dl-Asparaginium perchlorate.

Two enantiomeric counterparts (l- and d-asparginium cations related by glide planes) are present in the structure of the title compound, C(4)H(9)N(2)O(3) (+)·ClO(4) (-), with a 1:1 cation-anion ratio. The structure is built up from asparginium cations and perchlorate anions. In the crystal, mol-ecules assemble in double layers parallel to (100) through N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds. In the asparginium layers, hydrogen bonds generate alternating R(2) (2)(8) and R(4) (3)(18) graph-set motifs. Further hydrogen bonds involving the anions and cations result in the formation of a three-dimensional network.

Related literature

For the use of dl-asparagine in growth-media for bacteria, see: Gerhardt & Wilson (1948 ▶); Palleroni et al. (1973 ▶); van Wagtendonk et al. (1963 ▶). For related structures, see: Aarthy et al. (2005 ▶); Anitha et al. (2005 ▶); Bendjeddou et al. (2009 ▶); Verbist et al. (1972 ▶); Wang et al. (1985 ▶); Yamada et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C4H9N2O3 +·ClO4 −

M = 232.58

Orthorhombic,

a = 9.861 (5) Å

b = 10.289 (4) Å

c = 16.700 (5) Å

V = 1694.4 (12) Å3

Z = 8

Mo Kα radiation

μ = 0.47 mm−1

T = 100 K

0.09 × 0.04 × 0.02 mm

Data collection

Oxford Diffraction Xcalibur Saphire2 CCD diffractometer

Absorption correction: none

45509 measured reflections

2818 independent reflections

2205 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.100

S = 1.12

2818 reflections

127 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.68 e Å−3

Δρmin = −0.38 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: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PARST97 (Nardelli, 1995 ▶) and Mercury (Macrae et al., 2006 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033534/at2865sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033534/at2865Isup2.hkl

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

C4H9N2O3+·ClO4−	F(000) = 960
Mr = 232.58	Dx = 1.823 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2818 reflections
a = 9.861 (5) Å	θ = 3.1–31.5°
b = 10.289 (4) Å	µ = 0.47 mm−1
c = 16.700 (5) Å	T = 100 K
V = 1694.4 (12) Å3	Needle, colourless
Z = 8	0.09 × 0.04 × 0.02 mm

Oxford Diffraction Xcalibur Saphire2 CCD diffractometer	2205 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
graphite	θmax = 31.5°, θmin = 3.1°
φ and ω scans	h = −14→14
45509 measured reflections	k = −15→11
2818 independent reflections	l = −24→24

Refinement on F2	1 restraint
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034	w = 1/[σ2(Fo2) + (0.0538P)2 + 0.6998P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.100	(Δ/σ)max = 0.001
S = 1.12	Δρmax = 0.68 e Å−3
2818 reflections	Δρmin = −0.38 e Å−3
127 parameters

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O1	0.58079 (10)	0.69351 (10)	0.73615 (6)	0.0162 (3)
O2	0.45528 (9)	0.59815 (10)	0.63971 (6)	0.0139 (3)
O3	0.61640 (11)	0.32442 (10)	0.70705 (6)	0.0158 (3)
N1	0.67333 (11)	0.48834 (11)	0.57093 (6)	0.0115 (3)
N2	0.71473 (14)	0.37342 (13)	0.82581 (7)	0.0204 (4)
C1	0.56293 (14)	0.62144 (13)	0.67245 (8)	0.0117 (3)
C2	0.69857 (13)	0.56919 (13)	0.64328 (8)	0.0111 (3)
C3	0.77716 (13)	0.49753 (13)	0.70849 (8)	0.0126 (3)
C4	0.69625 (14)	0.39103 (13)	0.74834 (8)	0.0127 (3)
Cl	0.47309 (3)	0.19831 (3)	0.51836 (2)	0.0127 (1)
O4	0.40552 (10)	0.17287 (10)	0.44286 (6)	0.0158 (3)
O5	0.43440 (10)	0.32809 (10)	0.54535 (6)	0.0145 (3)
O6	0.43348 (15)	0.10450 (12)	0.57652 (7)	0.0315 (4)
O7	0.61761 (11)	0.19650 (11)	0.50614 (7)	0.0226 (3)
H1	0.50733	0.72120	0.75158	0.0243*
H1A	0.75164	0.45681	0.55290	0.0172*
H1B	0.63499	0.53694	0.53310	0.0172*
H1C	0.61828	0.42291	0.58350	0.0172*
H2	0.75352	0.64382	0.62663	0.0133*
H3A	0.85826	0.46000	0.68513	0.0151*
H3B	0.80548	0.55964	0.74887	0.0151*
H4N	0.67437	0.31063	0.84737	0.0246*
H5N	0.77523	0.41807	0.84813	0.0246*

	U11	U22	U33	U12	U13	U23
O1	0.0144 (5)	0.0187 (5)	0.0156 (5)	0.0014 (4)	0.0022 (4)	−0.0059 (4)
O2	0.0116 (4)	0.0155 (5)	0.0146 (5)	0.0008 (3)	0.0014 (3)	0.0001 (4)
O3	0.0162 (5)	0.0177 (5)	0.0135 (4)	−0.0048 (4)	−0.0012 (4)	0.0035 (4)
N1	0.0113 (5)	0.0127 (5)	0.0104 (5)	0.0015 (4)	0.0010 (4)	0.0002 (4)
N2	0.0253 (7)	0.0250 (7)	0.0110 (5)	0.0020 (5)	−0.0013 (4)	0.0023 (5)
C1	0.0134 (6)	0.0092 (5)	0.0125 (6)	−0.0007 (4)	0.0028 (4)	0.0024 (5)
C2	0.0104 (5)	0.0108 (5)	0.0120 (5)	−0.0010 (4)	0.0013 (4)	−0.0014 (4)
C3	0.0102 (5)	0.0141 (6)	0.0135 (6)	−0.0005 (4)	−0.0017 (4)	−0.0010 (5)
C4	0.0128 (5)	0.0133 (6)	0.0119 (6)	0.0045 (5)	0.0010 (4)	−0.0002 (5)
Cl	0.0164 (2)	0.0106 (2)	0.0112 (2)	−0.0003 (1)	−0.0021 (1)	0.0004 (1)
O4	0.0155 (5)	0.0178 (5)	0.0142 (5)	−0.0034 (4)	−0.0043 (4)	−0.0027 (4)
O5	0.0165 (5)	0.0125 (5)	0.0145 (5)	0.0006 (3)	−0.0008 (4)	−0.0023 (4)
O6	0.0588 (9)	0.0177 (5)	0.0179 (6)	−0.0056 (5)	0.0043 (5)	0.0082 (4)
O7	0.0145 (5)	0.0267 (6)	0.0265 (6)	0.0061 (4)	−0.0080 (4)	−0.0079 (4)

Cl—O5	1.4601 (13)	N1—H1C	0.8900
Cl—O6	1.4239 (15)	N1—H1B	0.8900
Cl—O4	1.4499 (13)	N2—H4N	0.8400
Cl—O7	1.4398 (13)	N2—H5N	0.8400
O1—C1	1.3086 (18)	C1—C2	1.522 (2)
O2—C1	1.2179 (18)	C2—C3	1.527 (2)
O3—C4	1.2511 (18)	C3—C4	1.510 (2)
O1—H1	0.8200	C2—H2	0.9800
N1—C2	1.4879 (19)	C3—H3A	0.9700
N2—C4	1.3190 (19)	C3—H3B	0.9700
N1—H1A	0.8900
O5—Cl—O6	109.74 (7)	O1—C1—C2	110.01 (11)
O5—Cl—O7	108.32 (6)	O1—C1—O2	126.42 (13)
O6—Cl—O7	111.07 (8)	N1—C2—C3	113.22 (11)
O4—Cl—O5	108.27 (6)	N1—C2—C1	108.09 (10)
O4—Cl—O6	110.17 (7)	C1—C2—C3	112.86 (11)
O4—Cl—O7	109.23 (6)	C2—C3—C4	113.37 (11)
C1—O1—H1	109.00	N2—C4—C3	117.32 (12)
C2—N1—H1A	109.00	O3—C4—N2	123.53 (13)
C2—N1—H1B	109.00	O3—C4—C3	119.16 (12)
H1B—N1—H1C	109.00	N1—C2—H2	107.00
H1A—N1—H1C	109.00	C1—C2—H2	107.00
C2—N1—H1C	109.00	C3—C2—H2	107.00
H1A—N1—H1B	109.00	H3A—C3—H3B	108.00
C4—N2—H5N	117.00	C2—C3—H3A	109.00
H4N—N2—H5N	125.00	C2—C3—H3B	109.00
C4—N2—H4N	117.00	C4—C3—H3A	109.00
O2—C1—C2	123.57 (12)	C4—C3—H3B	109.00

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3i	0.8200	1.7600	2.5485 (19)	161.00
N1—H1A···O4ii	0.8900	2.0200	2.837 (2)	152.00
N1—H1B···O5iii	0.8900	2.0300	2.910 (2)	171.00
N1—H1C···O3	0.8900	2.3000	2.886 (2)	123.00
N1—H1C···O5	0.8900	2.1600	2.907 (2)	142.00
N2—H4N···O2iv	0.8400	2.5400	3.341 (2)	159.00
N2—H5N···O2v	0.8400	2.5700	3.362 (2)	157.00
N2—H5N···O5v	0.8400	2.5500	3.089 (2)	123.00
C2—H2···O7vi	0.9800	2.4400	3.201 (2)	134.00
C3—H3A···O4ii	0.9700	2.5800	3.326 (2)	134.00
C3—H3B···O2v	0.9700	2.4100	3.253 (2)	145.00

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3i	0.82	1.76	2.5485 (19)	161
N1—H1A⋯O4ii	0.89	2.02	2.837 (2)	152
N1—H1B⋯O5iii	0.89	2.03	2.910 (2)	171
N1—H1C⋯O3	0.89	2.30	2.886 (2)	123
N1—H1C⋯O5	0.89	2.16	2.907 (2)	142
N2—H4N⋯O2iv	0.84	2.54	3.341 (2)	159
N2—H5N⋯O2v	0.84	2.57	3.362 (2)	157
N2—H5N⋯O5v	0.84	2.55	3.089 (2)	123
C2—H2⋯O7vi	0.98	2.44	3.201 (2)	134
C3—H3A⋯O4ii	0.97	2.58	3.326 (2)	134
C3—H3B⋯O2v	0.97	2.41	3.253 (2)	145

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .