Creatinium hydrogen oxalate.

The crystal structure of the title compound, C(4)H(10)N(3)O(2) (+)·C(2)HO(4) (-), is stabilized by N-H⋯O and O-H⋯O hydrogen bonds. The anions are connected by an O-H⋯O hydrogen bond, leading to C(5) chain extending along c axis. The cations are dimerized around the corners of the unit cell, leading to an R(2) (2)(14) ring motif. This leads to a cationic mol-ecular aggregation at x = 0 or 1 and an anionic mol-ecular aggregation at x = 1/2.

Related literature

For related structures see: Ali et al. (2011a ▶,b ▶); Bahadur, Kannan et al. (2007 ▶); Bahadur, Sivapragasam et al. (2007 ▶); Bahadur, Rajalakshmi et al. (2007 ▶). For hydrogen-bonding motifs, see Bernstein et al. (1995 ▶). For the biological importance of creatine, see: Cannan & Shore (1928 ▶); Greenhaff et al. (1993 ▶).

Experimental

Crystal data

C4H10N3O2 +·C2HO4 −

M = 221.18

Monoclinic,

a = 7.1545 (4) Å

b = 12.3681 (7) Å

c = 10.5151 (6) Å

β = 94.18 (1)°

V = 927.98 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 293 K

0.24 × 0.22 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

8631 measured reflections

1641 independent reflections

1587 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.102

S = 1.08

1641 reflections

162 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL/PC; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL/PC.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812000852/hg5159sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812000852/hg5159Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812000852/hg5159Isup3.cml

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

C4H10N3O2+·C2HO4−	F(000) = 464
Mr = 221.18	Dx = 1.583 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3216 reflections
a = 7.1545 (4) Å	θ = 2.1–24.7°
b = 12.3681 (7) Å	µ = 0.14 mm−1
c = 10.5151 (6) Å	T = 293 K
β = 94.18 (1)°	Block, colourless
V = 927.98 (9) Å3	0.24 × 0.22 × 0.18 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	1587 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
graphite	θmax = 25.0°, θmin = 2.6°
ω scans	h = −8→8
8631 measured reflections	k = −14→14
1641 independent reflections	l = −12→12

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.0629P)2 + 0.2614P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
1641 reflections	Δρmax = 0.25 e Å−3
162 parameters	Δρmin = −0.23 e Å−3
1 restraint	Extinction correction: SHELXTL/PC (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (6)

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 > 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
C1	0.83544 (18)	1.03293 (11)	0.10352 (12)	0.0299 (3)
C2	0.92061 (19)	1.05574 (11)	0.23633 (13)	0.0326 (3)
H2A	1.0542	1.0671	0.2321	0.039*
H2B	0.8676	1.1225	0.2661	0.039*
C3	0.7146 (2)	0.97346 (13)	0.38693 (16)	0.0440 (4)
H3A	0.6828	0.9015	0.4120	0.066*
H3B	0.6190	1.0005	0.3264	0.066*
H3C	0.7240	1.0195	0.4606	0.066*
C4	1.01280 (19)	0.88981 (11)	0.34586 (12)	0.0316 (3)
N1	0.89312 (16)	0.97171 (9)	0.32919 (11)	0.0323 (3)
N2	1.1567 (2)	0.87994 (13)	0.27569 (14)	0.0482 (4)
N3	0.9923 (2)	0.81801 (10)	0.43697 (13)	0.0403 (3)
O1	0.85571 (15)	1.09547 (8)	0.01761 (9)	0.0385 (3)
O2	0.74475 (17)	0.94241 (9)	0.09369 (11)	0.0460 (3)
H1N	1.163 (4)	0.912 (2)	0.208 (3)	0.083 (8)*
H2N	1.238 (3)	0.8321 (15)	0.2955 (19)	0.051 (5)*
H3N	1.061 (3)	0.7617 (18)	0.4380 (19)	0.053 (5)*
H4N	0.914 (2)	0.8210 (14)	0.495 (2)	0.056 (6)*
H2	0.705 (4)	0.9278 (19)	0.008 (3)	0.084 (7)*
C11	0.56186 (18)	0.81947 (11)	0.82074 (12)	0.0286 (3)
C12	0.58163 (18)	0.79173 (11)	0.67945 (12)	0.0284 (3)
O11	0.45079 (14)	0.76467 (9)	0.87863 (8)	0.0384 (3)
O12	0.66030 (19)	0.89487 (11)	0.86180 (11)	0.0566 (4)
O13	0.43397 (14)	0.74502 (9)	0.62504 (9)	0.0385 (3)
O14	0.72071 (16)	0.81332 (10)	0.62893 (10)	0.0490 (4)
H13O	0.449 (3)	0.7329 (19)	0.542 (2)	0.071 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0297 (7)	0.0292 (7)	0.0313 (7)	0.0010 (5)	0.0054 (5)	0.0002 (5)
C2	0.0375 (7)	0.0294 (7)	0.0306 (7)	−0.0027 (5)	0.0004 (5)	0.0042 (5)
C3	0.0418 (8)	0.0448 (9)	0.0472 (9)	0.0102 (7)	0.0160 (7)	0.0084 (7)
C4	0.0357 (7)	0.0355 (7)	0.0236 (6)	0.0037 (6)	0.0024 (5)	−0.0009 (5)
N1	0.0341 (6)	0.0333 (6)	0.0303 (6)	0.0037 (5)	0.0064 (5)	0.0058 (4)
N2	0.0442 (8)	0.0637 (9)	0.0384 (8)	0.0205 (7)	0.0147 (6)	0.0151 (7)
N3	0.0507 (8)	0.0353 (7)	0.0364 (7)	0.0121 (6)	0.0128 (6)	0.0077 (5)
O1	0.0498 (6)	0.0348 (5)	0.0308 (5)	−0.0016 (4)	0.0019 (4)	0.0058 (4)
O2	0.0615 (7)	0.0432 (6)	0.0335 (6)	−0.0218 (5)	0.0044 (5)	−0.0033 (5)
C11	0.0283 (6)	0.0346 (7)	0.0230 (6)	0.0007 (5)	0.0013 (5)	−0.0007 (5)
C12	0.0317 (7)	0.0304 (7)	0.0237 (6)	0.0000 (5)	0.0045 (5)	0.0012 (5)
O11	0.0429 (6)	0.0515 (6)	0.0215 (5)	−0.0093 (5)	0.0066 (4)	−0.0017 (4)
O12	0.0687 (8)	0.0683 (8)	0.0339 (6)	−0.0311 (7)	0.0101 (5)	−0.0161 (5)
O13	0.0363 (6)	0.0575 (7)	0.0220 (5)	−0.0070 (5)	0.0042 (4)	−0.0083 (4)
O14	0.0447 (6)	0.0712 (8)	0.0330 (6)	−0.0182 (5)	0.0148 (5)	−0.0060 (5)

C1—O1	1.2060 (17)	C4—N1	1.3296 (18)
C1—O2	1.2943 (17)	N2—H1N	0.82 (3)
C1—C2	1.5090 (19)	N2—H2N	0.85 (2)
C2—N1	1.4493 (17)	N3—H3N	0.85 (2)
C2—H2A	0.9700	N3—H4N	0.86 (2)
C2—H2B	0.9700	O2—H2	0.94 (3)
C3—N1	1.4540 (18)	C11—O12	1.2279 (17)
C3—H3A	0.9600	C11—O11	1.2377 (17)
C3—H3B	0.9600	C11—C12	1.5413 (18)
C3—H3C	0.9600	C12—O14	1.1920 (17)
C4—N2	1.3152 (19)	C12—O13	1.2996 (17)
C4—N3	1.3223 (19)	O13—H13O	0.90 (3)
O1—C1—O2	125.59 (13)	C4—N1—C2	121.16 (12)
O1—C1—C2	120.72 (12)	C4—N1—C3	122.23 (12)
O2—C1—C2	113.69 (11)	C2—N1—C3	115.92 (11)
N1—C2—C1	115.09 (11)	C4—N2—H1N	122.7 (19)
N1—C2—H2A	108.5	C4—N2—H2N	118.7 (14)
C1—C2—H2A	108.5	H1N—N2—H2N	118 (2)
N1—C2—H2B	108.5	C4—N3—H3N	117.5 (14)
C1—C2—H2B	108.5	C4—N3—H4N	126.7 (10)
H2A—C2—H2B	107.5	H3N—N3—H4N	115.7 (17)
N1—C3—H3A	109.5	C1—O2—H2	110.9 (15)
N1—C3—H3B	109.5	O12—C11—O11	127.98 (12)
H3A—C3—H3B	109.5	O12—C11—C12	114.67 (12)
N1—C3—H3C	109.5	O11—C11—C12	117.35 (11)
H3A—C3—H3C	109.5	O14—C12—O13	125.56 (12)
H3B—C3—H3C	109.5	O14—C12—C11	121.20 (12)
N2—C4—N3	118.47 (14)	O13—C12—C11	113.24 (11)
N2—C4—N1	121.30 (13)	C12—O13—H13O	110.6 (15)
N3—C4—N1	120.19 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O1i	0.82 (3)	2.37 (3)	3.094 (2)	148 (2)
N2—H2N···O11ii	0.85 (2)	2.08 (2)	2.910 (2)	168 (2)
N3—H3N···O1iii	0.85 (2)	2.18 (2)	2.985 (2)	157 (2)
N3—H4N···O14	0.86 (2)	2.04 (2)	2.903 (2)	174 (2)
O2—H2···O12iv	0.94 (3)	1.60 (3)	2.538 (2)	173 (2)
O13—H13O···O11v	0.90 (3)	1.72 (3)	2.605 (1)	168 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯O1i	0.82 (3)	2.37 (3)	3.094 (2)	148 (2)
N2—H2N⋯O11ii	0.85 (2)	2.08 (2)	2.910 (2)	168 (2)
N3—H3N⋯O1iii	0.85 (2)	2.18 (2)	2.985 (2)	157 (2)
N3—H4N⋯O14	0.86 (2)	2.04 (2)	2.903 (2)	174 (2)
O2—H2⋯O12iv	0.94 (3)	1.60 (3)	2.538 (2)	173 (2)
O13—H13O⋯O11v	0.90 (3)	1.72 (3)	2.605 (1)	168 (2)

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