Crystal structure of iso-butyl-ammonium hydrogen oxalate hemihydrate.

In the title hydrated mol-ecular salt, C4H12N(+)·C2HO4 (-)·0.5H2O, the O atom of the water mol-ecule lies on a crystallographic twofold axis. The dihedral angle between the CO2 and CO2H planes of the anion is 18.47 (8)°. In the crystal, the anions are connected to each other by strong near-linear O-H⋯O hydrogen bonds. The water mol-ecules are located between the chains of anions and iso-butyl-amine cations; their O atoms participate as donors and acceptors, respectively, in O-H⋯O and N-H⋯O hydrogen bonds, which form channels (dimensions = 4.615 and 3.387 Å) arranged parallel to [010].

Related literature

Structure versus properties research is an important area in material engineering, see: Desiraju (2010 ▶, 2013 ▶). For the crystal structures of oxalic acid salts with aliphatic amines, see: Dziuk et al. (2014a ▶,b ▶); Braga et al. (2012 ▶); Ejsmont (2006 ▶, 2007 ▶)); Ejsmont & Zaleski (2006a ▶,b ▶); MacDonald et al. (2001 ▶). For the characteristic structural motifs in ammonium di­carboxyl­ate salts, see: Ali et al. (2012 ▶). For motifs of hydrogen bonds containing carboxylate anions, see: Rodríguez-Cuamatzi et al. (2005 ▶).

Experimental

Crystal data

2C4H12N+·2C2HO4 −·H2O

M = 344.36

Monoclinic,

a = 21.2425 (9) Å

b = 5.6341 (1) Å

c = 16.5372 (6) Å

β = 119.141 (5)°

V = 1728.69 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.30 × 0.17 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

5536 measured reflections

1696 independent reflections

1370 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.070

S = 1.03

1696 reflections

125 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.20 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814022697/hb7298sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814022697/hb7298Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814022697/hb7298Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814022697/hb7298fig1.tif

The mol­ecular structure of (I), showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). Hydrogen bonds are shown as dotted lines.

Click here for additional data file.

b . DOI: 10.1107/S1600536814022697/hb7298fig2.tif

The packing diagram of (I), viewed along the b axis, showing the inter­molecular hydrogen-bonding scheme (dashed lines).

CCDC reference: 1029482

Additional supporting information: crystallographic information; 3D view; checkCIF report

2C4H12N+·2C2HO4−·H2O	F(000) = 744
Mr = 344.36	Dx = 1.323 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1696 reflections
a = 21.2425 (9) Å	θ = 3.8–26.0°
b = 5.6341 (1) Å	µ = 0.11 mm−1
c = 16.5372 (6) Å	T = 100 K
β = 119.141 (5)°	Prism, colourless
V = 1728.69 (10) Å3	0.30 × 0.17 × 0.16 mm
Z = 4

Oxford Diffraction Xcalibur diffractometer	1370 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 26.0°, θmin = 3.8°
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1	h = −26→26
ω scan	k = −5→6
5536 measured reflections	l = −20→20
1696 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0414P)2 + 0.1361P] where P = (Fo2 + 2Fc2)/3
1696 reflections	(Δ/σ)max < 0.001
125 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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.

	x	y	z	Uiso*/Ueq
N1	−0.06332 (5)	−0.08724 (18)	0.31560 (7)	0.0152 (2)
H1A	−0.0236 (8)	0.019 (2)	0.3483 (9)	0.031 (4)*
H1B	−0.0747 (8)	−0.146 (2)	0.3559 (10)	0.030 (4)*
H1C	−0.0464 (8)	−0.208 (3)	0.2919 (10)	0.036 (4)*
C2	−0.12455 (6)	0.0404 (2)	0.23817 (8)	0.0165 (3)
H2A	−0.1056	0.1504	0.2102	0.020*
H2B	−0.1500	0.1319	0.2628	0.020*
C3	−0.17707 (6)	−0.1272 (2)	0.16433 (8)	0.0171 (3)
H3A	−0.1503	−0.2241	0.1421	0.021*
C4	−0.23158 (7)	0.0228 (2)	0.08384 (9)	0.0284 (3)
H4A	−0.2066	0.1251	0.0625	0.043*
H4B	−0.2589	0.1170	0.1041	0.043*
H4C	−0.2635	−0.0794	0.0343	0.043*
C5	−0.21430 (7)	−0.2922 (2)	0.20040 (9)	0.0247 (3)
H5A	−0.1788	−0.3842	0.2509	0.037*
H5B	−0.2461	−0.3966	0.1517	0.037*
H5C	−0.2416	−0.2002	0.2214	0.037*
C6	0.07522 (6)	0.27767 (19)	0.47629 (8)	0.0119 (2)
C7	0.08118 (6)	0.52879 (19)	0.51722 (7)	0.0119 (2)
O8	0.05406 (4)	0.25554 (13)	0.39204 (5)	0.0149 (2)
O9	0.09169 (4)	0.11123 (13)	0.53399 (5)	0.0180 (2)
O10	0.08298 (4)	0.69868 (14)	0.46405 (5)	0.0155 (2)
H10	0.0884 (9)	0.855 (3)	0.4940 (12)	0.057 (5)*
O11	0.08261 (4)	0.55763 (14)	0.59056 (5)	0.0169 (2)
O12	0.0000	0.5785 (2)	0.2500	0.0165 (3)
H12	0.0198 (9)	0.486 (3)	0.2967 (10)	0.048 (5)*

	U11	U22	U33	U12	U13	U23
N1	0.0170 (5)	0.0171 (5)	0.0115 (5)	−0.0011 (4)	0.0070 (4)	0.0001 (4)
C2	0.0180 (6)	0.0156 (6)	0.0159 (6)	0.0012 (5)	0.0082 (5)	0.0039 (5)
C3	0.0170 (6)	0.0213 (6)	0.0130 (6)	0.0028 (5)	0.0073 (5)	−0.0003 (5)
C4	0.0218 (7)	0.0356 (8)	0.0207 (7)	0.0002 (6)	0.0048 (6)	0.0079 (6)
C5	0.0238 (7)	0.0195 (7)	0.0256 (7)	−0.0044 (5)	0.0080 (6)	0.0005 (5)
C6	0.0120 (6)	0.0123 (6)	0.0127 (6)	0.0000 (4)	0.0072 (5)	0.0004 (4)
C7	0.0098 (6)	0.0131 (6)	0.0117 (5)	0.0001 (4)	0.0043 (4)	0.0010 (4)
O8	0.0216 (4)	0.0129 (4)	0.0110 (4)	0.0002 (3)	0.0087 (4)	−0.0010 (3)
O9	0.0304 (5)	0.0111 (4)	0.0140 (4)	0.0002 (3)	0.0119 (4)	0.0015 (3)
O10	0.0248 (5)	0.0097 (4)	0.0137 (4)	−0.0006 (3)	0.0107 (4)	0.0008 (3)
O11	0.0252 (5)	0.0156 (4)	0.0119 (4)	−0.0009 (3)	0.0106 (4)	−0.0016 (3)
O12	0.0227 (7)	0.0142 (6)	0.0103 (6)	0.000	0.0062 (5)	0.000

N1—C2	1.4921 (14)	C4—H4C	0.9600
N1—H1A	0.959 (15)	C5—H5A	0.9600
N1—H1B	0.877 (15)	C5—H5B	0.9600
N1—H1C	0.940 (15)	C5—H5C	0.9600
C2—C3	1.5167 (16)	C6—O8	1.2445 (13)
C2—H2A	0.9700	C6—O9	1.2599 (13)
C2—H2B	0.9700	C6—C7	1.5468 (15)
C3—C5	1.5181 (17)	C7—O11	1.2092 (13)
C3—C4	1.5249 (16)	C7—O10	1.3128 (13)
C3—H3A	0.9800	O10—H10	0.988 (17)
C4—H4A	0.9600	O12—H12	0.853 (15)
C4—H4B	0.9600
C2—N1—H1A	110.0 (8)	C3—C4—H4B	109.5
C2—N1—H1B	112.6 (9)	H4A—C4—H4B	109.5
H1A—N1—H1B	107.4 (12)	C3—C4—H4C	109.5
C2—N1—H1C	110.0 (9)	H4A—C4—H4C	109.5
H1A—N1—H1C	106.2 (12)	H4B—C4—H4C	109.5
H1B—N1—H1C	110.4 (12)	C3—C5—H5A	109.5
N1—C2—C3	112.53 (9)	C3—C5—H5B	109.5
N1—C2—H2A	109.1	H5A—C5—H5B	109.5
C3—C2—H2A	109.1	C3—C5—H5C	109.5
N1—C2—H2B	109.1	H5A—C5—H5C	109.5
C3—C2—H2B	109.1	H5B—C5—H5C	109.5
H2A—C2—H2B	107.8	O8—C6—O9	126.09 (10)
C2—C3—C5	112.62 (9)	O8—C6—C7	119.31 (9)
C2—C3—C4	107.83 (10)	O9—C6—C7	114.58 (9)
C5—C3—C4	111.28 (10)	O11—C7—O10	125.39 (10)
C2—C3—H3A	108.3	O11—C7—C6	121.24 (10)
C5—C3—H3A	108.3	O10—C7—C6	113.37 (9)
C4—C3—H3A	108.3	C7—O10—H10	110.3 (10)
C3—C4—H4A	109.5
N1—C2—C3—C5	63.80 (13)	O9—C6—C7—O11	−18.47 (15)
N1—C2—C3—C4	−173.04 (10)	O8—C6—C7—O10	−18.64 (14)
O8—C6—C7—O11	160.16 (10)	O9—C6—C7—O10	162.72 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O8	0.959 (15)	1.963 (15)	2.9111 (13)	169.2 (12)
N1—H1B···O9i	0.877 (15)	2.031 (15)	2.8333 (13)	151.7 (12)
N1—H1B···O11i	0.877 (15)	2.518 (14)	3.1968 (13)	134.8 (11)
N1—H1C···O12ii	0.940 (15)	1.887 (16)	2.8202 (13)	171.4 (13)
O12—H12···O8	0.853 (15)	1.893 (15)	2.7423 (10)	173.0 (16)
O10—H10···O9iii	0.988 (17)	1.577 (17)	2.5625 (11)	175.3 (17)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1AO8	0.959(15)	1.963(15)	2.9111(13)	169.2(12)
N1H1BO9i	0.877(15)	2.031(15)	2.8333(13)	151.7(12)
N1H1BO11i	0.877(15)	2.518(14)	3.1968(13)	134.8(11)
N1H1CO12ii	0.940(15)	1.887(16)	2.8202(13)	171.4(13)
O12H12O8	0.853(15)	1.893(15)	2.7423(10)	173.0(16)
O10H10O9iii	0.988(17)	1.577(17)	2.5625(11)	175.3(17)

Symmetry codes: (i) ; (ii) ; (iii) .