Creatininium hydrogen maleate.

In the title compound, C(4)H(8)N(3)O(+)·C(4)H(3)O(4) (-), the cations and anions are linked through N-H⋯O hydrogen bonds making a ionic pair with an R(2) (2)(8) ring motif. These ionic pairs are further connected through another N-H⋯O hydrogen bond, leading to an R(6) (6)(16) ring motif around the inversion centres of the unit cell. These approximately planar aggregates are further connected through weak van der Waals inter-actions in the unit cell. The anions have a characteristic intra-molecular O-H⋯O hydrogen bond with a self-associated ring S(7) motif.

Related literature

For related structures, see: Ali et al. (2011 ▶); Bahadur, Kannan et al. (2007 ▶); Bahadur, Sivapragasam et al. (2007 ▶); Bahadur, Rajalakshmi et al. (2007 ▶). For hydrogen-bonding motif notation, see: Bernstein et al. (1995 ▶); Desiraju (1989 ▶). For the importance of creatinine, see: Madaras & Buck (1996 ▶); Sharma et al. (2004 ▶); Narayanan & Appleton (1980 ▶).

Experimental

Crystal data

C4H8N3O+·C4H3O4 −

M = 229.20

Monoclinic,

a = 5.6271 (4) Å

b = 24.8915 (17) Å

c = 7.7752 (6) Å

β = 108.69 (2)°

V = 1031.62 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 293 K

0.24 × 0.21 × 0.17 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

9754 measured reflections

1823 independent reflections

1699 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.102

S = 1.06

1823 reflections

162 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.22 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/S1600536811040050/hg5104sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040050/hg5104Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811040050/hg5104Isup3.cml

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

C4H8N3O+·C4H3O4−	F(000) = 480
Mr = 229.20	Dx = 1.476 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3738 reflections
a = 5.6271 (4) Å	θ = 2.3–24.6°
b = 24.8915 (17) Å	µ = 0.12 mm−1
c = 7.7752 (6) Å	T = 293 K
β = 108.69 (2)°	Block, colourless
V = 1031.62 (18) Å3	0.24 × 0.21 × 0.17 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	1699 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
graphite	θmax = 25.0°, θmin = 2.9°
ω scans	h = −6→6
9754 measured reflections	k = −29→29
1823 independent reflections	l = −9→9

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0593P)2 + 0.2134P] where P = (Fo2 + 2Fc2)/3
1823 reflections	(Δ/σ)max < 0.001
162 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.22 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
C11	0.7258 (3)	0.15606 (7)	−0.1940 (2)	0.0572 (4)
H11A	0.7728	0.1188	−0.1812	0.086*
H11B	0.8598	0.1769	−0.2113	0.086*
H11C	0.5775	0.1604	−0.2970	0.086*
N11	0.6762 (2)	0.17415 (4)	−0.03149 (16)	0.0437 (3)
C12	0.7738 (3)	0.22340 (5)	0.0666 (2)	0.0459 (3)
H12A	0.7215	0.2547	−0.0107	0.055*
H12B	0.9555	0.2227	0.1152	0.055*
C13	0.6576 (3)	0.22303 (5)	0.2162 (2)	0.0444 (3)
O13	0.6882 (2)	0.25506 (4)	0.33827 (17)	0.0623 (3)
N14	0.5068 (2)	0.17843 (4)	0.18824 (16)	0.0418 (3)
C15	0.5203 (2)	0.15060 (5)	0.04068 (18)	0.0390 (3)
N16	0.3960 (2)	0.10634 (5)	−0.01514 (19)	0.0489 (3)
H14	0.403 (3)	0.1680 (7)	0.255 (2)	0.056 (5)*
H15A	0.412 (3)	0.0883 (8)	−0.109 (3)	0.062 (5)*
H15B	0.296 (3)	0.0947 (7)	0.052 (2)	0.060 (5)*
O21	0.1034 (2)	0.07770 (4)	0.20235 (16)	0.0606 (3)
O22	0.1978 (2)	0.14924 (4)	0.37969 (15)	0.0555 (3)
C21	0.0833 (3)	0.10606 (5)	0.33167 (19)	0.0428 (3)
C22	−0.0877 (3)	0.08869 (6)	0.43292 (19)	0.0451 (3)
H22	−0.0881	0.1112	0.5284	0.054*
C23	−0.2406 (3)	0.04642 (6)	0.41017 (19)	0.0450 (3)
H23	−0.3351	0.0453	0.4887	0.054*
C24	−0.2848 (3)	0.00087 (5)	0.28009 (18)	0.0433 (3)
O23	−0.1681 (2)	−0.00175 (4)	0.16102 (15)	0.0601 (3)
O24	−0.4294 (2)	−0.03477 (4)	0.28982 (16)	0.0573 (3)
H23A	−0.056 (5)	0.0298 (11)	0.170 (3)	0.104 (8)*

	U11	U22	U33	U12	U13	U23
C11	0.0641 (10)	0.0581 (10)	0.0588 (9)	−0.0113 (7)	0.0330 (8)	−0.0079 (7)
N11	0.0461 (6)	0.0370 (6)	0.0523 (7)	−0.0057 (5)	0.0220 (5)	−0.0044 (5)
C12	0.0446 (7)	0.0338 (7)	0.0586 (8)	−0.0044 (5)	0.0157 (6)	−0.0021 (6)
C13	0.0428 (7)	0.0332 (7)	0.0550 (8)	0.0017 (5)	0.0126 (6)	−0.0044 (6)
O13	0.0661 (7)	0.0493 (7)	0.0743 (7)	−0.0085 (5)	0.0263 (6)	−0.0232 (6)
N14	0.0470 (6)	0.0343 (6)	0.0467 (6)	−0.0021 (5)	0.0188 (5)	−0.0025 (5)
C15	0.0404 (7)	0.0329 (7)	0.0439 (7)	0.0016 (5)	0.0139 (5)	0.0006 (5)
N16	0.0579 (8)	0.0412 (7)	0.0543 (7)	−0.0131 (5)	0.0274 (6)	−0.0098 (6)
O21	0.0827 (8)	0.0500 (6)	0.0664 (7)	−0.0229 (6)	0.0479 (6)	−0.0165 (5)
O22	0.0700 (7)	0.0399 (6)	0.0656 (7)	−0.0154 (5)	0.0345 (6)	−0.0100 (5)
C21	0.0505 (8)	0.0344 (7)	0.0458 (7)	−0.0009 (6)	0.0187 (6)	0.0002 (5)
C22	0.0579 (8)	0.0377 (7)	0.0452 (7)	−0.0016 (6)	0.0242 (6)	−0.0058 (6)
C23	0.0527 (8)	0.0413 (7)	0.0479 (7)	−0.0026 (6)	0.0255 (6)	−0.0015 (6)
C24	0.0495 (8)	0.0378 (7)	0.0455 (8)	−0.0041 (6)	0.0191 (6)	0.0000 (6)
O23	0.0839 (8)	0.0481 (6)	0.0638 (7)	−0.0241 (6)	0.0452 (6)	−0.0178 (5)
O24	0.0671 (7)	0.0485 (6)	0.0655 (7)	−0.0187 (5)	0.0340 (6)	−0.0107 (5)

C11—N11	1.450 (2)	C15—N16	1.3025 (18)
C11—H11A	0.9600	N16—H15A	0.89 (2)
C11—H11B	0.9600	N16—H15B	0.93 (2)
C11—H11C	0.9600	O21—C21	1.2630 (17)
N11—C15	1.3206 (18)	O22—C21	1.2471 (17)
N11—C12	1.4552 (17)	C21—C22	1.490 (2)
C12—C13	1.506 (2)	C22—C23	1.334 (2)
C12—H12A	0.9700	C22—H22	0.9300
C12—H12B	0.9700	C23—C24	1.4862 (19)
C13—O13	1.2090 (17)	C23—H23	0.9300
C13—N14	1.3719 (17)	C24—O24	1.2225 (17)
N14—C15	1.3631 (18)	C24—O23	1.2967 (17)
N14—H14	0.934 (19)	O23—H23A	1.00 (3)
N11—C11—H11A	109.5	C13—N14—H14	127.1 (11)
N11—C11—H11B	109.5	N16—C15—N11	126.35 (13)
H11A—C11—H11B	109.5	N16—C15—N14	122.80 (13)
N11—C11—H11C	109.5	N11—C15—N14	110.84 (12)
H11A—C11—H11C	109.5	C15—N16—H15A	121.2 (12)
H11B—C11—H11C	109.5	C15—N16—H15B	115.6 (11)
C15—N11—C11	124.88 (12)	H15A—N16—H15B	123.2 (16)
C15—N11—C12	109.99 (11)	O22—C21—O21	123.41 (13)
C11—N11—C12	124.93 (12)	O22—C21—C22	116.82 (12)
N11—C12—C13	102.44 (11)	O21—C21—C22	119.76 (12)
N11—C12—H12A	111.3	C23—C22—C21	131.07 (13)
C13—C12—H12A	111.3	C23—C22—H22	114.5
N11—C12—H12B	111.3	C21—C22—H22	114.5
C13—C12—H12B	111.3	C22—C23—C24	130.69 (13)
H12A—C12—H12B	109.2	C22—C23—H23	114.7
O13—C13—N14	125.67 (14)	C24—C23—H23	114.7
O13—C13—C12	127.94 (13)	O24—C24—O23	120.46 (13)
N14—C13—C12	106.40 (11)	O24—C24—C23	118.75 (12)
C15—N14—C13	110.25 (12)	O23—C24—C23	120.77 (12)
C15—N14—H14	122.6 (11)	C24—O23—H23A	111.2 (14)
C15—N11—C12—C13	2.95 (15)	C12—N11—C15—N14	−2.40 (16)
C11—N11—C12—C13	178.00 (14)	C13—N14—C15—N16	179.61 (13)
N11—C12—C13—O13	177.46 (14)	C13—N14—C15—N11	0.69 (16)
N11—C12—C13—N14	−2.45 (14)	O22—C21—C22—C23	177.12 (16)
O13—C13—N14—C15	−178.69 (14)	O21—C21—C22—C23	−1.9 (2)
C12—C13—N14—C15	1.22 (15)	C21—C22—C23—C24	2.8 (3)
C11—N11—C15—N16	3.7 (2)	C22—C23—C24—O24	177.17 (16)
C12—N11—C15—N16	178.73 (13)	C22—C23—C24—O23	−1.3 (2)
C11—N11—C15—N14	−177.45 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N14—H14···O22	0.93 (2)	1.79 (2)	2.725 (2)	178 (2)
N16—H15A···O24i	0.89 (2)	1.96 (2)	2.833 (2)	168 (2)
N16—H15B···O21	0.93 (2)	1.88 (2)	2.804 (2)	174 (2)
O23—H23A···O21	1.00 (3)	1.46 (3)	2.457 (2)	174 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N14—H14⋯O22	0.93 (2)	1.79 (2)	2.725 (2)	178 (2)
N16—H15A⋯O24i	0.89 (2)	1.96 (2)	2.833 (2)	168 (2)
N16—H15B⋯O21	0.93 (2)	1.88 (2)	2.804 (2)	174 (2)
O23—H23A⋯O21	1.00 (3)	1.46 (3)	2.457 (2)	174 (2)

Symmetry code: (i) .