.0201 (12)0.0003 (9)0.0064 (10)0.0006 (9)
P1H0.0177 (4)0.0191 (4)0.0138 (4)0.0029 (3)0.0048 (4)0.0017 (3)
O2H0.0216 (12)0.0288 (13)0.0166 (12)0.0076 (10)0.0082 (10)0.0050 (10)
O3H0.0287 (13)0.0257 (13)0.0311 (14)0.0097 (11)0.0053 (11)0.0064 (11)
O4H0.0204 (11)0.0198 (12)0.0159 (11)0.0052 (9)0.0025 (9)0.0021 (9)
O5H0.0274 (13)0.0264 (13)0.0155 (12)0.0022 (10)0.0094 (11)0.0066 (10)
Geometric parameters (Å, º) top
Cl1A—C8A1.730 (3)N11B—H11A0.99 (4)
N1A—C2A1.336 (4)C12B—C13B1.525 (4)
N1A—C10A1.382 (4)C12B—H12C0.9900
N1A—H1A0.98 (3)C12B—H12D0.9900
C2A—C3A1.362 (4)C13B—N14B1.503 (4)
C2A—H2A0.9500C13B—H13C0.9900
C3A—C4A1.417 (4)C13B—H13D0.9900
C3A—H3A0.9500N14B—C15B1.507 (4)
C4A—N11A1.338 (4)N14B—C17B1.507 (4)
C4A—C5A1.442 (4)N14B—H14B0.95 (3)
C5A—C10A1.411 (4)C15B—C16B1.512 (4)
C5A—C6A1.427 (4)C15B—H17C0.9900
C6A—C7A1.354 (4)C15B—H17D0.9900
C6A—H6A0.9500C16B—H18D0.9800
C7A—C8A1.398 (4)C16B—H18E0.9800
C7A—H7A0.9500C16B—H18F0.9800
C8A—C9A1.376 (4)C17B—C18B1.513 (4)
C9A—C10A1.406 (4)C17B—H15C0.9900
C9A—H9A0.9500C17B—H15D0.9900
N11A—C12A1.465 (4)C18B—H16D0.9800
N11A—H11B0.90 (4)C18B—H16E0.9800
C12A—C13A1.521 (4)C18B—H16F0.9800
C12A—H12A0.9900P1C—O2C1.497 (2)
C12A—H12B0.9900P1C—O3C1.509 (2)
C13A—N14A1.505 (4)P1C—O4C1.573 (2)
C13A—H13A0.9900P1C—O5C1.577 (2)
C13A—H13B0.9900O3C—H3H1.47 (3)
N14A—C15A1.506 (4)O4C—H4C1.01 (3)
N14A—C17A1.519 (4)O5C—H5C0.99 (3)
N14A—H14A0.87 (3)P1D—O3D1.501 (2)
C15A—C16A1.507 (4)P1D—O5D1.519 (2)
C15A—H15A0.9900P1D—O4D1.560 (2)
C15A—H15B0.9900P1D—O2D1.562 (2)
C16A—H16A0.9800O2D—H2D1.02 (4)
C16A—H16B0.9800O4D—H4D0.92 (4)
C16A—H16C0.9800P1E—O4E1.503 (2)
C17A—C18A1.516 (4)P1E—O2E1.531 (2)
C17A—H17A0.9900P1E—O5E1.544 (2)
C17A—H17B0.9900P1E—O3E1.556 (2)
C18A—H18A0.9800O2E—H2E1.00 (4)
C18A—H18B0.9800O3E—H3E0.92 (3)
C18A—H18C0.9800O5E—H5E0.88 (3)
Cl1B—C8B1.729 (3)P1F—O2F1.505 (2)
N1B—C2B1.333 (4)P1F—O3F1.512 (2)
N1B—C10B1.373 (4)P1F—O4F1.558 (2)
N1B—H1B0.90 (3)P1F—O5F1.568 (2)
C2B—C3B1.367 (4)O4F—H4F1.04 (3)
C2B—H2B0.9500O5F—H5F0.88 (3)
C3B—C4B1.413 (4)P1G—O4G1.492 (2)
C3B—H3B0.9500P1G—O5G1.513 (2)
C4B—N11B1.336 (4)P1G—O2G1.568 (2)
C4B—C5B1.444 (4)P1G—O3G1.573 (2)
C5B—C10B1.407 (4)O2G—H2G0.94 (3)
C5B—C6B1.423 (4)O3G—H3G0.90 (3)
C6B—C7B1.357 (4)O4G—H4F1.45 (3)
C6B—H6B0.9500P1H—O4H1.487 (2)
C7B—C8B1.406 (4)P1H—O5H1.545 (2)
C7B—H7B0.9500P1H—O3H1.547 (2)
C8B—C9B1.376 (4)P1H—O2H1.551 (2)
C9B—C10B1.407 (4)O2H—H2H0.97 (3)
C9B—H9B0.9500O3H—H3H1.04 (3)
N11B—C12B1.465 (4)O5H—H5H0.93 (4)
C2A—N1A—C10A120.8 (3)C10B—C9B—H9B120.7
C2A—N1A—H1A118.8 (19)N1B—C10B—C5B119.9 (3)
C10A—N1A—H1A120.4 (19)N1B—C10B—C9B119.0 (3)
N1A—C2A—C3A122.5 (3)C5B—C10B—C9B121.1 (3)
N1A—C2A—H2A118.8C4B—N11B—C12B123.0 (3)
C3A—C2A—H2A118.8C4B—N11B—H11A117 (2)
C2A—C3A—C4A120.5 (3)C12B—N11B—H11A120 (2)
C2A—C3A—H3A119.7N11B—C12B—C13B115.1 (3)
C4A—C3A—H3A119.7N11B—C12B—H12C108.5
N11A—C4A—C3A121.5 (3)C13B—C12B—H12C108.5
N11A—C4A—C5A121.4 (3)N11B—C12B—H12D108.5
C3A—C4A—C5A117.1 (3)C13B—C12B—H12D108.5
C10A—C5A—C6A117.3 (3)H12C—C12B—H12D107.5
C10A—C5A—C4A119.1 (3)N14B—C13B—C12B114.5 (2)
C6A—C5A—C4A123.6 (3)N14B—C13B—H13C108.6
C7A—C6A—C5A120.9 (3)C12B—C13B—H13C108.6
C7A—C6A—H6A119.5N14B—C13B—H13D108.6
C5A—C6A—H6A119.5C12B—C13B—H13D108.6
C6A—C7A—C8A120.6 (3)H13C—C13B—H13D107.6
C6A—C7A—H7A119.7C13B—N14B—C15B112.2 (2)
C8A—C7A—H7A119.7C13B—N14B—C17B111.7 (2)
C9A—C8A—C7A121.2 (3)C15B—N14B—C17B113.3 (2)
C9A—C8A—Cl1A119.6 (2)C13B—N14B—H14B101.6 (18)
C7A—C8A—Cl1A119.1 (2)C15B—N14B—H14B107.7 (18)
C8A—C9A—C10A118.5 (3)C17B—N14B—H14B109.6 (19)
C8A—C9A—H9A120.7N14B—C15B—C16B112.2 (3)
C10A—C9A—H9A120.7N14B—C15B—H17C109.2
N1A—C10A—C9A118.7 (3)C16B—C15B—H17C109.2
N1A—C10A—C5A119.9 (3)N14B—C15B—H17D109.2
C9A—C10A—C5A121.4 (3)C16B—C15B—H17D109.2
C4A—N11A—C12A124.1 (3)H17C—C15B—H17D107.9
C4A—N11A—H11B119 (3)C15B—C16B—H18D109.5
C12A—N11A—H11B116 (3)C15B—C16B—H18E109.5
N11A—C12A—C13A116.5 (3)H18D—C16B—H18E109.5
N11A—C12A—H12A108.2C15B—C16B—H18F109.5
C13A—C12A—H12A108.2H18D—C16B—H18F109.5
N11A—C12A—H12B108.2H18E—C16B—H18F109.5
C13A—C12A—H12B108.2N14B—C17B—C18B113.4 (3)
H12A—C12A—H12B107.3N14B—C17B—H15C108.9
N14A—C13A—C12A114.4 (2)C18B—C17B—H15C108.9
N14A—C13A—H13A108.7N14B—C17B—H15D108.9
C12A—C13A—H13A108.7C18B—C17B—H15D108.9
N14A—C13A—H13B108.7H15C—C17B—H15D107.7
C12A—C13A—H13B108.7C17B—C18B—H16D109.5
H13A—C13A—H13B107.6C17B—C18B—H16E109.5
C13A—N14A—C15A112.5 (2)H16D—C18B—H16E109.5
C13A—N14A—C17A111.7 (2)C17B—C18B—H16F109.5
C15A—N14A—C17A112.9 (2)H16D—C18B—H16F109.5
C13A—N14A—H14A107 (2)H16E—C18B—H16F109.5
C15A—N14A—H14A109 (2)O2C—P1C—O3C115.00 (12)
C17A—N14A—H14A103 (2)O2C—P1C—O4C106.63 (12)
N14A—C15A—C16A112.7 (3)O3C—P1C—O4C111.18 (12)
N14A—C15A—H15A109.0O2C—P1C—O5C112.34 (12)
C16A—C15A—H15A109.0O3C—P1C—O5C105.16 (12)
N14A—C15A—H15B109.0O4C—P1C—O5C106.27 (12)
C16A—C15A—H15B109.0P1C—O3C—H3H125.1 (17)
H15A—C15A—H15B107.8P1C—O4C—H4C116 (2)
C15A—C16A—H16A109.5P1C—O5C—H5C114 (3)
C15A—C16A—H16B109.5O3D—P1D—O5D115.12 (12)
H16A—C16A—H16B109.5O3D—P1D—O4D111.56 (13)
C15A—C16A—H16C109.5O5D—P1D—O4D104.57 (12)
H16A—C16A—H16C109.5O3D—P1D—O2D107.98 (12)
H16B—C16A—H16C109.5O5D—P1D—O2D111.77 (12)
C18A—C17A—N14A114.0 (3)O4D—P1D—O2D105.43 (13)
C18A—C17A—H17A108.8P1D—O2D—H2D109 (3)
N14A—C17A—H17A108.8P1D—O4D—H4D125 (4)
C18A—C17A—H17B108.8O4E—P1E—O2E109.70 (13)
N14A—C17A—H17B108.8O4E—P1E—O5E107.96 (12)
H17A—C17A—H17B107.6O2E—P1E—O5E112.11 (13)
C17A—C18A—H18A109.5O4E—P1E—O3E112.34 (12)
C17A—C18A—H18B109.5O2E—P1E—O3E106.65 (13)
H18A—C18A—H18B109.5O5E—P1E—O3E108.12 (13)
C17A—C18A—H18C109.5P1E—O2E—H2E124 (3)
H18A—C18A—H18C109.5P1E—O3E—H3E108 (3)
H18B—C18A—H18C109.5P1E—O5E—H5E124 (3)
C2B—N1B—C10B121.1 (3)O2F—P1F—O3F114.26 (12)
C2B—N1B—H1B119 (2)O2F—P1F—O4F110.17 (12)
C10B—N1B—H1B119 (2)O3F—P1F—O4F107.91 (12)
N1B—C2B—C3B122.4 (3)O2F—P1F—O5F107.62 (12)
N1B—C2B—H2B118.8O3F—P1F—O5F108.67 (13)
C3B—C2B—H2B118.8O4F—P1F—O5F108.03 (12)
C2B—C3B—C4B120.1 (3)P1F—O4F—H4F115.5 (19)
C2B—C3B—H3B120.0P1F—O5F—H5F118 (3)
C4B—C3B—H3B120.0O4G—P1G—O5G115.93 (13)
N11B—C4B—C3B122.2 (3)O4G—P1G—O2G107.56 (13)
N11B—C4B—C5B120.4 (3)O5G—P1G—O2G110.76 (12)
C3B—C4B—C5B117.4 (3)O4G—P1G—O3G109.84 (13)
C10B—C5B—C6B117.7 (3)O5G—P1G—O3G110.13 (12)
C10B—C5B—C4B119.0 (3)O2G—P1G—O3G101.64 (12)
C6B—C5B—C4B123.3 (3)P1G—O2G—H2G112 (3)
C7B—C6B—C5B121.4 (3)P1G—O3G—H3G121 (3)
C7B—C6B—H6B119.3P1G—O4G—H4F139.6 (14)
C5B—C6B—H6B119.3O4H—P1H—O5H114.84 (12)
C6B—C7B—C8B119.6 (3)O4H—P1H—O3H106.73 (13)
C6B—C7B—H7B120.2O5H—P1H—O3H110.16 (13)
C8B—C7B—H7B120.2O4H—P1H—O2H109.77 (12)
C9B—C8B—C7B121.6 (3)O5H—P1H—O2H105.22 (12)
C9B—C8B—Cl1B120.1 (2)O3H—P1H—O2H110.14 (13)
C7B—C8B—Cl1B118.3 (2)P1H—O2H—H2H126 (2)
C8B—C9B—C10B118.6 (3)P1H—O3H—H3H122 (2)
C8B—C9B—H9B120.7P1H—O5H—H5H126 (4)
C10A—N1A—C2A—C3A0.6 (5)C10B—N1B—C2B—C3B0.3 (5)
N1A—C2A—C3A—C4A2.7 (5)N1B—C2B—C3B—C4B2.1 (5)
C2A—C3A—C4A—N11A176.8 (3)C2B—C3B—C4B—N11B176.7 (3)
C2A—C3A—C4A—C5A2.5 (4)C2B—C3B—C4B—C5B3.0 (4)
N11A—C4A—C5A—C10A178.8 (3)N11B—C4B—C5B—C10B178.0 (3)
C3A—C4A—C5A—C10A0.4 (4)C3B—C4B—C5B—C10B1.7 (4)
N11A—C4A—C5A—C6A1.5 (5)N11B—C4B—C5B—C6B1.2 (5)
C3A—C4A—C5A—C6A179.2 (3)C3B—C4B—C5B—C6B179.1 (3)
C10A—C5A—C6A—C7A0.2 (4)C10B—C5B—C6B—C7B0.7 (5)
C4A—C5A—C6A—C7A179.4 (3)C4B—C5B—C6B—C7B180.0 (3)
C5A—C6A—C7A—C8A0.0 (5)C5B—C6B—C7B—C8B0.2 (5)
C6A—C7A—C8A—C9A0.4 (5)C6B—C7B—C8B—C9B0.1 (5)
C6A—C7A—C8A—Cl1A179.0 (2)C6B—C7B—C8B—Cl1B179.6 (2)
C7A—C8A—C9A—C10A0.9 (5)C7B—C8B—C9B—C10B0.1 (5)
Cl1A—C8A—C9A—C10A179.5 (2)Cl1B—C8B—C9B—C10B179.9 (2)
C2A—N1A—C10A—C9A179.0 (3)C2B—N1B—C10B—C5B1.7 (4)
C2A—N1A—C10A—C5A1.5 (4)C2B—N1B—C10B—C9B178.7 (3)
C8A—C9A—C10A—N1A178.5 (3)C6B—C5B—C10B—N1B178.7 (3)
C8A—C9A—C10A—C5A1.1 (4)C4B—C5B—C10B—N1B0.6 (4)
C6A—C5A—C10A—N1A178.8 (3)C6B—C5B—C10B—C9B1.0 (4)
C4A—C5A—C10A—N1A1.5 (4)C4B—C5B—C10B—C9B179.7 (3)
C6A—C5A—C10A—C9A0.7 (4)C8B—C9B—C10B—N1B179.0 (3)
C4A—C5A—C10A—C9A178.9 (3)C8B—C9B—C10B—C5B0.7 (4)
C3A—C4A—N11A—C12A8.7 (4)C3B—C4B—N11B—C12B2.4 (5)
C5A—C4A—N11A—C12A172.1 (3)C5B—C4B—N11B—C12B177.9 (3)
C4A—N11A—C12A—C13A81.8 (4)C4B—N11B—C12B—C13B78.0 (4)
N11A—C12A—C13A—N14A91.1 (3)N11B—C12B—C13B—N14B91.1 (3)
C12A—C13A—N14A—C15A64.0 (3)C12B—C13B—N14B—C15B62.4 (3)
C12A—C13A—N14A—C17A167.8 (3)C12B—C13B—N14B—C17B169.1 (3)
C13A—N14A—C15A—C16A177.0 (3)C13B—N14B—C15B—C16B179.0 (3)
C17A—N14A—C15A—C16A55.4 (4)C17B—N14B—C15B—C16B53.3 (3)
C13A—N14A—C17A—C18A73.7 (3)C13B—N14B—C17B—C18B71.3 (3)
C15A—N14A—C17A—C18A54.3 (3)C15B—N14B—C17B—C18B56.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O5Di0.98 (3)1.81 (3)2.787 (3)171 (3)
N11A—H11B···O3G0.90 (4)2.14 (4)3.026 (3)167 (4)
N14A—H14A···O2F0.87 (3)1.95 (3)2.777 (3)158 (3)
N1B—H1B···O5Gii0.90 (3)1.85 (3)2.742 (3)169 (3)
N11B—H11A···O3D0.99 (4)1.97 (4)2.908 (3)158 (3)
N14B—H14B···O4H0.95 (3)1.82 (3)2.747 (3)165 (3)
O4C—H4C···O3Fiii1.01 (3)1.56 (3)2.563 (3)176 (4)
O5C—H5C···O2Civ0.99 (3)1.69 (4)2.672 (3)168 (4)
O2D—H2D···O5Dv1.02 (4)1.53 (4)2.536 (3)167 (5)
O4D—H4D···O4H0.92 (4)1.71 (4)2.625 (3)172 (6)
O2E—H2E···O3F1.00 (4)1.49 (4)2.491 (3)174 (5)
O3E—H3E···O4Eiii0.92 (3)1.69 (3)2.601 (3)169 (4)
O5E—H5E···O3Ciii0.88 (3)1.66 (3)2.544 (3)173 (4)
O4F—H4F···O4G1.04 (3)1.45 (3)2.483 (3)171 (3)
O5F—H5F···O2Cvi0.88 (3)1.74 (3)2.625 (3)177 (4)
O2G—H2G···O5Gvii0.94 (3)1.65 (4)2.582 (3)172 (5)
O3G—H3G···O3Dv0.90 (3)1.63 (3)2.535 (3)175 (4)
O2H—H2H···O4E0.97 (3)1.56 (3)2.528 (3)173 (4)
O3H—H3H···O3C1.04 (3)1.47 (3)2.506 (3)176 (4)
O5H—H5H···O2Fviii0.93 (4)1.57 (4)2.501 (3)176 (6)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y1, z; (iii) x, y+1, z+2; (iv) x, y, z+2; (v) x+1, y+1, z+1; (vi) x, y+1, z; (vii) x+1, y+2, z+1; (viii) x+1, y+1, z+2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC15H20IN3C15H20BrN3·2H2OC15H22ClN32+·2H2O4P·H3O4P
Mr369.24358.28571.77
Crystal system, space groupOrthorhombic, PbcaMonoclinic, C2/cTriclinic, P1
Temperature (K)114113113
a, b, c (Å)13.2379 (7), 7.8883 (4), 29.4118 (17)28.0177 (4), 6.8221 (9), 18.9339 (4)11.0960 (2), 14.6481 (3), 15.1797 (4)
α, β, γ (°)90, 90, 9090, 113.61 (3), 9079.552 (1), 88.019 (1), 72.336 (1)
V3)3071.3 (3)3316.1 (9)2311.38 (9)
Z884
Radiation typeMo KαMo KαMo Kα
µ (mm1)2.082.490.44
Crystal size (mm)0.10 × 0.10 × 0.020.13 × 0.10 × 0.100.25 × 0.15 × 0.04
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Multi-scan
(SADABS; Sheldrick, 2000)
Multi-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.820, 0.9610.738, 0.7890.898, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections
34000, 3328, 2401 26586, 3403, 2470 42956, 9766, 6450
Rint0.0530.0740.128
(sin θ/λ)max1)0.6420.6260.635
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.081, 1.05 0.037, 0.080, 1.04 0.054, 0.140, 1.00
No. of reflections332834039766
No. of parameters178212697
No. of restraints0514
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.14, 1.020.38, 0.510.54, 0.75

Computer programs: COLLECT (Nonius, 1997), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), POV-RAY (Cason, 2003), SHELXL97 and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N11—H11···N1i0.83 (3)2.22 (3)3.019 (4)161 (3)
C6—H6···N1i0.952.593.504 (4)163
Symmetry code: (i) x1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O10.84 (2)2.22 (3)3.038 (3)166 (3)
O1—H11W···O2i0.93 (3)2.01 (3)2.924 (3)169 (3)
O1—H12W···O20.79 (3)2.03 (3)2.824 (3)176 (3)
O2—H22W···N1ii0.88 (3)1.86 (3)2.722 (3)166 (3)
O2—H21W···N14i0.84 (3)2.14 (3)2.977 (3)172 (3)
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x, y+2, z1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O5Di0.98 (3)1.81 (3)2.787 (3)171 (3)
N11A—H11B···O3G0.90 (4)2.14 (4)3.026 (3)167 (4)
N14A—H14A···O2F0.87 (3)1.95 (3)2.777 (3)158 (3)
N1B—H1B···O5Gii0.90 (3)1.85 (3)2.742 (3)169 (3)
N11B—H11A···O3D0.99 (4)1.97 (4)2.908 (3)158 (3)
N14B—H14B···O4H0.95 (3)1.82 (3)2.747 (3)165 (3)
O4C—H4C···O3Fiii1.01 (3)1.56 (3)2.563 (3)176 (4)
O5C—H5C···O2Civ0.99 (3)1.69 (4)2.672 (3)168 (4)
O2D—H2D···O5Dv1.02 (4)1.53 (4)2.536 (3)167 (5)
O4D—H4D···O4H0.92 (4)1.71 (4)2.625 (3)172 (6)
O2E—H2E···O3F1.00 (4)1.49 (4)2.491 (3)174 (5)
O3E—H3E···O4Eiii0.92 (3)1.69 (3)2.601 (3)169 (4)
O5E—H5E···O3Ciii0.88 (3)1.66 (3)2.544 (3)173 (4)
O4F—H4F···O4G1.04 (3)1.45 (3)2.483 (3)171 (3)
O5F—H5F···O2Cvi0.88 (3)1.74 (3)2.625 (3)177 (4)
O2G—H2G···O5Gvii0.94 (3)1.65 (4)2.582 (3)172 (5)
O3G—H3G···O3Dv0.90 (3)1.63 (3)2.535 (3)175 (4)
O2H—H2H···O4E0.97 (3)1.56 (3)2.528 (3)173 (4)
O3H—H3H···O3C1.04 (3)1.47 (3)2.506 (3)176 (4)
O5H—H5H···O2Fviii0.93 (4)1.57 (4)2.501 (3)176 (6)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y1, z; (iii) x, y+1, z+2; (iv) x, y, z+2; (v) x+1, y+1, z+1; (vi) x, y+1, z; (vii) x+1, y+2, z+1; (viii) x+1, y+1, z+2.
Selected torsion angles (°) top
Compoundτ1τ2τ3τ4τ5τ6
(I)-2.8 (2)80.6 (4)-171.2 (2)-74.8 (3)160.6 (3)-69.9 (4)
(II)-2.6 (3)-177.2 (2)-70.9 (3)156.2 (2)67.9 (3)176.5 (2)
(IIIA)8.6 (3)-81.5 (4)-91.3 (3)64.1 (3)-177.0 (3)-74.2 (3)
(IIIB)2.4 (2)78.0 (4)91.2 (3)62.5 (3)178.9 (2)71.1 (3)
τ1 = C3—C4—N11—C12 τ2 = C4—N11—C12—C13 τ3 = N11—C12—C13—N14 τ4 = C12—C13—N14—C15 τ5 = C13—N14—C15—C16 τ6 = C13—N14—C17—C18
 

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