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

Abstract

In the crystal structure of the title compound, C₁₀H₂₂N₂O₄ ²⁺·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

• C₁₀H₂₂N₂O₄ ²⁺·2Cl⁻

• M _r = 305.20

• Monoclinic,

• a = 8.9030 (8) Å

• b = 10.3327 (10) Å

• c = 8.3269 (10) Å

• β = 101.763 (10)°

• V = 749.93 (13) ų

• 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[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The amine and methylene H atoms were found in a difference map and refined while methyl H atoms were positioned geometrically and treated as riding, with C–H bond lengths constrained to 0.96 Å.

Figures

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.

Crystal data

C10H22N2O42+·2Cl–	F000 = 324
Mr = 305.20	Dx = 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 = 7.7–12.2º
b = 10.3327 (10) Å	µ = 0.44 mm−1
c = 8.3269 (10) Å	T = 293 (2) K
β = 101.763 (10)º	Needle, colourless
V = 749.93 (13) Å3	0.42 × 0.12 × 0.10 mm
Z = 2

Data collection

Stoe STADI4 diffractometer	Rint = 0.057
Radiation source: fine-focus sealed tube	θmax = 25.1º
Monochromator: graphite	θmin = 2.3º
T = 293(2) K	h = −10→10
ω/2θ scans	k = −12→12
Absorption correction: none	l = −9→9
5296 measured reflections	2 standard reflections
1324 independent reflections	every 60 min
1021 reflections with I > 2σ(I)	intensity decay: random variation +−5%

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.036	w = 1/[σ2(Fo2) + (0.0263P)2 + 0.2601P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085	(Δ/σ)max < 0.001
S = 1.13	Δρmax = 0.24 e Å−3
1324 reflections	Δρmin = −0.22 e Å−3
116 parameters	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)
Secondary atom site location: difference Fourier map

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

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.