N,N′-Bis[2-(methoxycarbonyl)ethyl]ethane-1,2-diammonium dichloride

Kaluderović, G.N.; Paethanom, A.; Wagner, C.; Sabo, T.J.; Schmidt, H.

doi:10.1107/S1600536808016565

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1232

doi:10.1107/S1600536808016565

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N,N′-Bis[2-(methoxycarbonyl)ethyl]ethane-1,2-diammonium dichloride

Goran N. Kaluderović,^a ^*‡ Anchan Paethanom,^a Christoph Wagner,^a Tibor J. Sabo ^b and Harry Schmidt ^a

^aInstitut für Chemie, Martin-Luther-Universität Halle-Wittenberg, Kurt-Mothes-Strasse 2, D-06120 Halle, Germany, and ^bFaculty of Chemistry, University of Belgrade, Studentski trg 12-14, PO Box 158, 11000 Belgrade, Serbia
^*Correspondence e-mail: goran.kaluderovic@chemie.uni-halle.de

(Received 9 May 2008; accepted 30 May 2008; online 7 June 2008)

In the crystal structure of the title compound, C₁₀H₂₂N₂O₄²⁺·2Cl⁻ or (H₂Me₂eddp)Cl₂ (H₂Me₂eddp²⁺ is the dimethyl N,N′-di-3-propanecarboxylatoethane-1,2-diyldiiminium cation), the packing is stabilized by an infinite two-dimensional ⋯Cl⋯H—N—H⋯Cl⋯ hydrogen-bonding network. In addition, short C—H⋯Cl contacts are observed.

Related literature

For related literature, see: Aakeröy et al. (1999 ); Bruhn et al. (2008 ); Kaluderović & Sabo (2002 ); Kaluderović et al. (2005 , 2007 , 2008 ); Krajčinović et al. (2008 ); Mijatović et al. (2005 ).

Experimental

Crystal data

C₁₀H₂₂N₂O₄²⁺·2Cl⁻
M_r = 305.20
Monoclinic, P 2₁ /c
a = 8.9030 (8) Å
b = 10.3327 (10) Å
c = 8.3269 (10) Å
β = 101.763 (10)°
V = 749.93 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 293 (2) K
0.42 × 0.12 × 0.10 mm

Data collection

Stoe STADI4 diffractometer
Absorption correction: none
5296 measured reflections
1324 independent reflections
1021 reflections with I > 2σ(I)
R_int = 0.057
2 standard reflections frequency: 60 min intensity decay: random variation ±5%

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.085
S = 1.13
1324 reflections
116 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H3⋯Clⁱ	0.97 (3)	2.10 (3)	3.064 (2)	171 (2)
N—H4⋯Cl	0.85 (2)	2.30 (2)	3.092 (2)	156 (2)
C3—H8⋯Clⁱⁱ	0.95 (2)	2.73 (3)	3.619 (3)	156.3 (18)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z.

Data collection: STADI4 (Stoe & Cie, 1996 ); cell refinement: STADI4; data reduction: STADI4; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808016565/pk2097sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016565/pk2097Isup2.hkl

checkCIF report

Comment top

The title compound (H₂Me₂eddp)Cl₂ belongs to a class of compounds that have recently been used as ligand precursors in the synthesis of Co(III), Pt(II) and Pt(IV) complexes (Kaluđerović & Sabo, 2002; Kaluđerović et al., 2008). The platinum complexes have been tested against various types of tumor cell lines and some of them have shown promising results in in vitro studies (Kaluđerović et al., 2005; Mijatović et al., 2005). There are few crystal structures of these ligand precursors, or indeed of the corresponding platinum complexes, reported in the literature. To date, only four solid state structures of metal complexes containing platinum(IV) (Kaluđerović et al., 2007, 2008; Krajčinović et al., 2008), and only one crystal structure of ligand precursor O,O'-diisopropyl-ethylenediammonium-(S,S)-di-2-propanoate dichloride, [(S,S)-H₂i-Pr₂eddp]Cl₂ (Krajčinović et al., 2008) have been described.

Bond lengths and angles for the title compound are in the same range as found for [(S,S)-H₂i-Pr₂eddp]Cl₂ (Krajčinović et al., 2008). All non H atoms in the H₂Me₂eddp²⁺ cation are essentially co-planar with the largest deviation being for the C1 atom (0.175 (2) Å). The solid-state structure is stabilized by H-bonds. The H₂Me₂eddp²⁺ cations are joined in infinite two-dimensional networks through H-bonds via N—H groups and chloride anions (···Cl···H—N—H···Cl···; Figs. 2 and 3). The structural parameters of these two hydrogen bonds (N—H3···Cl = 3.064 (2) Å, N—H3···Cl = 171 (2)°, N—H4···Cl = 3.092 (2) Å, N—H4···Cl = 156 (2)°) are in accord with analogous hydrogen bonds in [(S,S)-H₂i-Pr₂eddp]Cl₂ (Krajčinović et al., 2008). Furthermore, short C—H···Cl contacts (C—H···Cl = 3.619 (3) Å, C—H···Cl = 156 (2)°) provide additional stabilization to the structure (Aakeröy et al., 1999; Bruhn et al., 2008).

Related literature top

For related literature, see: Aakeröy et al. (1999); Bruhn et al. (2008); Kaluđerović & Sabo (2002); Kaluđerović et al. (2005, 2007, 2008); Krajčinović et al. (2008); Mijatović et al. (2005).

Experimental top

The title compound was obtained as described in literature (Kaluđerović & Sabo, 2002). Colourless single crystals suitable for X-ray structure determination were obtained from mother liquor by slow evaporation at room temperature over several days.

Computing details top

Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4 (Stoe & Cie, 1996); data reduction: STADI4 (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. DIAMOND representation of (H₂Me₂eddp)Cl₂. [Symmetry code: (i) -x + 1, -y + 1, -z + 1; (ii) 1 - x, y-1/2, -z + 1/2]
	Fig. 2. Network of H-bonding viewed along b-axis.
	Fig. 3. Network of H-bonding viewed along c-axis.

N,N'-Bis[2-(methoxycarbonyl)ethyl]ethane-1,2-diammonium dichloride top

Crystal data top

C₁₀H₂₂N₂O₄²⁺·2Cl⁻	F(000) = 324
M_r = 305.20	D_x = 1.352 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 26 reflections
a = 8.9030 (8) Å	θ = 7.7–12.2°
b = 10.3327 (10) Å	µ = 0.44 mm⁻¹
c = 8.3269 (10) Å	T = 293 K
β = 101.763 (10)°	Needle, colourless
V = 749.93 (13) Å³	0.42 × 0.12 × 0.10 mm
Z = 2

Data collection top

Stoe STADI4 diffractometer	R_int = 0.057
Radiation source: fine-focus sealed tube	θ_max = 25.1°, θ_min = 2.3°
Graphite monochromator	h = −10→10
ω/2θ scans	k = −12→12
5296 measured reflections	l = −9→9
1324 independent reflections	2 standard reflections every 60 min
1021 reflections with I > 2σ(I)	intensity decay: random variation +−5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0263P)² + 0.2601P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
1324 reflections	Δρ_max = 0.24 e Å⁻³
116 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (3)

Crystal data top

C₁₀H₂₂N₂O₄²⁺·2Cl⁻	V = 749.93 (13) Å³
M_r = 305.20	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.9030 (8) Å	µ = 0.44 mm⁻¹
b = 10.3327 (10) Å	T = 293 K
c = 8.3269 (10) Å	0.42 × 0.12 × 0.10 mm
β = 101.763 (10)°

Data collection top

Stoe STADI4 diffractometer	R_int = 0.057
5296 measured reflections	2 standard reflections every 60 min
1324 independent reflections	intensity decay: random variation +−5%
1021 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.24 e Å⁻³
1324 reflections	Δρ_min = −0.22 e Å⁻³
116 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. 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

	x	y	z	U_iso*/U_eq
C1	0.5853 (3)	0.4998 (2)	0.5051 (3)	0.0387 (6)
H2	0.624 (3)	0.586 (2)	0.507 (3)	0.046 (7)*
H1	0.636 (3)	0.454 (2)	0.596 (3)	0.051 (7)*
C2	0.7898 (3)	0.4385 (3)	0.3579 (3)	0.0401 (6)
H5	0.835 (3)	0.409 (2)	0.462 (3)	0.052 (8)*
H6	0.818 (3)	0.525 (3)	0.344 (3)	0.046 (7)*
C3	0.8277 (3)	0.3565 (3)	0.2221 (3)	0.0421 (6)
H8	0.756 (3)	0.376 (2)	0.126 (3)	0.047 (7)*
H7	0.819 (3)	0.272 (2)	0.248 (3)	0.045 (7)*
C4	0.9857 (3)	0.3853 (2)	0.1953 (3)	0.0417 (6)
C5	1.1771 (3)	0.3294 (3)	0.0491 (3)	0.0609 (8)
H9	1.1942	0.4207	0.0408	0.091*
H11	1.1832	0.2882	−0.0528	0.091*
H10	1.2539	0.2937	0.1356	0.091*
N	0.6217 (2)	0.43799 (19)	0.3563 (3)	0.0345 (5)
H3	0.585 (3)	0.349 (3)	0.352 (3)	0.051 (7)*
H4	0.577 (3)	0.480 (2)	0.271 (3)	0.047 (8)*
O1	1.0669 (2)	0.4681 (2)	0.2636 (3)	0.0799 (7)
O2	1.02593 (19)	0.30760 (17)	0.0849 (2)	0.0566 (5)
Cl	0.49596 (7)	0.66139 (5)	0.11984 (7)	0.0475 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0311 (12)	0.0375 (13)	0.0491 (15)	−0.0017 (10)	0.0122 (11)	−0.0005 (11)
C2	0.0277 (12)	0.0450 (15)	0.0488 (15)	−0.0014 (10)	0.0104 (11)	−0.0051 (12)
C3	0.0363 (13)	0.0453 (16)	0.0444 (14)	−0.0044 (11)	0.0076 (11)	−0.0059 (12)
C4	0.0340 (13)	0.0505 (14)	0.0390 (13)	0.0011 (11)	0.0038 (10)	−0.0028 (11)
C5	0.0503 (16)	0.0728 (19)	0.0679 (18)	0.0073 (14)	0.0312 (14)	−0.0037 (16)
N	0.0272 (10)	0.0305 (10)	0.0461 (12)	0.0013 (8)	0.0080 (8)	0.0056 (9)
O1	0.0440 (11)	0.1084 (17)	0.0928 (16)	−0.0259 (12)	0.0270 (11)	−0.0537 (14)
O2	0.0499 (11)	0.0618 (12)	0.0648 (12)	−0.0047 (9)	0.0271 (9)	−0.0190 (9)
Cl	0.0542 (4)	0.0336 (3)	0.0529 (4)	0.0092 (3)	0.0064 (3)	0.0026 (3)

Geometric parameters (Å, º) top

C1—N	1.487 (3)	C3—H7	0.91 (2)
C1—C1ⁱ	1.505 (4)	C4—O1	1.188 (3)
C1—H2	0.95 (2)	C4—O2	1.324 (3)
C1—H1	0.93 (3)	C5—O2	1.454 (3)
C2—N	1.494 (3)	C5—H9	0.9600
C2—C3	1.506 (3)	C5—H11	0.9600
C2—H5	0.93 (2)	C5—H10	0.9600
C2—H6	0.94 (3)	N—H3	0.97 (3)
C3—C4	1.498 (3)	N—H4	0.85 (3)
C3—H8	0.94 (2)

N—C1—C1ⁱ	110.0 (3)	H8—C3—H7	109 (2)
N—C1—H2	105.7 (14)	O1—C4—O2	123.0 (2)
C1ⁱ—C1—H2	111.0 (14)	O1—C4—C3	124.8 (2)
N—C1—H1	107.8 (15)	O2—C4—C3	112.2 (2)
C1ⁱ—C1—H1	111.5 (15)	O2—C5—H9	109.5
H2—C1—H1	111 (2)	O2—C5—H11	109.5
N—C2—C3	111.63 (19)	H9—C5—H11	109.5
N—C2—H5	104.7 (15)	O2—C5—H10	109.5
C3—C2—H5	113.1 (16)	H9—C5—H10	109.5
N—C2—H6	107.3 (15)	H11—C5—H10	109.5
C3—C2—H6	109.6 (15)	C1—N—C2	112.25 (18)
H5—C2—H6	110 (2)	C1—N—H3	108.0 (14)
C4—C3—C2	111.1 (2)	C2—N—H3	109.2 (14)
C4—C3—H8	108.8 (14)	C1—N—H4	109.2 (17)
C2—C3—H8	107.9 (15)	C2—N—H4	107.4 (16)
C4—C3—H7	110.7 (15)	H3—N—H4	111 (2)
C2—C3—H7	109.0 (15)	C4—O2—C5	116.20 (19)

N—C2—C3—C4	164.5 (2)	C3—C2—N—C1	170.4 (2)
C2—C3—C4—O1	−5.0 (4)	O1—C4—O2—C5	−0.5 (4)
C2—C3—C4—O2	175.3 (2)	C3—C4—O2—C5	179.2 (2)
C1ⁱ—C1—N—C2	178.3 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H3···Clⁱⁱ	0.97 (3)	2.10 (3)	3.064 (2)	171 (2)
N—H4···Cl	0.85 (2)	2.30 (2)	3.092 (2)	156 (2)
C3—H8···Clⁱⁱⁱ	0.95 (2)	2.73 (3)	3.619 (3)	156.3 (18)

Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₂₂N₂O₄²⁺·2Cl⁻
M_r	305.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.9030 (8), 10.3327 (10), 8.3269 (10)
β (°)	101.763 (10)
V (Å³)	749.93 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.42 × 0.12 × 0.10

Data collection
Diffractometer	Stoe STADI4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5296, 1324, 1021
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.085, 1.13
No. of reflections	1324
No. of parameters	116
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22

Computer programs: STADI4 (Stoe & Cie, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H3···Clⁱ	0.97 (3)	2.10 (3)	3.064 (2)	171 (2)
N—H4···Cl	0.85 (2)	2.30 (2)	3.092 (2)	156 (2)
C3—H8···Clⁱⁱ	0.95 (2)	2.73 (3)	3.619 (3)	156.3 (18)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z.

Footnotes

‡Permanent address: Department of Chemistry, Institute of Chemistry, Technology and Metallurgy, Studentski trg 14, 11000 Belgrade, Republic of Serbia. e-mail: goran@chem.bg.ac.yu.

Acknowledgements

GNK acknowledges financial support from the Alexander von Humboldt Foundation. The authors are grateful to the Ministry of Science and Environmental Protection of Serbia for financial support (grant No. 142010).

References

Aakeröy, C. B., Evans, T. A., Seddon, K. R. & Palinko, I. (1999). New J. Chem. pp. 145–152. Google Scholar
Brandenburg, K. (2001). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruhn, C., Küger, T. & Steinborn, D. (2008). Acta Cryst. E64, m455–m456. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kaluderović, G. N., Miljković, Dj., Momčilović, M., Đinović, V. M., Mostarica Stojković, M., Sabo, T. J. & Trajković, V. (2005). Int. J. Cancer, 116, 479–486. Web of Science PubMed Google Scholar
Kaluderović, G. N. & Sabo, T. J. (2002). Polyhedron, 21, 2277–2282. Google Scholar
Kaluderović, G. N., Schmidt, H., Schwieger, S., Wagner, Ch., Paschke, R., Dietrich, A., Mueller, T. & Steinborn, D. (2008). Inorg. Chim. Acta, 361, 1395–1404. Google Scholar
Kaluderović, G. N., Schmidt, H., Wagner, C. & Steinborn, D. (2007). Acta Cryst. E63, m1985. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krajčinović, B. B., Kaluderović, G. N., Steinborn, D., Schmidt, H., Wagner, Ch., Žižak, Ž., Juranić, Z. D., Trifunović, S. R. & Sabo, T. J. (2008). J. Inorg. Biochem. 102, 892–900. Web of Science PubMed Google Scholar
Mijatović, S., Maksimović-Ivanović, D., Radović, J., Miljković, Dj., Kaluderović, G. N., Sabo, T. J. & Trajković, V. (2005). Cell. Mol. Life Sci. 62, 1275–1282. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (1996). STADI4. Stoe & Cie, Darmstadt, Germany. Google Scholar