Propane-1,2-diaminium selenite monohydrate

Todd, M.J.; Harrison, W.T.A.

doi:10.1107/S160053680501278X

organic compounds

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ISSN: 2056-9890

Volume 61| Part 6| June 2005| Pages o1538-o1540

https://doi.org/10.1107/S160053680501278X

Propane-1,2-diaminium selenite monohydrate

Malcolm J. Todd ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 15 April 2005; accepted 22 April 2005; online 7 May 2005)

The title compound, C₃H₁₂N₂²⁺·SeO₃²⁻·H₂O, contains a network of propane-1,2-diaminium (C₃H₁₂N₂²⁺) cations, selenite (SeO₃²⁻) anions and water molecules. The crystal packing involves N—H⋯O [average H⋯O = 1.89 Å, N—H⋯O = 165° and N⋯O = 2.777 (3) Å] and O—H⋯O hydrogen bonds, resulting in a layered structure.

Comment

The title compound, (I), was prepared as part of our ongoing studies of hydrogen-bonding interactions in the crystal structures of (protonated) amine phosphates (Demir et al., 2003 ), phosphites (Harrison, 2003 ), selenites (Ritchie & Harrison, 2003 ) and arsenates (Lee & Harrison, 2003a ,b ,c ; Wilkinson & Harrison, 2004 ).

The asymmetric unit of (I) contains one C₃H₁₂N₂²⁺ cation, one SeO₂²⁻ anion and a water molecule (Fig. 1). The geometric parameters for the organic cation are unexceptional (Lee & Harrison, 2003a). This species is chiral (C1 has S configuration in the selected asymmetric unit), but crystal symmetry generates a 50:50 mix of enantiomers, consistent with the racemic starting material. The selenite group in (I) shows its standard (Lee & Harrison, 2003) pyramidal geometry (Table 1) [average Se—O = 1.687 (2) Å], with the Se atom displaced from the plane of its three attached O atoms by 0.7213 (12) Å.

As well as electrostatic attractions, the component species in (I) interact by means of a network of N—H⋯O and O—H⋯O hydrogen bonds (Table 2). The selenite anions and water molecules are linked into a polymeric chain in the [010] direction by hydrogen bonds (Fig. 2). The organic species interacts with the selenite/water chains by way of N—H⋯O hydrogen bonds (Table 2). All six of the –NH₃⁺ H atoms are involved in these links [mean H⋯O = 1.89 Å, N—H⋯O = 165° and N⋯O = 2.777 (3) Å]. These interactions result in (101) selenite/water/aminium layers sandwiched between the carbon backbones of the organic groups (Fig. 3), which themselves interact by way of van der Waals forces.

Propane-1,2-diaminium hydrogenarsenate monohydrate, C₃H₁₂N₂²⁺·HAsO₄²⁻·H₂O (Lee & Harrison, 2003a), has an equivalent stoichiometry to (I). As might be expected, where the oxo anion has hydrogen-bonding capability (i.e. as As—OH⋯O links), a quite different overall structure arises. An interesting difference also arises for the organic cation; in (I), the –NH₃⁺ and –CH₃ groups are trans about their linking C—C bond (Table 1), whereas in the hydrogenarsenate, they are gauche [C—C—C—N = −54.09 (18)°].

Figure 1
Asymmetric unit of (I)

, showing 50% displacement ellipsoids (arbitrary spheres for H atoms). Hydrogen bonds are indicated by dashed lines.

Figure 2
Detail of a hydrogen-bonded selenite/water chain in (I)

. Symmetry codes are as in Table 2

[additionally: (v) x, 1 + y, z]. Hydrogen bonds are indicated by dashed lines.

Figure 3
[010] projection of the packing for (I)

. C-bound H atoms have been omitted for clarity and hydrogen bonds are indicated by dashed lines.

Experimental

An aqueous 0.5 M propane-1,2-diamine solution (10 ml) was added to aqueous 0.5 M H₂SeO₃ solution (10 ml, dissolved SeO₂) to result in a clear solution. A mass of colourless platy crystals of (I), with a pale-pink tinge arising from a surface coating, grew as the water evaporated over the course of a few days.

Crystal data

C₃H₁₂N₂²⁺·SeO₃²⁻·H₂O
M_r = 221.12
Monoclinic, P 2/n
a = 11.5494 (7) Å
b = 6.1399 (4) Å
c = 11.6601 (6) Å
β = 92.213 (3)°
V = 826.23 (8) Å³
Z = 4
D_x = 1.778 Mg m⁻³
Mo Kα radiation
Cell parameters from 1941 reflections
θ = 2.9–27.5°
μ = 4.51 mm⁻¹
T = 120 (2) K
Plate, colourless
0.12 × 0.10 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan(SADABS; Bruker, 2003 )T_min = 0.613, T_max = 0.915
8108 measured reflections
1882 independent reflections
1617 reflections with I > 2σ(I)
R_int = 0.044
θ_max = 27.5°
h = −12 → 15
k = −7 → 7
l = −15 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.068
S = 1.07
1882 reflections
95 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0274P)² + 0.5437P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.51 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.0026 (7)

Table 1
Selected geometric parameters (Å, °)

Se1—O1	1.673 (2)
Se1—O3	1.6826 (19)
Se1—O2	1.7052 (18)

N1—C1—C2—N2	55.2 (3)
C3—C1—C2—N2	176.9 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.91	1.88	2.779 (3)	171
N1—H2⋯O1ⁱⁱ	0.91	1.81	2.701 (3)	165
N1—H3⋯O2	0.91	2.00	2.835 (3)	152
N2—H4⋯O4ⁱⁱⁱ	0.91	1.91	2.802 (3)	165
N2—H5⋯O3	0.91	1.87	2.777 (3)	173
N2—H6⋯O2ⁱⁱ	0.91	1.88	2.766 (3)	164
O4—H13⋯O3	0.88	1.96	2.840 (3)	178
O4—H14⋯O1^iv	0.76	2.04	2.747 (3)	157
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+2, -z; (iii) $[-x+{\script{3\over 2}}, y+1, -z+{\script{1\over 2}}]$ ; (iv) x, y-1, z.

The non-standard P2/n setting of the space group was chosen in preference to P2/c to avoid a unit cell with a very obtuse β angle of 133.6°. The water H atoms were found in a difference map and refined as riding in their as-found relative positions (Table 2). H atoms bonded to C and N atoms were placed in idealized positions (C—H = 0.98–1.00 Å and N—H = 0.91 Å) and refined as riding, allowing for free rotation of the rigid –XH₃ (X = C3, N1 and N2) groups. The constraint U_iso(H) = 1.2U_eq(carrier) or U_iso(H) = 1.2U_eq(methyl carrier) was applied as appropriate.

Data collection: COLLECT (Nonius, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053680501278X/hg6175sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680501278X/hg6175Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: COLLECT; data reduction: COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Propane-1,2-diaminium selenite monohydrate top

Crystal data top

C₃H₁₂N₂²⁺·SeO₃²⁻·H₂O	F(000) = 448
M_r = 221.12	D_x = 1.778 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 1941 reflections
a = 11.5494 (7) Å	θ = 2.9–27.5°
b = 6.1399 (4) Å	µ = 4.51 mm⁻¹
c = 11.6601 (6) Å	T = 120 K
β = 92.213 (3)°	Plate, colourless
V = 826.23 (8) Å³	0.12 × 0.10 × 0.02 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1882 independent reflections
Radiation source: fine-focus sealed tube	1617 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω and φ scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −12→15
T_min = 0.613, T_max = 0.915	k = −7→7
8108 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap (O-H) and geom (C-N and N-H)
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0274P)² + 0.5437P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1882 reflections	Δρ_max = 0.98 e Å⁻³
95 parameters	Δρ_min = −0.51 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (7)

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
Se1	0.44873 (2)	0.81651 (4)	0.21940 (2)	0.01546 (12)
O1	0.43374 (17)	1.0875 (3)	0.22349 (16)	0.0253 (5)
O2	0.42321 (16)	0.7560 (3)	0.07795 (16)	0.0204 (4)
O3	0.59257 (16)	0.7750 (3)	0.23366 (16)	0.0209 (4)
C1	0.7531 (2)	0.6926 (4)	0.0105 (2)	0.0180 (6)
H7	0.7578	0.6212	0.0876	0.022*
C2	0.7916 (2)	0.9266 (4)	0.0239 (2)	0.0169 (5)
H8	0.8708	0.9299	0.0595	0.020*
H9	0.7947	0.9943	−0.0529	0.020*
C3	0.8323 (2)	0.5718 (5)	−0.0684 (2)	0.0240 (6)
H10	0.8072	0.4198	−0.0755	0.036*
H11	0.9120	0.5769	−0.0364	0.036*
H12	0.8290	0.6407	−0.1443	0.036*
N1	0.63165 (19)	0.6781 (3)	−0.03598 (19)	0.0169 (5)
H1	0.6158	0.5383	−0.0573	0.020*
H2	0.6225	0.7671	−0.0981	0.020*
H3	0.5824	0.7199	0.0189	0.020*
N2	0.71339 (19)	1.0567 (4)	0.09542 (19)	0.0180 (5)
H4	0.7554	1.1595	0.1349	0.022*
H5	0.6784	0.9673	0.1458	0.022*
H6	0.6586	1.1229	0.0494	0.022*
O4	0.62226 (18)	0.3308 (3)	0.29602 (19)	0.0283 (5)
H13	0.6129	0.4666	0.2746	0.034*
H14	0.5633	0.2771	0.2923	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.01747 (18)	0.01530 (16)	0.01357 (16)	−0.00069 (11)	0.00008 (11)	0.00103 (10)
O1	0.0291 (11)	0.0169 (10)	0.0293 (11)	0.0055 (9)	−0.0071 (9)	−0.0067 (9)
O2	0.0239 (11)	0.0173 (9)	0.0194 (10)	0.0011 (8)	−0.0077 (8)	−0.0037 (8)
O3	0.0166 (10)	0.0209 (10)	0.0248 (10)	−0.0008 (8)	−0.0037 (8)	0.0036 (8)
C1	0.0180 (14)	0.0158 (13)	0.0203 (14)	0.0017 (11)	−0.0001 (11)	−0.0008 (11)
C2	0.0144 (13)	0.0173 (13)	0.0191 (13)	−0.0005 (11)	−0.0008 (10)	−0.0007 (11)
C3	0.0198 (15)	0.0236 (15)	0.0288 (15)	0.0048 (12)	0.0049 (12)	0.0005 (13)
N1	0.0175 (12)	0.0137 (11)	0.0195 (12)	0.0007 (9)	−0.0002 (9)	−0.0049 (9)
N2	0.0178 (12)	0.0142 (11)	0.0216 (11)	−0.0006 (9)	−0.0060 (9)	0.0000 (9)
O4	0.0199 (11)	0.0156 (10)	0.0482 (13)	0.0024 (8)	−0.0131 (10)	0.0040 (9)

Geometric parameters (Å, º) top

Se1—O1	1.673 (2)	C3—H11	0.9800
Se1—O3	1.6826 (19)	C3—H12	0.9800
Se1—O2	1.7052 (18)	N1—H1	0.9100
C1—N1	1.487 (3)	N1—H2	0.9100
C1—C2	1.510 (4)	N1—H3	0.9100
C1—C3	1.516 (4)	N2—H4	0.9100
C1—H7	1.0000	N2—H5	0.9100
C2—N2	1.485 (3)	N2—H6	0.9100
C2—H8	0.9900	O4—H13	0.8761
C2—H9	0.9900	O4—H14	0.7566
C3—H10	0.9800

O1—Se1—O3	104.52 (9)	H10—C3—H11	109.5
O1—Se1—O2	103.29 (9)	C1—C3—H12	109.5
O3—Se1—O2	101.28 (9)	H10—C3—H12	109.5
N1—C1—C2	111.4 (2)	H11—C3—H12	109.5
N1—C1—C3	109.4 (2)	C1—N1—H1	109.5
C2—C1—C3	110.3 (2)	C1—N1—H2	109.5
N1—C1—H7	108.6	H1—N1—H2	109.5
C2—C1—H7	108.6	C1—N1—H3	109.5
C3—C1—H7	108.6	H1—N1—H3	109.5
N2—C2—C1	112.8 (2)	H2—N1—H3	109.5
N2—C2—H8	109.0	C2—N2—H4	109.5
C1—C2—H8	109.0	C2—N2—H5	109.5
N2—C2—H9	109.0	H4—N2—H5	109.5
C1—C2—H9	109.0	C2—N2—H6	109.5
H8—C2—H9	107.8	H4—N2—H6	109.5
C1—C3—H10	109.5	H5—N2—H6	109.5
C1—C3—H11	109.5	H13—O4—H14	107.3

N1—C1—C2—N2	55.2 (3)	C3—C1—C2—N2	176.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.91	1.88	2.779 (3)	171
N1—H2···O1ⁱⁱ	0.91	1.81	2.701 (3)	165
N1—H3···O2	0.91	2.00	2.835 (3)	152
N2—H4···O4ⁱⁱⁱ	0.91	1.91	2.802 (3)	165
N2—H5···O3	0.91	1.87	2.777 (3)	173
N2—H6···O2ⁱⁱ	0.91	1.88	2.766 (3)	164
O4—H13···O3	0.88	1.96	2.840 (3)	178
O4—H14···O1^iv	0.76	2.04	2.747 (3)	157

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+2, −z; (iii) −x+3/2, y+1, −z+1/2; (iv) x, y−1, z.

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton, England) for the data collection.

References

Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Propane-1,2-diaminium selenite monohydrate

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds