Creatinium 4-methyl­benzene­sulfonate

Thayanithi, V.; Kumar, P.P.; Gunasekaran, B.

doi:10.1107/S2414314616016229

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161622

https://doi.org/10.1107/S2414314616016229

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Creatinium 4-methylbenzenesulfonate

V. Thayanithi,^a P. Praveen Kumar ^a ^* and B. Gunasekaran ^b ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, Tamil Nadu, India, and ^bDepartment of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist, Chennai 603 203 Tamil Nadu, India
^*Correspondence e-mail: ppkpresidency@gmail.com, phdguna@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 10 October 2016; accepted 12 October 2016; online 18 October 2016)

In the title molecular salt, C₄H₁₀N₃O₂⁺·C₇H₇O₃S⁻ (systematic name: {amino[(carboxymethyl)(methyl)amino]methylidene}azanium 4-methylbenzenesulfonate), the OH group of the carboxylic acid and central N atom of the cation are close to being eclipsed [N—C—C—O = 11.6 (3)°]. In the crystal, C—H⋯·O, O—H⋯O and N—H⋯O hydrogen bonds link the components into (001) sheets.

Keywords: crystal structure; creatine; methylbenzenesulfonate; hydrogen bonding.

CCDC reference: 1509564

Structure description

Creatine is extracted from several kinds of muscle and it is endogenously synthesized by the liver and pancreas in humans (Walker, 1979 ). As part of our studies of creatine chemistry, the synthesis and structure of the title molecular salt are now described.

The asymmetric unit comprises a protonated creatinium cation and deprotonated 4-methylbenzenesulfonate anion (Fig. 1). The geometric parameters of the component ions agree well with those reported for similar structures (Ali et al., 2012 ). In the anion, the O1—S1—C1—C2 torsion angle of 15.4 (2)° indicates that atom O1 lies close to the plane of the aromatic ring.

Figure 1
The molecular structure of the title compound, with 30% probability displacement ellipsoids for non-H atoms.

In the crystal, C—H⋯O, O—H⋯O and N—H⋯O hydrogen bonds (Fig. 2, Table 1) link the components into (001) sheets.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O2	0.97	2.45	3.297 (3)	146
O4—H4⋯O3ⁱ	0.82	1.82	2.630 (2)	167
N2—H2B⋯O5ⁱ	0.86	2.24	2.955 (2)	141
N1—H1A⋯O3ⁱⁱ	0.86	2.33	3.121 (3)	154
N2—H2A⋯O1ⁱⁱ	0.86	2.11	2.927 (2)	158
Symmetry codes: (i) -x+2, -y, -z; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 2
The packing, viewed along [100]. Hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

Creatine (0.01 mol) was dissolved in 20 ml of de-ionized water and p-toluenesulfonic acid monohydrate (0.01 mol) was added slowly. The solution was stirred for 4 h. The solution was filtered and colourless blocks were obtained from the mother liquor after seven days. Yield = 95%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₄H₁₀N₃O₂⁺·C₇H₇O₃S⁻
M_r	303.34
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	295
a, b, c (Å)	7.1432 (2), 13.3500 (5), 29.4794 (10)
V (Å³)	2811.21 (16)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.25
Crystal size (mm)	0.25 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.939, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	37602, 2469, 2118
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.108, 1.08
No. of reflections	2469
No. of parameters	185
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2008 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1509564

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016229/hb4086sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016229/hb4086Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616016229/hb4086Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

{Amino[(carboxymethyl)(methyl)amino]methylidene}azanium 4-methylbenzenesulfonate top

Crystal data top

C₄H₁₀N₃O₂⁺·C₇H₇O₃S⁻	F(000) = 1280
M_r = 303.34	D_x = 1.433 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2469 reflections
a = 7.1432 (2) Å	θ = 2.8–25.0°
b = 13.3500 (5) Å	µ = 0.25 mm⁻¹
c = 29.4794 (10) Å	T = 295 K
V = 2811.21 (16) Å³	Block, colourless
Z = 8	0.25 × 0.25 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	2469 independent reflections
Radiation source: fine-focus sealed tube	2118 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 0 pixels mm^-1	θ_max = 25.0°, θ_min = 2.8°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→15
T_min = 0.939, T_max = 0.951	l = −35→35
37602 measured reflections

Refinement top

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) = 0.108	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0471P)² + 2.2285P] where P = (F_o² + 2F_c²)/3
2469 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.82439 (7)	−0.10067 (4)	0.139590 (17)	0.03545 (19)
O1	0.7739 (3)	−0.20436 (14)	0.14653 (6)	0.0633 (6)
O2	1.0097 (2)	−0.08774 (13)	0.12117 (6)	0.0522 (5)
O3	0.6850 (3)	−0.05069 (16)	0.11132 (5)	0.0621 (6)
O4	1.2752 (3)	0.09972 (13)	−0.02547 (5)	0.0562 (5)
H4	1.2775	0.0770	−0.0513	0.084*
O5	1.2004 (3)	−0.05660 (12)	−0.00736 (6)	0.0524 (5)
N1	1.1562 (2)	0.30601 (13)	0.09852 (6)	0.0376 (4)
H1A	1.0666	0.3387	0.1112	0.045*
H1B	1.2672	0.3309	0.0979	0.045*
N2	0.9508 (2)	0.18133 (13)	0.08163 (6)	0.0394 (4)
H2A	0.8631	0.2151	0.0945	0.047*
H2B	0.9266	0.1239	0.0698	0.047*
N3	1.2622 (2)	0.16613 (12)	0.06048 (5)	0.0312 (4)
C1	0.8211 (3)	−0.04052 (16)	0.19269 (6)	0.0311 (4)
C2	0.8196 (4)	−0.0955 (2)	0.23192 (8)	0.0502 (6)
H2	0.8164	−0.1651	0.2306	0.060*
C3	0.8228 (4)	−0.0475 (2)	0.27340 (8)	0.0571 (7)
H3	0.8204	−0.0855	0.2998	0.069*
C4	0.8294 (3)	0.0539 (2)	0.27651 (8)	0.0515 (7)
C5	0.8338 (4)	0.1082 (2)	0.23673 (9)	0.0619 (8)
H5	0.8406	0.1777	0.2382	0.074*
C6	0.8284 (4)	0.06204 (18)	0.19472 (8)	0.0470 (6)
H6	0.8296	0.1000	0.1683	0.056*
C7	0.8319 (5)	0.1050 (3)	0.32238 (10)	0.0872 (12)
H7A	0.7168	0.0914	0.3380	0.131*
H7B	0.8454	0.1760	0.3183	0.131*
H7C	0.9351	0.0801	0.3399	0.131*
C8	1.2364 (3)	0.02815 (15)	0.00308 (7)	0.0327 (5)
C9	1.2474 (3)	0.05934 (15)	0.05220 (6)	0.0335 (5)
H9A	1.1367	0.0347	0.0676	0.040*
H9B	1.3549	0.0267	0.0658	0.040*
C10	1.1233 (3)	0.21775 (14)	0.08008 (6)	0.0289 (4)
C11	1.4454 (3)	0.21214 (19)	0.05409 (9)	0.0492 (6)
H11A	1.4299	0.2796	0.0434	0.074*
H11B	1.5155	0.1744	0.0322	0.074*
H11C	1.5116	0.2128	0.0824	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0350 (3)	0.0435 (3)	0.0279 (3)	−0.0040 (2)	0.0028 (2)	−0.0102 (2)
O1	0.0878 (14)	0.0527 (11)	0.0493 (10)	−0.0304 (10)	0.0037 (10)	−0.0147 (8)
O2	0.0440 (9)	0.0592 (10)	0.0534 (10)	−0.0044 (8)	0.0176 (8)	−0.0220 (8)
O3	0.0640 (12)	0.0919 (14)	0.0302 (8)	0.0234 (10)	−0.0108 (8)	−0.0151 (9)
O4	0.0903 (14)	0.0509 (10)	0.0274 (8)	−0.0180 (9)	0.0005 (9)	−0.0052 (7)
O5	0.0748 (12)	0.0355 (9)	0.0468 (9)	−0.0019 (8)	−0.0025 (8)	−0.0156 (7)
N1	0.0326 (9)	0.0343 (9)	0.0459 (10)	−0.0004 (8)	0.0039 (8)	−0.0138 (8)
N2	0.0333 (9)	0.0377 (10)	0.0470 (11)	−0.0043 (8)	0.0055 (8)	−0.0144 (8)
N3	0.0320 (9)	0.0312 (9)	0.0302 (9)	−0.0025 (7)	0.0020 (7)	−0.0091 (7)
C1	0.0266 (10)	0.0420 (11)	0.0248 (10)	−0.0016 (9)	0.0004 (8)	−0.0050 (8)
C2	0.0639 (16)	0.0525 (14)	0.0342 (12)	−0.0156 (12)	−0.0017 (11)	0.0028 (10)
C3	0.0621 (16)	0.083 (2)	0.0262 (12)	−0.0152 (15)	0.0002 (11)	0.0033 (12)
C4	0.0391 (13)	0.084 (2)	0.0317 (12)	0.0040 (13)	0.0005 (10)	−0.0203 (12)
C5	0.080 (2)	0.0487 (15)	0.0572 (17)	0.0140 (14)	−0.0059 (15)	−0.0211 (12)
C6	0.0644 (16)	0.0452 (13)	0.0315 (11)	0.0073 (12)	−0.0013 (11)	−0.0031 (10)
C7	0.076 (2)	0.137 (3)	0.0486 (17)	0.009 (2)	−0.0010 (15)	−0.0472 (19)
C8	0.0323 (10)	0.0333 (11)	0.0325 (10)	0.0029 (9)	−0.0012 (9)	−0.0089 (9)
C9	0.0416 (11)	0.0303 (10)	0.0286 (10)	0.0041 (9)	0.0002 (9)	−0.0041 (8)
C10	0.0340 (10)	0.0301 (10)	0.0225 (9)	0.0004 (8)	−0.0023 (8)	−0.0026 (8)
C11	0.0333 (12)	0.0552 (14)	0.0592 (15)	−0.0067 (11)	0.0086 (11)	−0.0237 (12)

Geometric parameters (Å, º) top

S1—O2	1.4410 (17)	C1—C6	1.371 (3)
S1—O2	1.4410 (17)	C2—C3	1.381 (3)
S1—O1	1.4451 (19)	C2—H2	0.9300
S1—O3	1.4599 (18)	C3—C4	1.357 (4)
S1—C1	1.7596 (19)	C3—H3	0.9300
O2—O2	0.000 (4)	C4—C5	1.379 (4)
O4—C8	1.303 (3)	C4—C7	1.515 (3)
O4—H4	0.8200	C5—C6	1.384 (3)
O5—C8	1.200 (2)	C5—H5	0.9300
N1—C10	1.319 (2)	C6—H6	0.9300
N1—H1A	0.8600	C7—H7A	0.9600
N1—H1B	0.8600	C7—H7B	0.9600
N2—C10	1.325 (3)	C7—H7C	0.9600
N2—H2A	0.8600	C8—C9	1.509 (3)
N2—H2B	0.8600	C9—H9A	0.9700
N3—C10	1.339 (3)	C9—H9B	0.9700
N3—C9	1.450 (3)	C11—H11A	0.9600
N3—C11	1.458 (3)	C11—H11B	0.9600
C1—C2	1.370 (3)	C11—H11C	0.9600

O2—S1—O2	0.00 (13)	C5—C4—C7	121.4 (3)
O2—S1—O1	113.42 (12)	C4—C5—C6	121.7 (3)
O2—S1—O1	113.42 (12)	C4—C5—H5	119.1
O2—S1—O3	110.89 (11)	C6—C5—H5	119.1
O2—S1—O3	110.89 (11)	C1—C6—C5	119.0 (2)
O1—S1—O3	110.38 (12)	C1—C6—H6	120.5
O2—S1—C1	107.03 (9)	C5—C6—H6	120.5
O2—S1—C1	107.03 (9)	C4—C7—H7A	109.5
O1—S1—C1	107.93 (10)	C4—C7—H7B	109.5
O3—S1—C1	106.86 (10)	H7A—C7—H7B	109.5
O2—O2—S1	0 (10)	C4—C7—H7C	109.5
C8—O4—H4	109.5	H7A—C7—H7C	109.5
C10—N1—H1A	120.0	H7B—C7—H7C	109.5
C10—N1—H1B	120.0	O5—C8—O4	124.82 (19)
H1A—N1—H1B	120.0	O5—C8—C9	121.16 (19)
C10—N2—H2A	120.0	O4—C8—C9	113.98 (17)
C10—N2—H2B	120.0	N3—C9—C8	115.89 (17)
H2A—N2—H2B	120.0	N3—C9—H9A	108.3
C10—N3—C9	121.62 (17)	C8—C9—H9A	108.3
C10—N3—C11	120.28 (17)	N3—C9—H9B	108.3
C9—N3—C11	117.26 (17)	C8—C9—H9B	108.3
C2—C1—C6	119.9 (2)	H9A—C9—H9B	107.4
C2—C1—S1	120.43 (18)	N1—C10—N2	118.62 (18)
C6—C1—S1	119.60 (16)	N1—C10—N3	120.38 (18)
C1—C2—C3	119.9 (2)	N2—C10—N3	121.00 (17)
C1—C2—H2	120.0	N3—C11—H11A	109.5
C3—C2—H2	120.0	N3—C11—H11B	109.5
C4—C3—C2	121.6 (2)	H11A—C11—H11B	109.5
C4—C3—H3	119.2	N3—C11—H11C	109.5
C2—C3—H3	119.2	H11A—C11—H11C	109.5
C3—C4—C5	117.9 (2)	H11B—C11—H11C	109.5
C3—C4—C7	120.7 (3)

O1—S1—O2—O2	0.0 (2)	C2—C3—C4—C7	179.7 (3)
O3—S1—O2—O2	0.0 (2)	C3—C4—C5—C6	1.2 (4)
C1—S1—O2—O2	0.0 (2)	C7—C4—C5—C6	−178.9 (3)
O2—S1—C1—C2	−107.0 (2)	C2—C1—C6—C5	−0.1 (4)
O2—S1—C1—C2	−107.0 (2)	S1—C1—C6—C5	−177.2 (2)
O1—S1—C1—C2	15.4 (2)	C4—C5—C6—C1	−1.0 (4)
O3—S1—C1—C2	134.1 (2)	C10—N3—C9—C8	112.1 (2)
O2—S1—C1—C6	70.1 (2)	C11—N3—C9—C8	−78.4 (2)
O2—S1—C1—C6	70.1 (2)	O5—C8—C9—N3	−170.6 (2)
O1—S1—C1—C6	−167.45 (19)	O4—C8—C9—N3	11.6 (3)
O3—S1—C1—C6	−48.7 (2)	C9—N3—C10—N1	161.24 (18)
C6—C1—C2—C3	0.9 (4)	C11—N3—C10—N1	−8.0 (3)
S1—C1—C2—C3	178.0 (2)	C9—N3—C10—N2	−18.3 (3)
C1—C2—C3—C4	−0.7 (4)	C11—N3—C10—N2	172.5 (2)
C2—C3—C4—C5	−0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O2	0.97	2.45	3.297 (3)	146
O4—H4···O3ⁱ	0.82	1.82	2.630 (2)	167
N2—H2B···O5ⁱ	0.86	2.24	2.955 (2)	141
N1—H1A···O3ⁱⁱ	0.86	2.33	3.121 (3)	154
N2—H2A···O1ⁱⁱ	0.86	2.11	2.927 (2)	158

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+3/2, y+1/2, z.

Acknowledgements

The authors acknowledge the SAIF, IIT, Madras, for the data collection.

References

Ali, A. J., Athimoolam, S. & Bahadur, S. A. (2012). Acta Cryst. E68, o416. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Walker, J. B. (1979). Adv. Enzymol. Relat. Areas Mol. Med. 50, 177–242. CAS Google Scholar

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