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The structures of 3-amino-1,2R,4S,5-tetra­ammoniopentane tetrachloride monohydrate, C5H21N54+·4Cl·H2O, and 1,2R,3,4S,5-penta­ammoniopentane tetra­chloro­zincate tri­chlor­ide monohydrate, (C5H22N5)[ZnCl4]Cl3·H2O, have been determined from single-crystal X-ray diffraction data. Both compounds show a complex network of N—H...O, O—H...Cl and N—H...Cl hydrogen bonds. There are a total of 14 H atoms of the tetra-cation and 15 H atoms of the penta-cation available for hydrogen bonding. However, due to the particular shape of the primary linear poly­ammonium cations, only a certain number of H atoms can be involved in hydrogen-bond formation. It is further shown that hydrogen bonding has an influence on the conformation of such alkyl­ammonium cations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015024/jz1372sup1.cif
Contains datablocks I, II, alle

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015024/jz1372Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015024/jz1372IIsup3.hkl
Contains datablock kasaci~1

CCDC references: 143219; 143220

Comment top

Polyamines such as spermidine, spermine, or caldopentamine are widespread in nature (Geneste & Hesse, 1998) and are of importance in a variety of physiological processes. Their presence is essential for the growth and division of cells and it is believed that hydrogen bonding between the positively charged ammonium groups and the phosphate moieties of the DNA is of particular importance. It has therefore been suggested that these compounds could have a considerable potential as anti-tumour drugs (Labarre, 1985). All these compounds have the general composition NH2-(CH2)m-{[NH-(CH2)n]q-NH}r-(CH2)p-NH2 (3 = m,n,p = 5; 0 = q = 2; r = 0,1), i.e. they carry both primary and secondary amino groups within their structure. A related class of polymeric compounds are the linear polyethyleneimines (NH2—CH2—CH2-(NH—CH2—CH2)n-NH2) which have been intensively investigated as polyelectrolytes and as metal complexing agents (Zelewsky et al., 1993). However, besides the simple 1,2-diaminoethane, linear primary polyamines of composition NH2—CH2-[CH—NH2]n-CH2—NH2 which contain solely primary amino groups, have received scant attention. This is particularly remarkable, since the corresponding polyalcohols (sugar alcohols) have been well known for many years. A structural report of the protonated triamine (n = 1) appeared some years ago (Cini et al., 1991) and the structure of a fully protonated tetraamine (n = 2) has been elucidated very recently in our own laboratory (Zimmer et al., 1998). Linear primary polyamines with n > 1 could be of particular interest with regard to metal complex formation. As a result of steric constraints, it is not possible for the entire donor set to be coordinated to the same metal cation and consequently the formation of polynuclear species is to be expected. The protonated forms of these ligands are of further interest because the charge to molecular weight ratio of these cations is rather high. It should be kept in mind that the N: C ratio of the primary polyamines is double that of the above mentioned linear polyethyleneimines, and consequently, linear primary polyamines have an exceptionally high charge density. This can be seen by the dramatic increase of acidity which is observed for the increasing number of amino groups. The first pKa values for the fully protonated forms have been found to be 7.1, 3.6, 1.4, and < 1 for the di-, tri-, tetra- and pentaamine, respectively (Zimmer et al., 1998). The combination of the high acidity, the high charge density and the high number of N—H protons means that these compounds could also serve as novel hydrogen-donating building blocks in a hydrogen-bonding network. Consequently they represent an interesting class of compounds in the context of supramolecular chemistry and crystal engineering. In this contribution we report the structure and the hydrogen-bonding scheme of the chloride hydrate and the chloride-tetrachlorozincate hydrate salt of the tetra- and pentaprotonated 1,2R,3,4S,5-pentaamine, respectively.

3-Amino-1,2R,4S,5-tetraammonio-pentane tetrachloride monohydrate, (I): As expected from simple electrostatic considerations, the non-protonated amino group was located in the middle of the molecule at the 3 position. The fourfold protonated cation (Fig. 1a) is surrounded by seven chloride anions forming N—H···Cl hydrogen bonds to the ammonium groups and to the amino group, respectively. Additionally, one water molecule accepts an N—H···O hydrogen from one of the ammonium groups (N4). It is well known that the ammonium group is a significantly stronger hydrogen-bond donor than an amino group (Reiss et al., 1999) and consequently each ammonium group is capable of binding to two or three hydrogen acceptors while the amino group is involved in only one weak hydrogen bond [H···Cl 2.55 (3)/2.43 (3) Å] to the disordered chloride counter ion Cl4/Cl4" (Tab. 2). It is further noteworthy that in accord with the low basicity of the free amino group, N3 does not act as a hydrogen-acceptor in this structure.

It has been pointed out previously for a variety of solid-state structures that the conformation of aliphatic diammonium cations is arranged in a way that maximizes the number of hydrogen bonds to the counter ions or water molecules, and - if conformational flexibility is possible - the observed conformation in the solid state does not necessarily correspond to the lowest energy structure of an isolated molecule (Frank & Reiss, 1997). This is also true for the tetra-cation of (I), where the observed conformation proceeds from an all-trans arrangement of the carbon chain C1—C4 with additional rotation around the C3—C4 bond of 120°. Comparison with the structure of xylitol (Kim & Jeffrey, 1969) shows similar behaviour: the first four carbon atoms of both molecules form an approximately planar zigzag chain, whereas the carbon atom C5 is turned out of this plane. The angle between the mean plane defined by C1—C4 and the C4—C5 vector is 56 for xylitol and 60° for the cation of (I). The nitrogen atom N4 is also located within this plane. Clearly, this conformation results in an optimal distribution of the ammonium groups and the amino group over the molecular surface with regard to hydrogen-bond formation (Fig. 1a). All C—C bond lengths are in the normal range [1.520 (2)–1.548 (2) Å], the C—N bond lengths of the ammonium groups vary between [1.481 (2)–1.499 (2) Å], while the C—N distance of the amino group is somewhat shorter [1.459 (2) Å].

Three of the total of seven counter ions that are hydrogen bonded to the cation of (I) are involved in a chelate ring of the type N—H···Cl···H—N. According to Etter's nomenclature (Etter, 1990) this can be described as R12(7) (N5, C5, C4, N4, Cl2), R12 (7) (N2, C2, C3, N3, Cl4) and R12 (9) (N2, C2, C3, C4, C5, N5, Cl3). N2 and N5 both exhibit the maximum of each three N—H···Cl interactions. N1 binds two chloride ions, whereas N3 and N4 are involved in only one hydrogen bond to a chloride anion. In addition, N4 exhibits a hydrogen bond (N···O 2.79 Å) with a water molecule (O1). Cl4 is disordered with a site occupancy ratio of 0.12:0.88. This is plausible, if it is considered that the ammonium groups N2 and N3 interact with both possible positions Cl4 and Cl4" in such a way that the anion forms either a shorter contact to H23 (Cl4) or a shorter contact to H32 (Cl4") (Table 2).

1,2R,3,4S,5-pentammoniopentane trichloride tetrachlorozincate monohydrate, (II):

The pentaammonium cation of (II), the completely protonated form of the tetra-cation of (I), also exhibits a partially planar zigzag (all trans) structure (C1—C4). The torsional angle C1—C2—C3—C4 is 179.8°. Again, the C5—N5 vector is rotated out of the plane spanned by the first four carbon atoms by an angle of 61.3° into a syn-clinal conformation. Also the C1—N1 vector is rotated out of plane by an angle of 59.5°. All C—C bond lengths within the cation [1.539 (2)–1.559 (2) Å] fall in the expected range. The cation is surrounded by six chloride ions, three tetrachlorozincate anions and one water molecule (Table 4). N—H···O distances of 1.84 (3) and 1.87 (3) Å indicate strong hydrogen bonding. Neglecting some weak N—H···Cl interactions, classification according to Etter's rules (Etter, 1990) yields one large ring structure [R42 (18)], a water- containing ring [R44 (10)] and three rings in which the water molecule and the two Cl-anions Cl6 and Cl5 are chelated [R12 (7), R12 (8), R12 (9)] (Fig. 2a). The tetrachlorozincate anion shows some trigonal distortion (C3v) with an elongated Zn—Cl3 bond [Zn—Cl 2.3197 (13) Å, other Zn—Cl distances: 2.2587 (11)–2.2721 (14) Å]. This deformation of the complex anion can be explained by the fact that only Cl3 shows a significant interaction with the protons of the cation (Table 4). The packing of (II) can be described in terms of wavy layers of the ZnCl42- anions perpendicular to the a axis, which form only weak hydrogen-bonding interactions. The ZnCl42- anions form channels along [100] accommodating stacks of cations and chloride anions which are connected by hydrogen bonds (Table 4).

The present investigations established that protonated linear primary polyamines can serve as novel and interesting building blocks for extended hydrogen-bonded structures. In contrast to the neutral amino group, the positively charged ammonium groups exhibit a high tendency to be involved in mulitple N—H···Cl and N—H···O interactions. This type of hydrogen bonding is probably one of the major driving forces for the solid-state structure. It is, however, noteworthy that in both structures (I) and (II) not all of the N—H protons are involved in hydrogen bonding. The compact structure of the cations and the steric crowding do not allow for all the potential hydrogen-bonding interactions to take place.

Experimental top

Preparation of 1,2R,3,4S,5-pentaammonio-pentane pentachloride according to the literature (Zimmer et al., 1998).

3-Amino-1,2R,4S,5-tetraammonio-pentane tetrachloride monohydrate, (I):

1,2R,3,4S,5-pentammonio-pentane pentachloride (50 mg, 0.15 mmol) were dissolved in water (1 ml) and a few ml of ethanol were then added. The resulting microcrystalline precipitate was redissolved carefully by refluxing the suspension and adding small portions of 0.1 M HCl. Colourless, needle-shaped crystals grew from this solution at 277 K after a few days.

1,2R,3,4S,5-pentammonio-pentane trichloride tetrachlorozincate monohydrate, (II):

1,2R,3,4S,5-pentammonio-pentane pentachloride (30 mg, 0.09 mmol) were dissolved in a minimum amount of water and a solution of ZnCl2 (1.5 g) in HCl (8 ml, 6M) was added. After cooling to about 277 K a voluminous precipitate was formed. The liquid phase was decanted and the precipitate was redissolved in HCl (3 ml, 3 M) with heating. Colourless isometric crystals were formed during cooling of this solution to room temperature.

Computing details top

For both compounds, data collection: IPDS-Software (Stoe, 1998); cell refinement: IPDS-Software; data reduction: IPDS-Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: Diamond (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. a. The tetraammonio-amino-pentane cation of (I) with its hydrogen-bond accepting environment (seven chloride anions and one water molecule). Displacement ellipsoids are drawn at the 50% probability level, radii of the hydrogen atoms are of arbitrary size. Symmetry codes: a: x + 1, y, z; b: -x, -y, -z + 1.
[Figure 2] Fig. 2. b. Packing of compound (I) with a view along the a axis.
[Figure 3] Fig. 3. a. The pentaammonio-pentane cation of II with its hydrogen bond accepting environment (six chloride anions, one water molecule and three tetrachlorozincates). Displacement ellipsoids are drawn at the 50% probability level, radius of the hydrogen atoms are of arbitrary size. Symmetry codes:a: 1 - x, 1 - y, -1 - z; b: 1 + x, y, z; c: 2 - x, 1 - y, -z; d: 1 - x, 2 - y, -z
[Figure 4] Fig. 4. b. Packing of compound (II) with a view along the a axis.
(I) 1,2R,4S,5-tetraammonio-3-amino-pentane tetrachloride - hydrate top
Crystal data top
C5H21N54+·4Cl·H2OZ = 2
Mr = 311.08F(000) = 328
Triclinic, P1Dx = 1.459 Mg m3
a = 6.374 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.588 (2) ÅCell parameters from 5000 quasi centered reflections which were automatically selected from the whole data set and used in least squares refinement calculation. reflections
c = 11.303 (2) ŵ = 0.82 mm1
α = 71.35 (3)°T = 293 K
β = 78.45 (3)°Isometric, colourless
γ = 85.97 (3)°0.40 × 0.34 × 0.30 mm
V = 708.1 (2) Å3
Data collection top
Stoe IPDS
diffractometer
2361 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
Graphite monochromatorθmax = 27.0°, θmin = 4.1°
Detector resolution: 50 pixels mm-1h = 77
phi–scank = 1313
9244 measured reflectionsl = 1414
2870 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: difference Fourier map
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.02Calculated w = 1/[σ2(Fo2) + (0.0431P)2 + 0.1127P]
where P = (Fo2 + 2Fc2)/3
2870 reflections(Δ/σ)max < 0.001
196 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C5H21N54+·4Cl·H2Oγ = 85.97 (3)°
Mr = 311.08V = 708.1 (2) Å3
Triclinic, P1Z = 2
a = 6.374 (1) ÅMo Kα radiation
b = 10.588 (2) ŵ = 0.82 mm1
c = 11.303 (2) ÅT = 293 K
α = 71.35 (3)°0.40 × 0.34 × 0.30 mm
β = 78.45 (3)°
Data collection top
Stoe IPDS
diffractometer
2361 reflections with I > 2σ(I)
9244 measured reflectionsRint = 0.035
2870 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.32 e Å3
2870 reflectionsΔρmin = 0.33 e Å3
196 parameters
Special details top

Experimental. Compound (I): 238 exposures were taken in the 0–309.4 phi range with a crystal-to-detector distance of 60 mm and an exposure time of 4 min. Dynamic integration profiles (11–17 pixels) without allowing to overlap were used for integration. 92.6% completeness of data has been achieved in a theta range of 4.10–27.00°.

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*/UeqOcc. (<1)
Cl10.22644 (7)0.30291 (4)0.66123 (4)0.03529 (11)
Cl20.24971 (7)0.10030 (4)0.11024 (3)0.03921 (12)
Cl30.22416 (7)0.05132 (4)0.37812 (4)0.03821 (12)
Cl40.17143 (11)0.52173 (7)0.22431 (8)0.05063 (18)0.88
Cl4"0.1433 (8)0.4936 (4)0.1735 (5)0.0429 (10)0.12
O10.8400 (3)0.25422 (18)0.01087 (16)0.0709 (5)
H1W0.92040.24810.04500.106*
H2W0.84480.31880.02420.106*
N10.3112 (3)0.26730 (15)0.60187 (13)0.0349 (3)
H110.207 (5)0.292 (3)0.636 (2)0.063 (4)*
H120.412 (5)0.280 (2)0.636 (2)0.063 (4)*
H130.305 (4)0.177 (3)0.621 (2)0.063 (4)*
N20.0318 (2)0.27804 (15)0.40516 (13)0.0319 (3)
H210.030 (4)0.282 (2)0.482 (2)0.047 (3)*
H220.023 (4)0.214 (2)0.389 (2)0.047 (3)*
H230.008 (3)0.358 (2)0.353 (2)0.047 (3)*
N30.3614 (3)0.45028 (12)0.18035 (12)0.0293 (3)
H310.438 (4)0.490 (2)0.204 (2)0.042 (6)*
H320.231 (4)0.479 (2)0.195 (2)0.055 (7)*
N40.3964 (3)0.28567 (15)0.03587 (12)0.0335 (3)
H410.350 (4)0.252 (2)0.014 (2)0.050 (3)*
H420.534 (4)0.272 (2)0.028 (2)0.050 (3)*
H430.379 (4)0.373 (2)0.012 (2)0.050 (3)*
N50.1816 (3)0.00329 (14)0.18196 (14)0.0359 (3)
H510.049 (4)0.017 (2)0.213 (2)0.048 (3)*
H520.207 (4)0.082 (2)0.214 (2)0.048 (3)*
H530.197 (4)0.023 (2)0.098 (2)0.048 (3)*
C10.3612 (3)0.33606 (15)0.46157 (13)0.0298 (3)
H1A0.51520.34240.43330.039*
H1B0.30280.42590.44330.039*
C20.2689 (2)0.26218 (13)0.38854 (12)0.0238 (3)
H20.30090.16710.42380.029*
C30.3751 (2)0.30780 (13)0.24639 (12)0.0229 (3)
H30.52760.28510.24190.027*
C40.2857 (2)0.23092 (13)0.17172 (13)0.0241 (3)
H40.13170.24860.17720.029*
C50.3229 (3)0.08066 (13)0.22218 (14)0.0301 (3)
H5A0.47100.06070.19220.039*
H5B0.29830.05300.31430.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0344 (2)0.03620 (19)0.0352 (2)0.00120 (15)0.00455 (15)0.01267 (15)
Cl20.0477 (3)0.0444 (2)0.0267 (2)0.00096 (18)0.00543 (16)0.01344 (16)
Cl30.0367 (3)0.0358 (2)0.0400 (2)0.00715 (15)0.00870 (16)0.00670 (15)
Cl40.0329 (4)0.0435 (4)0.0739 (5)0.0006 (2)0.0174 (3)0.0119 (3)
Cl4"0.033 (2)0.0291 (19)0.068 (3)0.0062 (14)0.022 (2)0.0117 (18)
O10.0558 (11)0.0802 (11)0.0626 (10)0.0134 (8)0.0027 (8)0.0109 (8)
N10.0390 (10)0.0420 (8)0.0220 (6)0.0061 (6)0.0075 (6)0.0054 (5)
N20.0272 (8)0.0419 (7)0.0285 (7)0.0054 (6)0.0015 (5)0.0148 (6)
N30.0345 (9)0.0241 (6)0.0269 (6)0.0043 (5)0.0056 (5)0.0038 (5)
N40.0406 (9)0.0358 (7)0.0244 (6)0.0069 (6)0.0031 (6)0.0100 (5)
N50.0505 (11)0.0286 (6)0.0288 (7)0.0087 (6)0.0066 (6)0.0080 (5)
C10.0332 (10)0.0330 (7)0.0215 (7)0.0088 (6)0.0058 (6)0.0039 (5)
C20.0244 (8)0.0230 (6)0.0229 (6)0.0008 (5)0.0046 (5)0.0056 (5)
C30.0216 (8)0.0235 (6)0.0226 (6)0.0002 (5)0.0048 (5)0.0056 (5)
C40.0231 (8)0.0262 (6)0.0222 (6)0.0001 (5)0.0042 (5)0.0065 (5)
C50.0352 (10)0.0259 (7)0.0314 (7)0.0019 (6)0.0106 (6)0.0099 (6)
Geometric parameters (Å, º) top
O1—H1W0.7463N4—H430.88 (2)
O1—H2W0.7500N5—C51.481 (2)
N1—C11.496 (2)N5—H510.87 (2)
N1—H110.77 (3)N5—H520.87 (2)
N1—H120.85 (3)N5—H530.89 (2)
N1—H130.91 (3)C1—C21.520 (2)
N2—C21.489 (2)C1—H1A0.9700
N2—H210.89 (2)C1—H1B0.9700
N2—H220.86 (2)C2—C31.545 (2)
N2—H230.92 (2)C2—H20.9800
N3—C31.459 (2)C3—C41.548 (2)
N3—H310.80 (2)C3—H30.9800
N3—H320.87 (3)C4—C51.528 (2)
N4—C41.499 (2)C4—H40.9800
N4—H410.87 (2)C5—H5A0.9700
N4—H420.87 (3)C5—H5B0.9700
H1W—O1—H2W114.1N1—C1—H1A109.3
C1—N1—H11114 (2)C2—C1—H1A109.3
C1—N1—H12110.0 (17)N1—C1—H1B109.3
H11—N1—H12107 (3)C2—C1—H1B109.3
C1—N1—H13112.2 (15)H1A—C1—H1B107.9
H11—N1—H13109 (2)N2—C2—C1111.09 (13)
H12—N1—H13104 (2)N2—C2—C3111.22 (12)
C2—N2—H21113.6 (15)C1—C2—C3111.08 (12)
C2—N2—H22109.9 (15)N2—C2—H2107.8
H21—N2—H22110 (2)C1—C2—H2107.8
C2—N2—H23112.2 (14)C3—C2—H2107.8
H21—N2—H23101.9 (19)N3—C3—C2115.61 (12)
H22—N2—H23109 (2)N3—C3—C4108.50 (11)
C3—N3—H31109.3 (15)C2—C3—C4111.48 (11)
C3—N3—H32110.5 (15)N3—C3—H3106.9
H31—N3—H32109 (2)C2—C3—H3106.9
C4—N4—H41113.0 (15)C4—C3—H3106.9
C4—N4—H42111.5 (15)N4—C4—C5110.61 (13)
H41—N4—H42107 (2)N4—C4—C3106.48 (12)
C4—N4—H43107.7 (14)C5—C4—C3112.50 (11)
H41—N4—H43111 (2)N4—C4—H4109.1
H42—N4—H43106 (2)C5—C4—H4109.1
C5—N5—H51109.1 (15)C3—C4—H4109.1
C5—N5—H52109.7 (15)N5—C5—C4112.76 (13)
H51—N5—H52107 (2)N5—C5—H5A109.0
C5—N5—H53113.9 (14)C4—C5—H5A109.0
H51—N5—H53109 (2)N5—C5—H5B109.0
H52—N5—H53108.3 (19)C4—C5—H5B109.0
N1—C1—C2111.76 (12)H5A—C5—H5B107.8
N1—C1—C2—N272.60 (16)N3—C3—C4—N450.31 (16)
N1—C1—C2—C3163.04 (13)C2—C3—C4—N4178.74 (12)
N2—C2—C3—N367.57 (16)N3—C3—C4—C5171.63 (13)
C1—C2—C3—N356.71 (17)C2—C3—C4—C559.94 (16)
N2—C2—C3—C456.96 (15)N4—C4—C5—N579.66 (17)
C1—C2—C3—C4178.75 (12)C3—C4—C5—N5161.40 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H12···Cl1i0.85 (3)2.42 (3)3.2229 (18)158 (2)
N1—H13···Cl3ii0.91 (3)2.51 (3)3.3860 (18)163 (2)
N2—H21···Cl10.89 (2)2.23 (2)3.1104 (17)172 (2)
N2—H22···Cl30.86 (2)2.27 (2)3.1205 (17)168 (2)
N2—H23···Cl40.92 (2)2.22 (2)3.120 (2)165.7 (19)
N2—H23···Cl4"0.92 (2)2.36 (2)3.210 (5)153.5 (18)
N3—H32···Cl40.87 (3)2.55 (3)3.3995 (19)168 (2)
N3—H32···Cl4"0.87 (3)2.43 (3)3.230 (5)152 (2)
N4—H41···Cl20.87 (2)2.38 (2)3.2254 (17)163.7 (19)
N4—H42···O10.87 (3)1.93 (3)2.792 (3)175 (2)
N5—H51···Cl30.87 (2)2.38 (2)3.179 (2)152 (2)
N5—H52···Cl1ii0.87 (2)2.33 (2)3.1830 (18)167.1 (19)
N5—H53···Cl20.89 (2)2.20 (2)3.0774 (17)171.8 (19)
Symmetry codes: (i) x+1, y, z; (ii) x, y, z+1.
(II) 1,2R,3,4S,5-pentaammonio-pentane trichloride tetrachlorozinkate - hydrate top
Crystal data top
(C5H22N5)Cl3[ZnCl4]·H2OZ = 2
Mr = 483.81F(000) = 492
Triclinic, P1Dx = 1.767 Mg m3
a = 7.255 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.893 (6) ÅCell parameters from 5000 quasi centered reflections which were automatically selected from the whole data set and used in least squares refinement calculation. reflections
c = 12.173 (6) ŵ = 2.38 mm1
α = 107.49 (4)°T = 293 K
β = 91.52 (4)°Isometrically, colourless
γ = 96.67 (4)°0.87 × 0.60 × 0.45 mm
V = 909.4 (8) Å3
Data collection top
STOE IPDS difractometer
diffractometer
4012 independent reflections
Radiation source: fine-focus sealed tube3892 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 50 pixels mm-1θmax = 28.0°, θmin = 5.2°
phi–scanh = 99
Absorption correction: numerical
using indexed faces and a gaussian integration method (Stoe & Cie, 1996)
k = 1414
Tmin = 0.232, Tmax = 0.413l = 1616
15919 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.072Calculated w = 1/[σ2(Fo2) + (0.0371P)2 + 0.446P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.040
4012 reflectionsΔρmax = 0.43 e Å3
238 parametersΔρmin = 0.61 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.022 (2)
Crystal data top
(C5H22N5)Cl3[ZnCl4]·H2Oγ = 96.67 (4)°
Mr = 483.81V = 909.4 (8) Å3
Triclinic, P1Z = 2
a = 7.255 (4) ÅMo Kα radiation
b = 10.893 (6) ŵ = 2.38 mm1
c = 12.173 (6) ÅT = 293 K
α = 107.49 (4)°0.87 × 0.60 × 0.45 mm
β = 91.52 (4)°
Data collection top
STOE IPDS difractometer
diffractometer
4012 independent reflections
Absorption correction: numerical
using indexed faces and a gaussian integration method (Stoe & Cie, 1996)
3892 reflections with I > 2σ(I)
Tmin = 0.232, Tmax = 0.413Rint = 0.057
15919 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0272 restraints
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.43 e Å3
4012 reflectionsΔρmin = 0.61 e Å3
238 parameters
Special details top

Experimental. Compound (II): 720 exposures were taken in the 0–360 phi range with a crystal-to-detector distance of 55 mm and an exposure time of 3 min. Dynamic integration profiles (11–19 pixels) without allowing to overlap were used for integration. 91.2% completeness of data has been achieved in a theta range of 5.16–28.00°.

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
Zn10.72370 (3)0.74869 (2)0.146366 (17)0.02069 (9)
Cl10.75753 (6)0.54574 (4)0.03299 (4)0.02541 (11)
Cl20.71882 (8)0.88982 (5)0.04346 (4)0.03432 (13)
Cl30.44423 (5)0.73238 (4)0.23242 (4)0.02390 (11)
Cl40.95299 (5)0.80924 (4)0.28949 (4)0.02242 (11)
Cl50.18610 (5)0.74079 (4)0.12231 (4)0.02068 (10)
Cl60.28399 (6)0.89591 (5)0.41628 (4)0.03189 (13)
Cl70.27096 (6)0.47144 (5)0.40370 (4)0.02924 (12)
N10.6550 (2)0.82221 (17)0.52099 (13)0.0219 (3)
H110.679 (4)0.864 (3)0.569 (2)0.034 (4)*
H120.538 (4)0.823 (3)0.505 (2)0.034 (4)*
H130.680 (4)0.744 (3)0.551 (2)0.034 (4)*
N20.96015 (19)0.89237 (15)0.24864 (14)0.0193 (3)
H211.054 (4)0.926 (3)0.276 (2)0.031 (4)*
H221.003 (3)0.848 (3)0.207 (2)0.031 (4)*
H230.908 (4)0.956 (3)0.203 (2)0.031 (4)*
N30.53594 (19)0.83528 (16)0.23390 (14)0.0207 (3)
H310.448 (4)0.799 (3)0.198 (2)0.039 (4)*
H320.479 (4)0.862 (3)0.281 (3)0.039 (4)*
H330.609 (4)0.910 (3)0.176 (3)0.039 (4)*
N40.54253 (19)0.58922 (15)0.18522 (14)0.0194 (3)
H410.571 (4)0.541 (3)0.149 (3)0.041 (4)*
H420.464 (4)0.545 (3)0.244 (3)0.041 (4)*
H430.483 (4)0.650 (3)0.135 (3)0.041 (4)*
N50.9176 (2)0.47758 (16)0.22821 (15)0.0224 (3)
H510.987 (5)0.424 (4)0.273 (3)0.054 (5)*
H520.851 (5)0.439 (4)0.198 (3)0.054 (5)*
H530.998 (5)0.527 (4)0.176 (3)0.054 (5)*
C10.7748 (2)0.89445 (17)0.41572 (14)0.0189 (3)
H1A0.71140.96360.36880.025*
H1B0.88870.93400.43790.025*
C20.8240 (2)0.80764 (16)0.34304 (14)0.0156 (3)
H20.89030.74010.39180.019*
C30.6566 (2)0.73795 (16)0.29870 (14)0.0154 (3)
H30.58140.68070.36690.018*
C40.7136 (2)0.65090 (15)0.22602 (13)0.0151 (3)
H40.79490.70420.15900.018*
C50.8171 (2)0.54225 (18)0.29961 (15)0.0210 (3)
H5A0.72840.47780.35420.027*
H5B0.90590.57870.34330.027*
O10.7471 (2)1.07171 (15)0.12735 (13)0.0298 (3)
H1W0.722 (5)1.125 (3)0.151 (3)0.061 (10)*
H2W0.771 (4)1.107 (3)0.064 (2)0.053 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02359 (12)0.01990 (13)0.02018 (13)0.00183 (8)0.00034 (8)0.00903 (10)
Cl10.0319 (2)0.0226 (2)0.0216 (2)0.00666 (17)0.00143 (16)0.00567 (18)
Cl20.0506 (3)0.0292 (3)0.0297 (2)0.0053 (2)0.0002 (2)0.0189 (2)
Cl30.01950 (18)0.0262 (2)0.0271 (2)0.00038 (15)0.00032 (15)0.01085 (19)
Cl40.02072 (18)0.0217 (2)0.0238 (2)0.00103 (15)0.00142 (15)0.00628 (18)
Cl50.01859 (17)0.0202 (2)0.0238 (2)0.00257 (14)0.00064 (14)0.00756 (17)
Cl60.0235 (2)0.0486 (3)0.0348 (2)0.0145 (2)0.00772 (17)0.0255 (2)
Cl70.0325 (2)0.0283 (2)0.0245 (2)0.00433 (18)0.00123 (17)0.0046 (2)
N10.0225 (7)0.0286 (8)0.0160 (7)0.0040 (6)0.0001 (5)0.0089 (7)
N20.0155 (6)0.0213 (7)0.0231 (7)0.0006 (5)0.0028 (5)0.0111 (7)
N30.0167 (6)0.0257 (8)0.0256 (7)0.0067 (6)0.0042 (6)0.0151 (7)
N40.0180 (6)0.0206 (7)0.0251 (7)0.0030 (5)0.0028 (6)0.0147 (7)
N50.0210 (6)0.0188 (7)0.0307 (8)0.0048 (6)0.0012 (6)0.0116 (7)
C10.0209 (7)0.0205 (8)0.0180 (8)0.0004 (6)0.0015 (6)0.0111 (7)
C20.0153 (6)0.0162 (7)0.0167 (7)0.0008 (5)0.0011 (5)0.0076 (6)
C30.0150 (6)0.0165 (7)0.0163 (7)0.0000 (6)0.0010 (5)0.0082 (6)
C40.0142 (6)0.0172 (7)0.0157 (7)0.0013 (6)0.0002 (5)0.0081 (6)
C50.0238 (7)0.0224 (8)0.0190 (7)0.0088 (7)0.0016 (6)0.0075 (7)
O10.0439 (8)0.0253 (7)0.0215 (7)0.0097 (6)0.0026 (6)0.0069 (6)
Geometric parameters (Å, º) top
Zn1—Cl22.2587 (11)N4—H430.92 (3)
Zn1—Cl42.2668 (14)N5—C51.496 (2)
Zn1—Cl12.2721 (14)N5—H510.89 (4)
Zn1—Cl32.3197 (13)N5—H520.78 (4)
N1—C11.481 (2)N5—H530.85 (4)
N1—H110.85 (3)C1—C21.539 (2)
N1—H120.88 (3)C1—H1A0.9700
N1—H130.86 (3)C1—H1B0.9700
N2—C21.496 (2)C2—C31.552 (2)
N2—H210.85 (3)C2—H20.9800
N2—H220.88 (3)C3—C41.559 (2)
N2—H230.88 (3)C3—H30.9800
N3—C31.504 (2)C4—C51.540 (2)
N3—H310.90 (3)C4—H40.9800
N3—H320.83 (3)C5—H5A0.9700
N3—H330.99 (3)C5—H5B0.9700
N4—C41.509 (2)O1—H1W0.76 (2)
N4—H410.82 (3)O1—H2W0.75 (2)
N4—H420.88 (3)
Cl2—Zn1—Cl4113.25 (4)H51—N5—H53102 (3)
Cl2—Zn1—Cl1111.96 (4)H52—N5—H53107 (3)
Cl4—Zn1—Cl1107.69 (5)N1—C1—C2112.85 (15)
Cl2—Zn1—Cl3109.74 (4)N1—C1—H1A109.0
Cl4—Zn1—Cl3107.06 (5)C2—C1—H1A109.0
Cl1—Zn1—Cl3106.82 (5)N1—C1—H1B109.0
C1—N1—H11105.4 (19)C2—C1—H1B109.0
C1—N1—H12109.6 (18)H1A—C1—H1B107.8
H11—N1—H12109 (2)N2—C2—C1105.46 (13)
C1—N1—H13113.0 (18)N2—C2—C3113.54 (13)
H11—N1—H13108 (2)C1—C2—C3115.76 (12)
H12—N1—H13111 (2)N2—C2—H2107.2
C2—N2—H21111.6 (18)C1—C2—H2107.2
C2—N2—H22111.2 (17)C3—C2—H2107.2
H21—N2—H22107 (2)N3—C3—C2110.10 (13)
C2—N2—H23111.0 (17)N3—C3—C4111.58 (13)
H21—N2—H23108 (2)C2—C3—C4113.78 (12)
H22—N2—H23108 (2)N3—C3—H3107.0
C3—N3—H31111.7 (18)C2—C3—H3107.0
C3—N3—H32108.8 (19)C4—C3—H3107.0
H31—N3—H32106 (2)N4—C4—C5108.50 (14)
C3—N3—H33112.0 (15)N4—C4—C3109.95 (12)
H31—N3—H33109 (2)C5—C4—C3110.27 (13)
H32—N3—H33109 (3)N4—C4—H4109.4
C4—N4—H41110.5 (19)C5—C4—H4109.4
C4—N4—H42110.7 (18)C3—C4—H4109.4
H41—N4—H42110 (3)N5—C5—C4112.57 (14)
C4—N4—H43111.6 (18)N5—C5—H5A109.1
H41—N4—H43105 (3)C4—C5—H5A109.1
H42—N4—H43109 (3)N5—C5—H5B109.1
C5—N5—H51109 (2)C4—C5—H5B109.1
C5—N5—H52113 (2)H5A—C5—H5B107.8
H51—N5—H52109 (3)H1W—O1—H2W103 (4)
C5—N5—H53116 (2)
N1—C1—C2—N2174.09 (13)N3—C3—C4—N453.74 (18)
N1—C1—C2—C359.50 (18)C2—C3—C4—N4179.06 (13)
N2—C2—C3—N368.10 (16)N3—C3—C4—C5173.34 (13)
C1—C2—C3—N354.12 (18)C2—C3—C4—C561.34 (18)
N2—C2—C3—C458.01 (18)N4—C4—C5—N574.45 (18)
C1—C2—C3—C4179.78 (14)C3—C4—C5—N5165.08 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H12···Cl60.88 (3)2.26 (3)3.095 (2)158 (2)
N1—H13···Cl7i0.86 (3)2.32 (3)3.166 (3)168 (2)
N2—H21···Cl6ii0.85 (3)2.40 (3)3.157 (2)148 (2)
N2—H22···Cl5ii0.88 (3)2.28 (3)3.131 (2)165 (2)
N2—H23···O10.88 (3)1.87 (3)2.734 (3)166 (3)
N3—H31···Cl50.90 (3)2.24 (3)3.125 (2)166 (2)
N3—H32···Cl60.83 (3)2.29 (3)3.107 (2)168 (3)
N3—H33···O10.99 (3)1.84 (3)2.763 (3)155 (2)
N4—H41···Cl10.82 (3)2.55 (3)3.228 (2)141 (3)
N4—H42···Cl70.88 (3)2.24 (3)3.112 (3)168 (3)
N4—H43···Cl50.92 (3)2.46 (3)3.215 (2)140 (2)
N5—H51···Cl4iii0.89 (4)2.57 (4)3.243 (2)133 (3)
N5—H53···Cl5ii0.85 (4)2.45 (4)3.166 (3)141 (3)
O1—H1W···Cl3iv0.76 (2)2.48 (3)3.217 (2)165 (3)
O1—H2W···Cl5iv0.75 (2)2.36 (3)3.099 (2)166 (3)
Symmetry codes: (i) x+1, y+1, z1; (ii) x+1, y, z; (iii) x+2, y+1, z; (iv) x+1, y+2, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC5H21N54+·4Cl·H2O(C5H22N5)Cl3[ZnCl4]·H2O
Mr311.08483.81
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)293293
a, b, c (Å)6.374 (1), 10.588 (2), 11.303 (2)7.255 (4), 10.893 (6), 12.173 (6)
α, β, γ (°)71.35 (3), 78.45 (3), 85.97 (3)107.49 (4), 91.52 (4), 96.67 (4)
V3)708.1 (2)909.4 (8)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.822.38
Crystal size (mm)0.40 × 0.34 × 0.300.87 × 0.60 × 0.45
Data collection
DiffractometerStoe IPDS
diffractometer
STOE IPDS difractometer
diffractometer
Absorption correctionNumerical
using indexed faces and a gaussian integration method (Stoe & Cie, 1996)
Tmin, Tmax0.232, 0.413
No. of measured, independent and
observed [I > 2σ(I)] reflections
9244, 2870, 2361 15919, 4012, 3892
Rint0.0350.057
(sin θ/λ)max1)0.6390.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.075, 1.02 0.027, 0.072, 1.06
No. of reflections28704012
No. of parameters196238
No. of restraints02
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.330.43, 0.61

Computer programs: IPDS-Software (Stoe, 1998), IPDS-Software, SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997a), Diamond (Brandenburg, 1998), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
N1—C11.496 (2)C1—C21.520 (2)
N2—C21.489 (2)C2—C31.545 (2)
N3—C31.459 (2)C3—C41.548 (2)
N4—C41.499 (2)C4—C51.528 (2)
N5—C51.481 (2)
N1—C1—C2111.76 (12)C2—C3—C4111.48 (11)
N2—C2—C1111.09 (13)N4—C4—C5110.61 (13)
N2—C2—C3111.22 (12)N4—C4—C3106.48 (12)
C1—C2—C3111.08 (12)C5—C4—C3112.50 (11)
N3—C3—C2115.61 (12)N5—C5—C4112.76 (13)
N3—C3—C4108.50 (11)
N1—C1—C2—N272.60 (16)N3—C3—C4—N450.31 (16)
N1—C1—C2—C3163.04 (13)C2—C3—C4—N4178.74 (12)
N2—C2—C3—N367.57 (16)N3—C3—C4—C5171.63 (13)
C1—C2—C3—N356.71 (17)C2—C3—C4—C559.94 (16)
N2—C2—C3—C456.96 (15)N4—C4—C5—N579.66 (17)
C1—C2—C3—C4178.75 (12)C3—C4—C5—N5161.40 (13)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H12···Cl1i0.85 (3)2.42 (3)3.2229 (18)158 (2)
N1—H13···Cl3ii0.91 (3)2.51 (3)3.3860 (18)163 (2)
N2—H21···Cl10.89 (2)2.23 (2)3.1104 (17)172 (2)
N2—H22···Cl30.86 (2)2.27 (2)3.1205 (17)168 (2)
N2—H23···Cl40.92 (2)2.22 (2)3.120 (2)165.7 (19)
N2—H23···Cl4"0.92 (2)2.36 (2)3.210 (5)153.5 (18)
N3—H32···Cl40.87 (3)2.55 (3)3.3995 (19)168 (2)
N3—H32···Cl4"0.87 (3)2.43 (3)3.230 (5)152 (2)
N4—H41···Cl20.87 (2)2.38 (2)3.2254 (17)163.7 (19)
N4—H42···O10.87 (3)1.93 (3)2.792 (3)175 (2)
N5—H51···Cl30.87 (2)2.38 (2)3.179 (2)152 (2)
N5—H52···Cl1ii0.87 (2)2.33 (2)3.1830 (18)167.1 (19)
N5—H53···Cl20.89 (2)2.20 (2)3.0774 (17)171.8 (19)
Symmetry codes: (i) x+1, y, z; (ii) x, y, z+1.
Selected geometric parameters (Å, º) for (II) top
Zn1—Cl22.2587 (11)N4—C41.509 (2)
Zn1—Cl42.2668 (14)N5—C51.496 (2)
Zn1—Cl12.2721 (14)C1—C21.539 (2)
Zn1—Cl32.3197 (13)C2—C31.552 (2)
N1—C11.481 (2)C3—C41.559 (2)
N2—C21.496 (2)C4—C51.540 (2)
N3—C31.504 (2)
Cl2—Zn1—Cl4113.25 (4)C1—C2—C3115.76 (12)
Cl2—Zn1—Cl1111.96 (4)N3—C3—C2110.10 (13)
Cl4—Zn1—Cl1107.69 (5)N3—C3—C4111.58 (13)
Cl2—Zn1—Cl3109.74 (4)C2—C3—C4113.78 (12)
Cl4—Zn1—Cl3107.06 (5)N4—C4—C5108.50 (14)
Cl1—Zn1—Cl3106.82 (5)N4—C4—C3109.95 (12)
N1—C1—C2112.85 (15)C5—C4—C3110.27 (13)
N2—C2—C1105.46 (13)N5—C5—C4112.57 (14)
N2—C2—C3113.54 (13)
N1—C1—C2—N2174.09 (13)N3—C3—C4—N453.74 (18)
N1—C1—C2—C359.50 (18)C2—C3—C4—N4179.06 (13)
N2—C2—C3—N368.10 (16)N3—C3—C4—C5173.34 (13)
C1—C2—C3—N354.12 (18)C2—C3—C4—C561.34 (18)
N2—C2—C3—C458.01 (18)N4—C4—C5—N574.45 (18)
C1—C2—C3—C4179.78 (14)C3—C4—C5—N5165.08 (13)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H12···Cl60.88 (3)2.26 (3)3.095 (2)158 (2)
N1—H13···Cl7i0.86 (3)2.32 (3)3.166 (3)168 (2)
N2—H21···Cl6ii0.85 (3)2.40 (3)3.157 (2)148 (2)
N2—H22···Cl5ii0.88 (3)2.28 (3)3.131 (2)165 (2)
N2—H23···O10.88 (3)1.87 (3)2.734 (3)166 (3)
N3—H31···Cl50.90 (3)2.24 (3)3.125 (2)166 (2)
N3—H32···Cl60.83 (3)2.29 (3)3.107 (2)168 (3)
N3—H33···O10.99 (3)1.84 (3)2.763 (3)155 (2)
N4—H41···Cl10.82 (3)2.55 (3)3.228 (2)141 (3)
N4—H42···Cl70.88 (3)2.24 (3)3.112 (3)168 (3)
N4—H43···Cl50.92 (3)2.46 (3)3.215 (2)140 (2)
N5—H51···Cl4iii0.89 (4)2.57 (4)3.243 (2)133 (3)
N5—H53···Cl5ii0.85 (4)2.45 (4)3.166 (3)141 (3)
O1—H1W···Cl3iv0.76 (2)2.48 (3)3.217 (2)165 (3)
O1—H2W···Cl5iv0.75 (2)2.36 (3)3.099 (2)166 (3)
Symmetry codes: (i) x+1, y+1, z1; (ii) x+1, y, z; (iii) x+2, y+1, z; (iv) x+1, y+2, z.
 

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