(S,S)-N,N′-Bis(1-carb­oxy-2-methyl­prop­yl)ethyl­enediammonium dihalide cyclo­penta­nol tetra­solvate (halide = bromide/chloride ≃ 1:12)

Zmejkovski, B.B.; Kaluderović, G.N.; Gómez-Ruiz, S.; Sabo, T.J.

doi:10.1107/S1600536809006679

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages o656-o657

doi:10.1107/S1600536809006679

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(S,S)-N,N′-Bis(1-carboxy-2-methylpropyl)ethylenediammonium dihalide cyclopentanol tetrasolvate (halide = bromide/chloride ≃ 1:12)

Bojana B. Zmejkovski,^a Goran N. Kaluderović,^a Santiago Gómez-Ruiz ^b and Tibor J. Sabo ^c ^*

^aDepartment of Chemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Studentski trg 14, 11000 Belgrade, Serbia, ^bDepartamento de Química Inorgánica y Analítica, ESCET, Universidad, Rey Juan Carlos, 28933 Móstoles, Madrid, Spain, and ^cFaculty of Chemistry, University of Belgrade, Studentski trg 12-14, PO Box 158, 11000 Belgrade, Serbia
^*Correspondence e-mail: goran@chem.bg.ac.yu

(Received 5 February 2009; accepted 23 February 2009; online 28 February 2009)

In the crystal structure of the title compound, C₁₂H₂₆N₂O₄²⁺·2(Br_0.085Cl_0.915)⁻·4C₅H₉OH, the complete cation is generated by crystallographic twofold symmetry. Contamination of the chloride counter-anion with bromide occured during the preparation, due to the use of 1,2-dibromoethane. One of the solvent molecules is disordered, with occupancies 0.53 (3):0.47 (3). The crystal packing is stabilized by an infinite two dimensional ⋯X⋯H—N—H⋯X⋯ hydrogen-bonding network (X: Br⁻/Cl⁻ ≃ 1:12). In addition, O—H⋯X and O—H⋯O hydrogen bonds involving solvent molecules are observed.

Related literature

For dihydrochloride salts of the analog ethylenediamine-N,N′-diacetic acid and ethylenediamine-N,N′-di-3-propionic acid, see: Mistryukov et al. (1987 ); Shkol'nikova et al. (1989 , 1990 , 1992 ). For bond lengths and angles in ethylenediammonium-N,N′-di-3-propanoic acid dichloride and similar compounds, see: Kaluderović et al. (2004 , 2007 ). For the synthesis, see: Schoenberg et al. (1968 ).

Experimental

Crystal data

C₁₂H₂₆N₂O₄²⁺·2(Br_0.09Cl_0.91)⁻·4C₅H₁₀O
M_r = 685.41
Monoclinic, C 2
a = 21.2037 (5) Å
b = 5.2166 (1) Å
c = 17.2517 (5) Å
β = 97.037 (2)°
V = 1893.86 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 130 K
0.7 × 0.04 × 0.04 mm

Data collection

Oxford Diffraction CCD Oxford Xcalibur S diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.981, T_max = 0.985
28298 measured reflections
5795 independent reflections
4851 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.104
S = 0.98
5795 reflections
232 parameters
92 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 2602 Friedel pairs
Flack parameter: −0.04 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯X1	0.88 (2)	2.37 (2)	3.253 (2)	175 (2)
N1—H2N⋯X1ⁱ	0.93 (2)	2.32 (2)	3.209 (2)	161 (2)
O1—H1O⋯O4ⁱⁱ	0.95 (4)	2.50 (4)	3.446 (3)	172 (5)
O4—H4O⋯O3	0.86 (3)	1.89 (3)	2.728 (2)	165 (3)
O3—H3O⋯Cl1	0.94 (3)	2.29 (3)	3.204 (2)	163 (2)
O3—H3O⋯Br1	0.94 (3)	2.29 (3)	3.204 (2)	163 (2)
Symmetry codes: (i) x, y-1, z; (ii) -x+1, y-1, -z. X1 is the disordered Cl/Br atom.

Data collection: CrysAlisPro (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlisPro; data reduction: CrysAlisPro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006679/fj2196sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006679/fj2196Isup2.hkl

checkCIF report

Comment top

Dihydrochloride salts of the analog ethylenediamine-N,N'-diacetic acid and ethylenediamine-N,N'-di-3-propionic acid are reported in the literature, see (Shkol'nikova et al., 1989; Shkol'nikova et al., 1990; Shkol'nikova et al., 1992; Mistryukov et al., 1987).

Crude (S,S)-ethylenediammonium-N,N'-di-2-(3-methyl)-butanoic acid dihalide, [(H₄eddv)X₂], obtained from the reaction of L-valine and 1,2-dibromethane (Schoenberg et al.,1968), was used for the synthesis of dicyclopentyl ester. The title compound is isolated from the mother liquor as a mixture of Cl and Br salts. The structure consists of several species: one dicationic, C₁₂H₂₆N₂O₄²⁺, 0.17 Br^– and 1.83 Cl^– anions and four cyclopentanol molecules (Fig. 1). Bond lengths and angles are comparable with those of ethylenediammonium-N,N'-di-3-propanoic acid dichloride and similar compounds (Kaluđerović et al., 2004, 2007). All of the mentioned species are stabilizing the structure by intramolecular and intermolecular H-bonds (Table 1). The solvent molecules are involved in hydrogen bonding, through O4–H4O···O3 atoms (Fig. 2). Furthermore, the H3O atom bonded to O3 is participating in hydrogen bonding with X atom (X: Br^–/Cl^– ≈ 1:12), which is on the other side interacting via hydrogen bond with the H1N–N1 moiety. The cyclopentyl rings are in envelope conformations.

Related literature top

For dihydrochloride salts of the analog ethylenediamine-N,N'-diacetic acid and ethylenediamine-N,N'-di-3-propionic acid, see: Mistryukov et al. (1987); Shkol'nikova et al. (1989, 1990, 1992). For bond lengths and angles in ethylenediammonium-N,N'-di-3-propanoic acid dichloride and similar compounds, see: Kaluđerović et al. (2004); Kaluderović et al. (2007). For the synthesis, see: Schoenberg et al. (1968);

Experimental top

(S,S)-ethylenediammonium-N,N'-di-2-(3-methyl)-butanoic acid dihalide is obtained as earlier described in literature (Schoenberg et al.,1968), by combining the solutions of L-valine and 1,2-dibromoethane. The title compound is obtained unintentionally. The goal was to synthesize a dicyclopentyl ester of (S,S)-ethylenediammonium-N,N'-di-2-(3-methyl)-butanoic acid dichloride. Thionyl chloride (4.0 ml, 55 mmol) was introduced into a flask containing cyclopentanol (50 ml, anhydrous conditions) over 1 h. After that (S,S)-ethylenediammonium-N,N'-di-2-(3-methyl)-butanoic acid dihalide (calculated for X=Cl: 2.0 g, 6.00 mmol) was added to the flask and the suspension was refluxed 16 h. The mixture was filtered off and the filtrate was left for a few days at 4 °C yielding crystals suitable for X-ray measurements.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP representation of [(H₄eddv)X₂]^.4C₅H₉OH. The structure contains a 1:12 Br/Cl (X) disorder. The figure displays the Cl-part of this disorder (Cl1). Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Network of H-bonding.

(S,S)-N,N'-Bis(1-carboxy-2- methylpropyl)ethylenediammonium 0.09-bromide 0.91-chloride cyclopentanol tetrasolvate top

Crystal data top

C₁₂H₂₆N₂O₄²⁺·2(Br_0.09Cl_0.91⁻)·4(C₅H₁₀O)	F(000) = 745.4
M_r = 685.41	D_x = 1.202 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 12428 reflections
a = 21.2037 (5) Å	θ = 2.9–32.3°
b = 5.2166 (1) Å	µ = 0.39 mm⁻¹
c = 17.2517 (5) Å	T = 130 K
β = 97.037 (2)°	Needles, colourless
V = 1893.86 (8) Å³	0.7 × 0.04 × 0.04 mm
Z = 2

Data collection top

Oxford Diffraction CCD Oxford Xcalibur S diffractometer	5795 independent reflections
Graphite monochromator	4851 reflections with I > 2σ(I)
Detector resolution: 16.356 pixels mm^-1	R_int = 0.035
ω and ϕ scans	θ_max = 30.5°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −30→30
T_min = 0.981, T_max = 0.985	k = −7→7
28298 measured reflections	l = −24→24

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)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0675P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max = 0.001
5795 reflections	Δρ_max = 0.62 e Å⁻³
232 parameters	Δρ_min = −0.37 e Å⁻³
92 restraints	Absolute structure: Flack (1983), 2602 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (2)

Crystal data top

C₁₂H₂₆N₂O₄²⁺·2(Br_0.09Cl_0.91⁻)·4(C₅H₁₀O)	V = 1893.86 (8) Å³
M_r = 685.41	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 21.2037 (5) Å	µ = 0.39 mm⁻¹
b = 5.2166 (1) Å	T = 130 K
c = 17.2517 (5) Å	0.7 × 0.04 × 0.04 mm
β = 97.037 (2)°

Data collection top

Oxford Diffraction CCD Oxford Xcalibur S diffractometer	5795 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	4851 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.985	R_int = 0.035
28298 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.104	Δρ_max = 0.62 e Å⁻³
S = 0.98	Δρ_min = −0.37 e Å⁻³
5795 reflections	Absolute structure: Flack (1983), 2602 Friedel pairs
232 parameters	Absolute structure parameter: −0.04 (2)
92 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Cl1	0.597627 (15)	0.42698 (6)	−0.072483 (19)	0.02203 (10)	0.914 (2)
Br1	0.597627 (15)	0.42698 (6)	−0.072483 (19)	0.02203 (10)	0.086 (2)
O1	0.63329 (7)	0.1414 (3)	0.23276 (8)	0.0340 (3)
O2	0.58689 (6)	0.3389 (2)	0.12648 (7)	0.0267 (3)
O3	0.52079 (7)	0.6832 (3)	−0.22443 (9)	0.0422 (4)
O4	0.40459 (9)	0.5428 (4)	−0.29775 (10)	0.0513 (5)
N1	0.58713 (5)	−0.0783 (3)	0.03571 (7)	0.0172 (2)
C1	0.51770 (7)	−0.1047 (4)	0.04083 (9)	0.0201 (3)
H1A	0.5029	0.0396	0.0712	0.024*
H1B	0.5094	−0.2666	0.0677	0.024*
C2	0.62661 (6)	−0.0867 (4)	0.11390 (8)	0.0184 (3)
H2	0.6129	−0.2374	0.1435	0.022*
C3	0.61327 (8)	0.1557 (3)	0.15757 (10)	0.0205 (3)
C4	0.69721 (7)	−0.1218 (3)	0.10265 (10)	0.0224 (4)
H4	0.6993	−0.2621	0.0636	0.027*
C5	0.72565 (9)	0.1159 (4)	0.07002 (13)	0.0325 (4)
H5A	0.7252	0.2571	0.1074	0.049*
H5B	0.7006	0.1637	0.0206	0.049*
H5C	0.7696	0.0805	0.061	0.049*
C6	0.73642 (9)	−0.2077 (4)	0.17799 (12)	0.0352 (5)
H6A	0.7802	−0.2417	0.168	0.053*
H6B	0.718	−0.3643	0.1971	0.053*
H6C	0.7364	−0.0724	0.2174	0.053*
C7	0.56429 (12)	0.8890 (5)	−0.23271 (13)	0.0457 (6)
H7	0.5722	0.9917	−0.1835	0.055*
C8	0.53654 (16)	1.0530 (6)	−0.29992 (19)	0.0644 (8)
H8A	0.4897	1.0364	−0.3083	0.077*
H8B	0.5477	1.2354	−0.2903	0.077*
C9	0.5648 (3)	0.9555 (15)	−0.3675 (2)	0.137 (2)
H9A	0.5313	0.8773	−0.405	0.164*
H9B	0.5837	1.0998	−0.394	0.164*
C10	0.6126 (5)	0.7700 (16)	−0.3447 (4)	0.065 (3)	0.53 (3)
H10A	0.6514	0.8074	−0.3693	0.078*	0.53 (3)
H10B	0.5974	0.5964	−0.3608	0.078*	0.53 (3)
C10B	0.6295 (7)	0.875 (6)	−0.3364 (7)	0.120 (6)	0.47 (3)
H10C	0.6441	0.7349	−0.3687	0.144*	0.47 (3)
H10D	0.6594	1.0202	−0.3365	0.144*	0.47 (3)
C11	0.62670 (13)	0.7854 (7)	−0.2568 (2)	0.0678 (8)
H11A	0.6369	0.6143	−0.2337	0.081*
H11B	0.6625	0.9036	−0.2408	0.081*
C12	0.38374 (13)	0.6636 (5)	−0.37004 (13)	0.0477 (6)
H12	0.3969	0.8479	−0.3686	0.057*
C13	0.40779 (19)	0.5284 (12)	−0.4380 (2)	0.115 (2)
H13A	0.446	0.4245	−0.4205	0.138*
H13B	0.4182	0.6525	−0.478	0.138*
C14	0.3485 (2)	0.3475 (7)	−0.47177 (19)	0.0811 (11)
H14A	0.3321	0.3974	−0.5259	0.097*
H14B	0.3616	0.1653	−0.4716	0.097*
C15	0.30020 (19)	0.3870 (9)	−0.41962 (19)	0.0827 (11)
H15A	0.3037	0.2558	−0.3779	0.099*
H15B	0.257	0.3791	−0.4488	0.099*
C16	0.31332 (17)	0.6412 (7)	−0.38706 (19)	0.0699 (9)
H16A	0.2933	0.6627	−0.3386	0.084*
H16B	0.2964	0.7743	−0.4249	0.084*
H1N	0.5902 (10)	0.065 (4)	0.0092 (12)	0.018 (5)*
H2N	0.6002 (12)	−0.213 (4)	0.0066 (14)	0.044 (7)*
H4O	0.4439 (15)	0.568 (6)	−0.2807 (17)	0.060 (9)*
H3O	0.5371 (13)	0.581 (6)	−0.1818 (14)	0.062 (9)*
H1O	0.627 (3)	−0.029 (6)	0.250 (4)	0.23 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02064 (15)	0.01766 (14)	0.02759 (17)	0.00010 (16)	0.00212 (11)	0.00040 (17)
Br1	0.02064 (15)	0.01766 (14)	0.02759 (17)	0.00010 (16)	0.00212 (11)	0.00040 (17)
O1	0.0468 (8)	0.0297 (7)	0.0232 (7)	0.0082 (6)	−0.0050 (6)	−0.0016 (5)
O2	0.0360 (7)	0.0161 (5)	0.0271 (6)	0.0043 (5)	−0.0004 (5)	−0.0021 (5)
O3	0.0404 (8)	0.0446 (9)	0.0399 (9)	−0.0104 (7)	−0.0017 (7)	0.0096 (7)
O4	0.0491 (10)	0.0571 (10)	0.0427 (10)	−0.0191 (9)	−0.0137 (8)	0.0288 (8)
N1	0.0150 (5)	0.0144 (5)	0.0218 (6)	−0.0013 (7)	0.0011 (4)	−0.0021 (8)
C1	0.0136 (6)	0.0233 (9)	0.0234 (7)	−0.0005 (6)	0.0017 (5)	0.0009 (7)
C2	0.0182 (6)	0.0148 (6)	0.0214 (6)	−0.0010 (8)	−0.0008 (5)	0.0001 (8)
C3	0.0189 (7)	0.0184 (7)	0.0241 (8)	−0.0038 (6)	0.0018 (6)	−0.0020 (6)
C4	0.0170 (6)	0.0190 (10)	0.0302 (8)	0.0027 (5)	−0.0004 (6)	−0.0008 (6)
C5	0.0180 (8)	0.0337 (10)	0.0461 (12)	0.0008 (7)	0.0057 (8)	0.0089 (9)
C6	0.0255 (9)	0.0337 (11)	0.0439 (12)	0.0065 (8)	−0.0057 (8)	0.0047 (9)
C7	0.0586 (13)	0.0411 (15)	0.0388 (11)	−0.0170 (11)	0.0114 (10)	−0.0112 (10)
C8	0.075 (2)	0.0423 (14)	0.079 (2)	0.0001 (14)	0.0223 (16)	0.0113 (14)
C9	0.146 (4)	0.217 (7)	0.055 (2)	0.058 (5)	0.040 (2)	0.043 (3)
C10	0.082 (5)	0.067 (5)	0.053 (4)	−0.013 (3)	0.039 (4)	−0.018 (3)
C10B	0.075 (6)	0.197 (15)	0.097 (7)	0.001 (10)	0.043 (5)	−0.011 (10)
C11	0.0410 (14)	0.076 (2)	0.086 (2)	−0.0124 (14)	0.0061 (14)	0.0102 (18)
C12	0.0605 (15)	0.0477 (14)	0.0316 (11)	−0.0060 (12)	−0.0078 (10)	0.0176 (10)
C13	0.085 (3)	0.205 (6)	0.056 (2)	0.059 (3)	0.0158 (18)	0.038 (3)
C14	0.132 (3)	0.0586 (19)	0.0527 (17)	−0.0053 (19)	0.011 (2)	−0.0057 (14)
C15	0.097 (2)	0.085 (3)	0.0592 (18)	−0.005 (2)	−0.0168 (17)	0.0057 (18)
C16	0.075 (2)	0.071 (2)	0.0564 (17)	0.0054 (17)	−0.0213 (15)	0.0075 (16)

Geometric parameters (Å, º) top

O1—C3	1.317 (2)	C8—C9	1.466 (5)
O1—H1O	0.95 (2)	C8—H8A	0.99
O2—C3	1.200 (2)	C8—H8B	0.99
O3—C7	1.434 (3)	C9—C10	1.421 (9)
O3—H3O	0.939 (17)	C9—C10B	1.472 (12)
O4—C12	1.419 (2)	C9—H9A	0.99
O4—H4O	0.86 (3)	C9—H9B	0.99
N1—C1	1.4919 (18)	C10—C11	1.512 (8)
N1—C2	1.4986 (18)	C10—H10A	0.99
N1—H1N	0.88 (2)	C10—H10B	0.99
N1—H2N	0.925 (17)	C10B—C11	1.458 (11)
C1—C1ⁱ	1.513 (3)	C10B—H10C	0.99
C1—H1A	0.99	C10B—H10D	0.99
C1—H1B	0.99	C11—H11A	0.99
C2—C3	1.516 (3)	C11—H11B	0.99
C2—C4	1.544 (2)	C12—C16	1.491 (4)
C2—H2	1	C12—C13	1.510 (5)
C4—C5	1.517 (2)	C12—H12	1
C4—C6	1.522 (3)	C13—C14	1.622 (6)
C4—H4	1	C13—H13A	0.99
C5—H5A	0.98	C13—H13B	0.99
C5—H5B	0.98	C14—C15	1.458 (5)
C5—H5C	0.98	C14—H14A	0.99
C6—H6A	0.98	C14—H14B	0.99
C6—H6B	0.98	C15—C16	1.454 (5)
C6—H6C	0.98	C15—H15A	0.99
C7—C8	1.502 (4)	C15—H15B	0.99
C7—C11	1.533 (4)	C16—H16A	0.99
C7—H7	1	C16—H16B	0.99

C3—O1—H1O	108 (4)	C8—C9—H9A	109.4
C7—O3—H3O	108.9 (19)	C10B—C9—H9A	133.1
C12—O4—H4O	115 (2)	C10—C9—H9B	109.4
C1—N1—C2	112.98 (11)	C8—C9—H9B	109.4
C1—N1—H1N	104.2 (14)	C10B—C9—H9B	88.7
C2—N1—H1N	114.9 (14)	H9A—C9—H9B	108
C1—N1—H2N	109.0 (16)	C9—C10—C11	106.7 (4)
C2—N1—H2N	107.1 (17)	C9—C10—H10A	110.4
H1N—N1—H2N	108.5 (18)	C11—C10—H10A	110.4
N1—C1—C1ⁱ	108.99 (15)	C9—C10—H10B	110.4
N1—C1—H1A	109.9	C11—C10—H10B	110.4
C1ⁱ—C1—H1A	109.9	H10A—C10—H10B	108.6
N1—C1—H1B	109.9	C11—C10B—C9	106.9 (7)
C1ⁱ—C1—H1B	109.9	C11—C10B—H10C	110.3
H1A—C1—H1B	108.3	C9—C10B—H10C	110.3
N1—C2—C3	107.77 (15)	C11—C10B—H10D	110.3
N1—C2—C4	109.49 (12)	C9—C10B—H10D	110.3
C3—C2—C4	113.84 (14)	H10C—C10B—H10D	108.6
N1—C2—H2	108.5	C10B—C11—C7	106.2 (5)
C3—C2—H2	108.5	C7—C11—C10	102.7 (4)
C4—C2—H2	108.5	C10B—C11—H11A	129.4
O2—C3—O1	124.15 (16)	C7—C11—H11A	111.2
O2—C3—C2	123.18 (15)	C10—C11—H11A	111.2
O1—C3—C2	112.66 (14)	C10B—C11—H11B	86.8
C5—C4—C6	110.92 (15)	C7—C11—H11B	111.2
C5—C4—C2	112.68 (14)	C10—C11—H11B	111.2
C6—C4—C2	111.35 (15)	H11A—C11—H11B	109.1
C5—C4—H4	107.2	O4—C12—C16	109.6 (2)
C6—C4—H4	107.2	O4—C12—C13	112.1 (3)
C2—C4—H4	107.2	C16—C12—C13	103.6 (3)
C4—C5—H5A	109.5	O4—C12—H12	110.4
C4—C5—H5B	109.5	C16—C12—H12	110.4
H5A—C5—H5B	109.5	C13—C12—H12	110.4
C4—C5—H5C	109.5	C12—C13—C14	103.3 (3)
H5A—C5—H5C	109.5	C12—C13—H13A	111.1
H5B—C5—H5C	109.5	C14—C13—H13A	111.1
C4—C6—H6A	109.5	C12—C13—H13B	111.1
C4—C6—H6B	109.5	C14—C13—H13B	111.1
H6A—C6—H6B	109.5	H13A—C13—H13B	109.1
C4—C6—H6C	109.5	C15—C14—C13	105.6 (3)
H6A—C6—H6C	109.5	C15—C14—H14A	110.6
H6B—C6—H6C	109.5	C13—C14—H14A	110.6
O3—C7—C8	107.9 (2)	C15—C14—H14B	110.6
O3—C7—C11	110.5 (2)	C13—C14—H14B	110.6
C8—C7—C11	105.2 (2)	H14A—C14—H14B	108.8
O3—C7—H7	111	C14—C15—C16	104.6 (4)
C8—C7—H7	111	C14—C15—H15A	110.8
C11—C7—H7	111	C16—C15—H15A	110.8
C9—C8—C7	104.9 (3)	C14—C15—H15B	110.8
C9—C8—H8A	110.8	C16—C15—H15B	110.8
C7—C8—H8A	110.8	H15A—C15—H15B	108.9
C9—C8—H8B	110.8	C15—C16—C12	106.7 (3)
C7—C8—H8B	110.8	C15—C16—H16A	110.4
H8A—C8—H8B	108.8	C12—C16—H16A	110.4
C10—C9—C8	111.3 (4)	C15—C16—H16B	110.4
C8—C9—C10B	105.3 (7)	C12—C16—H16B	110.4
C10—C9—H9A	109.4	H16A—C16—H16B	108.6

Symmetry code: (i) −x+1, y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1	0.88 (2)	2.37 (2)	3.253 (2)	175 (2)
N1—H2N···Cl1ⁱⁱ	0.93 (2)	2.32 (2)	3.209 (2)	161 (2)
N1—H2N···Br1ⁱⁱ	0.93 (2)	2.32 (2)	3.209 (2)	161 (2)
N1—H1N···Br1	0.88 (2)	2.37 (2)	3.253 (2)	175 (2)
O1—H1O···O4ⁱⁱⁱ	0.95 (4)	2.50 (4)	3.446 (3)	172 (5)
O4—H4O···O3	0.86 (3)	1.89 (3)	2.728 (2)	165 (3)
O3—H3O···Cl1	0.94 (3)	2.29 (3)	3.204 (2)	163 (2)
O3—H3O···Br1	0.94 (3)	2.29 (3)	3.204 (2)	163 (2)
C1—H1A···O2	0.99	2.47	3.027 (2)	115
C1—H1B···Cl1ⁱⁱⁱ	0.99	2.79	3.5460 (18)	134
C2—H2···O2ⁱⁱ	1.00	2.29	3.127 (2)	141
C6—H6C···O1	0.98	2.50	3.082 (3)	118

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

Experimental details

Crystal data
Chemical formula	C₁₂H₂₆N₂O₄²⁺·2(Br_0.09Cl_0.91⁻)·4(C₅H₁₀O)
M_r	685.41
Crystal system, space group	Monoclinic, C2
Temperature (K)	130
a, b, c (Å)	21.2037 (5), 5.2166 (1), 17.2517 (5)
β (°)	97.037 (2)
V (Å³)	1893.86 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.7 × 0.04 × 0.04

Data collection
Diffractometer	Oxford Diffraction CCD Oxford Xcalibur S diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.981, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	28298, 5795, 4851
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.104, 0.98
No. of reflections	5795
No. of parameters	232
No. of restraints	92
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.37
Absolute structure	Flack (1983), 2602 Friedel pairs
Absolute structure parameter	−0.04 (2)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1	0.88 (2)	2.37 (2)	3.253 (2)	175 (2)
N1—H2N···Cl1ⁱ	0.93 (2)	2.32 (2)	3.209 (2)	161 (2)
N1—H2N···Br1ⁱ	0.93 (2)	2.32 (2)	3.209 (2)	161 (2)
N1—H1N···Br1	0.88 (2)	2.37 (2)	3.253 (2)	175 (2)
O1—H1O···O4ⁱⁱ	0.95 (4)	2.50 (4)	3.446 (3)	172 (5)
O4—H4O···O3	0.86 (3)	1.89 (3)	2.728 (2)	165 (3)
O3—H3O···Cl1	0.94 (3)	2.29 (3)	3.204 (2)	163 (2)
O3—H3O···Br1	0.94 (3)	2.29 (3)	3.204 (2)	163 (2)

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

Acknowledgements

The authors are grateful to the Ministry of Science and Technological Development of the Republic of Serbia for financial support (grant No. 142010).

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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Kaluderović, G. N., Gómez-Ruiz, S., Schmidt, H. & Steinborn, D. (2007). Acta Cryst. E63, o3491. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Volume 65| Part 3| March 2009| Pages o656-o657

doi:10.1107/S1600536809006679

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(S,S)-N,N′-Bis(1-carb­­oxy-2-methyl­prop­yl)ethyl­enedi­ammonium dihalide cyclo­penta­nol tetra­solvate (halide = bromide/chloride ≃ 1:12)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(S,S)-N,N′-Bis(1-carboxy-2-methylpropyl)ethylenediammonium dihalide cyclopentanol tetrasolvate (halide = bromide/chloride ≃ 1:12)