organic compounds
Creatinium hydrogen oxalate
aDepartment of Science and Humanities, National College of Engineering, Maruthakulam, Tirunelveli 627 151, India, bDepartment of Physics, University College of Engineering Nagercoil, Anna University of Technology Tirunelveli, Nagercoil 629 004, India, and cDepartment of Physics, Kalasalingam University, Anand Nagar, Krishnan Koil 626 190, India
*Correspondence e-mail: athi81s@yahoo.co.in
The 4H10N3O2+·C2HO4−, 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 leading to an R22(14) ring motif. This leads to a cationic molecular aggregation at x = 0 or 1 and an anionic molecular aggregation at x = 1/2.
of the title compound, CRelated 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
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Data collection
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Refinement
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Data collection: SMART (Bruker, 2001); cell 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.
Supporting information
10.1107/S1600536812000852/hg5159sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812000852/hg5159Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812000852/hg5159Isup3.cml
The title compound was crystallized from an aqueous mixture containing creatine (0.13g) and oxalic acid (0.09g) in the stoichiometric ratio of 1:1 (20 ml of water) at room temperature by slow evaporation technique.
All the H atoms except the atoms involved in hydrogen bonds were positioned geometrically and refined using a riding model, with C—H = 0.96 (–CH3) and 0.97 Å (–CH2) and Uiso(H) = 1.2–1.5 Ueq (parent atom). H atoms involved in hydrogen bonds were located from differential Fourier maps and refined isotropically.
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008); program(s) used to refine structure: SHELXTL/PC (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound (I) with the numbering scheme for the atoms and 50% probability displacement ellipsoids. H bonds are drawn as dashed lines. | |
Fig. 2. Packing diagram of the molecules viewed down the b-axis. H atoms not involved in the H-bonds (dashed lines) are omitted for clarity. |
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 monochromator | 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) |
C4H10N3O2+·C2HO4− | V = 927.98 (9) Å3 |
Mr = 221.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.1545 (4) Å | µ = 0.14 mm−1 |
b = 12.3681 (7) Å | T = 293 K |
c = 10.5151 (6) Å | 0.24 × 0.22 × 0.18 mm |
β = 94.18 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 1587 reflections with I > 2σ(I) |
8631 measured reflections | Rint = 0.018 |
1641 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 1 restraint |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.25 e Å−3 |
1641 reflections | Δρmin = −0.23 e Å−3 |
162 parameters |
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) |
Symmetry codes: (i) −x+2, −y+2, −z; (ii) x+1, −y+3/2, z−1/2; (iii) −x+2, y−1/2, −z+1/2; (iv) x, y, z−1; (v) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C4H10N3O2+·C2HO4− |
Mr | 221.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.1545 (4), 12.3681 (7), 10.5151 (6) |
β (°) | 94.18 (1) |
V (Å3) | 927.98 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.24 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8631, 1641, 1587 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.102, 1.08 |
No. of reflections | 1641 |
No. of parameters | 162 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.23 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL/PC (Sheldrick, 2008), PLATON (Spek, 2009).
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) −x+2, −y+2, −z; (ii) x+1, −y+3/2, z−1/2; (iii) −x+2, y−1/2, −z+1/2; (iv) x, y, z−1; (v) x, −y+3/2, z−1/2. |
Acknowledgements
AJA and SAB sincerely thank the Vice Chancellor and Management of the Kalasalingam University, Anand Nagar, Krishnan Koil, for their support and encouragement. AJA thanks the Principal and Management of the National College of Engineering for their support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Creatine is a nitrogenous organic acid that occurs naturally in vertebrates and helps to supply energy to all cells in the body, primarily muscle (Cannan, 1928; Greenhaff et al.,1993)). We are interested in the specificity of recognition between organic acids and cretine and creatinine molecules and have reported a number of creatinine related structures (Ali et al., 2011a,b; Bahadur, Kannan et al., 2007; Bahadur, Sivapragasam et al., 2007; Bahadur, Rajalakshmi et al., 2007).
The asymmetric part of the title compound, (I), contains one creatinium cation and one hydrogen oxalate anion (Fig. 1). The protonation of the N site of the cation is evident from C—N bond distances. The deprotonation on the one of the –COOH groups of the oxalic acid is confirmed from that –COO- bond geometry. The planes of –COOH and –COO- groups are twisted out from each other with an angle of 25.1 (2)°. This twisting of planes may be caused due to the hydrogen bonding association and molecular aggregation. The crystal structure and the molecular aggregations are stabilized through intricate three dimensional hydrogen bonding network (Fig. 2; Table 1). All the N and O atoms of the cation and anion participate in the hydrogen bonding interactions.
Hydrogen oxalate anions are connected themselves through a O—H···O hydrogen bond leading to a linear chain C(5) motif extending along c axis of the unit cell (Bernstein et al., 1995). Creatinium cations are dimerized around inversion centres of the unit cell, especially at the corners of the unit cell and making a ring R22(4) motif through N2—H1N···O1 (2 - x, 2 - y, -z) hydrogen bond. Also, these cationic dimers are connected themselves through another N—H···O hydrogen bond leading to a zigzag chain C(7) motif extending along b axis of the unit cell [N3—H3N···O1(-x + 2, y - 1/2, -z + 1/2)]. These interconnected cationic dimers are connected with oxalate anion leading to a zigzag chain C22(11) motif extending along ac-plane of the unit cell through N2—H2N···O11(1 + x, 3/2 - y, -1/2 + z) and O2—H2···O12(x, y, -1 + z). Another pair of N—H···O and O—H···O hydrogen bonds between cation and anion leading to a linear chain C22(12) motifs extending along c axis of the unit cell [N3—H3N···O14 and O2—H2···O12(x, y, -1 + z)]. Dimerization of cations and anionic chain motifs lead to cationic molecular aggregation at x=0 or 1 and molecular aggregation of anions at x=1/2. These cationic and anionic aggregations are connected further through other N—H···O hydrogen bonds leading to a three dimensional hydrogen bonding network.