Synthesis, crystal structure determination and Hirshfeld surface analysis of three new salt forms of creatinine with hydro­bromic acid, 3-amino­benzoic acid and 3,5-di­nitro­benzoic acid

Jeyaraman Selvaraj, N.; Sathya, U.; Gomathi, S.; Jegan Jennifer, S.; Mathivathanan, L.; Abdul Razak, I.

doi:10.1107/S2053229622006684

Synthesis, crystal structure determination and Hirshfeld surface analysis of three new salt forms of creatinine with hydrobromic acid, 3-aminobenzoic acid and 3,5-dinitrobenzoic acid

N. Jeyaraman Selvaraj, U. Sathya, S. Gomathi, S. Jegan Jennifer, L. Mathivathanan and I. Abdul Razak

Creatinine, a biologically important compound, is used to analyze kidney function and kidney diseases in the human body. The salt form of creatinine is used in the formation of drug materials like anti-HIV, antifungal, antiprotozoal, antiviral and antitumour compounds. Here we report the solid-state structures of three new crystalline salts, namely, creatininium (2-amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium) bromide, C₄H₈N₃O⁺·Br⁻, (I), creatininium 3-aminobenzoate, C₄H₈N₃O⁺·C₇H₆NO₂⁻, (II), and creatininium 3,5-dinitrobenzoate, C₄H₈N₃O⁺·C₇H₃N₂O₆⁻, (III). These salts have been synthesized and characterized by single-crystal X-ray diffraction and Hirshfeld surface analysis. The structural chemistry of salts (I)–(III) and their crystal packing are discussed in detail. The primary interaction between the creatinine cation and the acid anion in the three salts is N—H

Br/O hydrogen bonds. In salt (I), the creatinine cation and bromide anion are connected through a pair of N—H

Br hydrogen bonds forming R₄²(8) and R₄²(12) ring motifs. In salts (II) and (III), the creatinine cation interacts with the corresponding anion via a pair of N—H

O hydrogen bonds. The crystal structure is further stabilized by C—H

O and O—H

O hydrogen bonds with the ring motifs R₂²(8), R₂¹(7) and R₂¹(6). Furthermore, the crystal structures are stabilized by π–π, C—H

π, C—O

π and N—O

π stacking interactions. The contributions made by each hydrogen bond in maintaining the crystal structure stability has been quantified by Hirshfeld surface analysis.

Keywords: creatinine; intermolecular interactions; crystal structure; comparative analysis; Hirshfeld surface analysis; two-dimensional fingerprint plot; salt; bromide; benzoate.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229622006684/dg3030sup1.cif Contains datablocks I, II, III, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229622006684/dg3030Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229622006684/dg3030IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229622006684/dg3030IIIsup4.hkl Contains datablock III
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229622006684/dg3030Isup5.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229622006684/dg3030IIsup6.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229622006684/dg3030IIIsup7.cml Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229622006684/dg3030sup8.pdf Additional schemes

CCDC references: 2182644; 2182643; 2182642

Computing details top

For all structures, data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020), Mercury (Macrae et al., 2020) and POVRay (Cason, 2004); software used to prepare material for publication: PLATON (Spek, 2020) and publCIF (Westrip, 2010).

2-Amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium bromide (I) top

Crystal data top

C₄H₈N₃O⁺·Br⁻	F(000) = 384
M_r = 194.04	D_x = 1.786 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.7252 (4) Å	Cell parameters from 1473 reflections
b = 7.7772 (4) Å	θ = 2.8–26.4°
c = 10.7406 (5) Å	µ = 5.62 mm⁻¹
β = 97.969 (1)°	T = 293 K
V = 721.79 (6) Å³	Plate, colourless
Z = 4	0.25 × 0.25 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1258 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.029
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 26.4°, θ_min = 2.8°
T_min = 0.626, T_max = 0.936	h = −10→10
8609 measured reflections	k = −9→9
1473 independent reflections	l = −13→13

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0212P)² + 0.322P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.049	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.24 e Å⁻³
1473 reflections	Δρ_min = −0.30 e Å⁻³
88 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0158 (10)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Br1	0.13199 (2)	0.72299 (3)	0.04499 (2)	0.04228 (11)
N3	0.48199 (19)	0.1452 (2)	0.15946 (17)	0.0352 (4)
N1	0.3696 (2)	0.3966 (3)	0.1251 (2)	0.0431 (5)
O5	0.5736 (2)	0.5805 (2)	0.1800 (2)	0.0783 (7)
N2	0.2176 (2)	0.1490 (3)	0.0829 (2)	0.0505 (5)
H2B	0.211603	0.038614	0.081112	0.061*
H2A	0.136571	0.210092	0.059521	0.061*
C2	0.3502 (3)	0.2241 (3)	0.1214 (2)	0.0354 (5)
C4	0.6017 (2)	0.2711 (3)	0.2003 (2)	0.0411 (5)
H4A	0.689357	0.258356	0.154495	0.049*
H4B	0.637259	0.261043	0.289679	0.049*
C3	0.5049 (3)	−0.0373 (3)	0.1823 (3)	0.0479 (6)
H3B	0.522699	−0.058188	0.271244	0.072*
H3C	0.592789	−0.075710	0.145111	0.072*
H3A	0.414424	−0.098978	0.145721	0.072*
C5	0.5206 (3)	0.4386 (3)	0.1701 (2)	0.0467 (6)
H1	0.306 (3)	0.472 (3)	0.101 (2)	0.044 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03312 (14)	0.03972 (16)	0.05203 (17)	0.00201 (9)	−0.00112 (9)	0.00022 (10)
N3	0.0294 (9)	0.0284 (9)	0.0464 (11)	0.0023 (7)	0.0004 (8)	0.0004 (8)
N1	0.0422 (11)	0.0305 (11)	0.0553 (13)	0.0076 (8)	0.0015 (9)	0.0052 (9)
O5	0.0697 (13)	0.0376 (11)	0.126 (2)	−0.0135 (9)	0.0097 (13)	−0.0058 (11)
N2	0.0332 (10)	0.0411 (11)	0.0718 (14)	0.0030 (8)	−0.0117 (10)	−0.0003 (10)
C2	0.0347 (11)	0.0352 (11)	0.0355 (11)	0.0053 (9)	0.0025 (9)	0.0009 (9)
C4	0.0291 (11)	0.0413 (13)	0.0528 (14)	−0.0017 (9)	0.0054 (10)	−0.0028 (10)
C3	0.0416 (12)	0.0322 (13)	0.0670 (17)	0.0075 (9)	−0.0021 (11)	0.0014 (11)
C5	0.0473 (13)	0.0370 (14)	0.0568 (16)	−0.0043 (10)	0.0111 (11)	−0.0019 (11)

Geometric parameters (Å, º) top

N3—C2	1.317 (3)	N2—H2B	0.8600
N3—C3	1.450 (3)	N2—H2A	0.8600
N3—C4	1.455 (3)	C4—C5	1.496 (3)
N1—C2	1.352 (3)	C4—H4A	0.9700
N1—C5	1.379 (3)	C4—H4B	0.9700
N1—H1	0.83 (2)	C3—H3B	0.9600
O5—C5	1.195 (3)	C3—H3C	0.9600
N2—C2	1.311 (3)	C3—H3A	0.9600

C2—N3—C3	127.06 (19)	C5—C4—H4A	111.2
C2—N3—C4	109.85 (18)	N3—C4—H4B	111.2
C3—N3—C4	122.12 (17)	C5—C4—H4B	111.2
C2—N1—C5	110.81 (19)	H4A—C4—H4B	109.1
C2—N1—H1	128.4 (18)	N3—C3—H3B	109.5
C5—N1—H1	120.7 (18)	N3—C3—H3C	109.5
C2—N2—H2B	120.0	H3B—C3—H3C	109.5
C2—N2—H2A	120.0	N3—C3—H3A	109.5
H2B—N2—H2A	120.0	H3B—C3—H3A	109.5
N2—C2—N3	125.8 (2)	H3C—C3—H3A	109.5
N2—C2—N1	123.5 (2)	O5—C5—N1	126.1 (2)
N3—C2—N1	110.67 (19)	O5—C5—C4	128.2 (2)
N3—C4—C5	102.86 (17)	N1—C5—C4	105.64 (19)
N3—C4—H4A	111.2

C3—N3—C2—N2	−8.5 (4)	C2—N3—C4—C5	−4.3 (2)
C4—N3—C2—N2	−177.3 (2)	C3—N3—C4—C5	−173.8 (2)
C3—N3—C2—N1	172.5 (2)	C2—N1—C5—O5	177.3 (3)
C4—N3—C2—N1	3.7 (3)	C2—N1—C5—C4	−1.5 (3)
C5—N1—C2—N2	179.6 (2)	N3—C4—C5—O5	−175.4 (3)
C5—N1—C2—N3	−1.3 (3)	N3—C4—C5—N1	3.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.82	2.50	3.315 (2)	173.4 (19)
N2—H2B···Br1ⁱ	0.86	2.57	3.408 (2)	167
N2—H2A···Br1ⁱⁱ	0.86	2.51	3.3197 (19)	158
C3—H3A···Br1ⁱ	0.96	2.90	3.861 (3)	177
C4—H4A···Br1ⁱⁱⁱ	0.97	2.82	3.747 (2)	160

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

2-Amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium 3-aminobenzoate (II) top

Crystal data top

C₇H₆NO₂⁺·C₄H₈N₃O⁻	F(000) = 264
M_r = 250.26	D_x = 1.403 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.9887 (4) Å	Cell parameters from 3487 reflections
b = 6.6098 (3) Å	θ = 1.8–30.2°
c = 11.4753 (6) Å	µ = 0.11 mm⁻¹
β = 102.080 (2)°	T = 296 K
V = 592.52 (5) Å³	Plate, colourless
Z = 2	0.58 × 0.31 × 0.29 mm

Data collection top

Bruker APEXII CCD diffractometer	2802 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.029
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 30.2°, θ_min = 1.8°
T_min = 0.526, T_max = 0.745	h = −11→11
12356 measured reflections	k = −9→9
3487 independent reflections	l = −16→16

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0741P)² + 0.0054P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.126	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.21 e Å⁻³
3487 reflections	Δρ_min = −0.23 e Å⁻³
168 parameters	Absolute structure: Flack x determined using 1054 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.3 (5)

Special details top

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

	x	y	z	U_iso*/U_eq
O2	1.1891 (2)	0.7538 (3)	0.10917 (14)	0.0422 (4)
O1	1.2878 (2)	0.7301 (3)	0.30461 (14)	0.0443 (4)
O5	1.2219 (2)	0.2816 (3)	0.50838 (15)	0.0510 (5)
N1	1.1233 (3)	0.3877 (3)	0.31563 (17)	0.0364 (4)
N2	0.9891 (3)	0.4032 (3)	0.11484 (17)	0.0411 (5)
H2A	0.922002	0.350684	0.053936	0.062*
H2B	1.037368	0.517785	0.108395	0.062*
N3	0.9538 (2)	0.1330 (3)	0.24130 (17)	0.0371 (4)
N8	1.6643 (3)	1.3369 (4)	0.4223 (2)	0.0498 (6)
H8A	1.719074	1.449209	0.423439	0.075*
H8B	1.673196	1.266985	0.486449	0.075*
C6	1.3765 (3)	1.0129 (3)	0.20618 (19)	0.0305 (4)
C7	1.4772 (3)	1.0823 (4)	0.31201 (19)	0.0333 (5)
H7	1.488580	1.004053	0.380574	0.040*
C2	1.0178 (3)	0.3089 (3)	0.21715 (18)	0.0319 (5)
C10	1.4491 (3)	1.3093 (4)	0.1069 (2)	0.0437 (6)
H10	1.440669	1.385072	0.037659	0.052*
C3	0.8375 (3)	0.0046 (4)	0.1598 (2)	0.0437 (6)
H3A	0.746392	−0.038874	0.196803	0.066*
H3B	0.898264	−0.111474	0.140027	0.066*
H3C	0.790681	0.078849	0.088556	0.066*
C8	1.5621 (3)	1.2689 (4)	0.31709 (19)	0.0347 (5)
C5	1.1348 (3)	0.2577 (4)	0.4100 (2)	0.0373 (5)
C9	1.5462 (3)	1.3803 (4)	0.2121 (2)	0.0413 (6)
H9	1.601932	1.504059	0.213370	0.050*
C4	1.0170 (3)	0.0832 (4)	0.3665 (2)	0.0394 (5)
H4A	1.078528	−0.044220	0.375370	0.047*
H4B	0.924136	0.075954	0.408945	0.047*
C11	1.3629 (3)	1.1249 (4)	0.1027 (2)	0.0385 (5)
H11	1.297219	1.077792	0.031180	0.046*
C12	1.2785 (3)	0.8179 (3)	0.20560 (18)	0.0326 (5)
H1	1.188 (5)	0.505 (8)	0.314 (3)	0.080 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0490 (9)	0.0366 (8)	0.0361 (8)	−0.0059 (8)	−0.0022 (7)	−0.0018 (7)
O1	0.0590 (11)	0.0374 (9)	0.0340 (8)	−0.0112 (8)	0.0038 (7)	0.0003 (7)
O5	0.0641 (11)	0.0475 (11)	0.0357 (9)	0.0069 (10)	−0.0026 (8)	−0.0004 (8)
N1	0.0396 (11)	0.0331 (10)	0.0338 (10)	0.0006 (8)	0.0014 (8)	0.0009 (8)
N2	0.0450 (11)	0.0404 (11)	0.0339 (10)	−0.0033 (9)	−0.0008 (8)	0.0034 (9)
N3	0.0376 (10)	0.0340 (10)	0.0379 (9)	−0.0028 (8)	0.0035 (8)	0.0009 (8)
N8	0.0569 (13)	0.0476 (12)	0.0408 (11)	−0.0137 (11)	0.0006 (9)	−0.0083 (10)
C6	0.0296 (10)	0.0292 (10)	0.0327 (10)	0.0023 (8)	0.0063 (8)	−0.0010 (8)
C7	0.0362 (11)	0.0323 (11)	0.0315 (10)	0.0020 (8)	0.0071 (8)	−0.0006 (9)
C2	0.0300 (10)	0.0316 (11)	0.0331 (10)	0.0036 (8)	0.0045 (8)	−0.0014 (8)
C10	0.0430 (13)	0.0451 (14)	0.0408 (13)	−0.0015 (11)	0.0039 (10)	0.0132 (11)
C3	0.0370 (12)	0.0431 (12)	0.0499 (14)	−0.0057 (11)	0.0066 (10)	−0.0110 (12)
C8	0.0324 (11)	0.0327 (11)	0.0390 (11)	−0.0003 (9)	0.0076 (9)	−0.0061 (9)
C5	0.0437 (12)	0.0342 (11)	0.0330 (11)	0.0061 (10)	0.0057 (9)	−0.0009 (9)
C9	0.0407 (13)	0.0318 (12)	0.0507 (14)	−0.0032 (10)	0.0080 (11)	0.0028 (11)
C4	0.0463 (13)	0.0346 (11)	0.0376 (11)	0.0011 (10)	0.0093 (10)	0.0044 (10)
C11	0.0335 (11)	0.0437 (13)	0.0360 (11)	0.0000 (10)	0.0020 (9)	0.0030 (10)
C12	0.0336 (11)	0.0305 (10)	0.0326 (10)	0.0016 (8)	0.0046 (8)	−0.0040 (9)

Geometric parameters (Å, º) top

O2—C12	1.259 (3)	C6—C7	1.387 (3)
O1—C12	1.264 (3)	C6—C12	1.507 (3)
O5—C5	1.206 (3)	C7—C8	1.402 (3)
N1—C2	1.364 (3)	C7—H7	0.9300
N1—C5	1.370 (3)	C10—C9	1.374 (3)
N1—H1	0.93 (5)	C10—C11	1.396 (4)
N2—C2	1.306 (3)	C10—H10	0.9300
N2—H2A	0.8600	C3—H3A	0.9600
N2—H2B	0.8600	C3—H3B	0.9600
N3—C2	1.323 (3)	C3—H3C	0.9600
N3—C3	1.447 (3)	C8—C9	1.395 (3)
N3—C4	1.457 (3)	C5—C4	1.506 (4)
N8—C8	1.383 (3)	C9—H9	0.9300
N8—H8A	0.8600	C4—H4A	0.9700
N8—H8B	0.8600	C4—H4B	0.9700
C6—C11	1.385 (3)	C11—H11	0.9300

C2—N1—C5	110.0 (2)	H3A—C3—H3B	109.5
C2—N1—H1	123 (2)	N3—C3—H3C	109.5
C5—N1—H1	126 (2)	H3A—C3—H3C	109.5
C2—N2—H2A	120.0	H3B—C3—H3C	109.5
C2—N2—H2B	120.0	N8—C8—C9	120.8 (2)
H2A—N2—H2B	120.0	N8—C8—C7	121.0 (2)
C2—N3—C3	127.2 (2)	C9—C8—C7	118.2 (2)
C2—N3—C4	109.61 (19)	O5—C5—N1	126.0 (2)
C3—N3—C4	123.2 (2)	O5—C5—C4	127.4 (2)
C8—N8—H8A	120.0	N1—C5—C4	106.55 (19)
C8—N8—H8B	120.0	C10—C9—C8	120.7 (2)
H8A—N8—H8B	120.0	C10—C9—H9	119.6
C11—C6—C7	120.1 (2)	C8—C9—H9	119.6
C11—C6—C12	120.4 (2)	N3—C4—C5	102.54 (19)
C7—C6—C12	119.49 (19)	N3—C4—H4A	111.3
C6—C7—C8	120.9 (2)	C5—C4—H4A	111.3
C6—C7—H7	119.5	N3—C4—H4B	111.3
C8—C7—H7	119.5	C5—C4—H4B	111.3
N2—C2—N3	127.2 (2)	H4A—C4—H4B	109.2
N2—C2—N1	121.6 (2)	C6—C11—C10	119.2 (2)
N3—C2—N1	111.17 (19)	C6—C11—H11	120.4
C9—C10—C11	120.9 (2)	C10—C11—H11	120.4
C9—C10—H10	119.6	O2—C12—O1	123.4 (2)
C11—C10—H10	119.6	O2—C12—C6	119.4 (2)
N3—C3—H3A	109.5	O1—C12—C6	117.14 (18)
N3—C3—H3B	109.5

C11—C6—C7—C8	2.1 (3)	N8—C8—C9—C10	177.8 (2)
C12—C6—C7—C8	−176.24 (19)	C7—C8—C9—C10	0.4 (3)
C3—N3—C2—N2	0.1 (4)	C2—N3—C4—C5	−2.1 (2)
C4—N3—C2—N2	−179.4 (2)	C3—N3—C4—C5	178.4 (2)
C3—N3—C2—N1	−180.0 (2)	O5—C5—C4—N3	−177.7 (2)
C4—N3—C2—N1	0.5 (3)	N1—C5—C4—N3	2.9 (2)
C5—N1—C2—N2	−178.5 (2)	C7—C6—C11—C10	−1.1 (3)
C5—N1—C2—N3	1.5 (3)	C12—C6—C11—C10	177.2 (2)
C6—C7—C8—N8	−179.1 (2)	C9—C10—C11—C6	−0.1 (4)
C6—C7—C8—C9	−1.7 (3)	C11—C6—C12—O2	2.6 (3)
C2—N1—C5—O5	177.8 (2)	C7—C6—C12—O2	−179.0 (2)
C2—N1—C5—C4	−2.8 (2)	C11—C6—C12—O1	−175.5 (2)
C11—C10—C9—C8	0.5 (4)	C7—C6—C12—O1	2.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.93 (5)	1.70 (5)	2.633 (3)	174 (4)
N2—H2A···O2ⁱ	0.86	2.00	2.842 (3)	166
N2—H2B···O2	0.86	1.97	2.823 (3)	169
N8—H8A···O5ⁱⁱ	0.86	2.35	3.130 (3)	152
N8—H8B···O1	0.86	2.36	3.157 (3)	153
C3—H3C···O2ⁱ	0.96	2.58	3.466 (3)	153

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

2-Amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium 3,5-dinitrobenzoate (III) top

Crystal data top

C₇H₃N₂O₆⁺·C₄H₈N₃O⁻	F(000) = 672
M_r = 325.25	D_x = 1.568 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.4175 (8) Å	Cell parameters from 3163 reflections
b = 22.634 (3) Å	θ = 1.8–27.5°
c = 11.3668 (16) Å	µ = 0.13 mm⁻¹
β = 98.696 (3)°	T = 293 K
V = 1377.8 (3) Å³	PLATE, colour less
Z = 4	0.28 × 0.28 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	2272 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.037
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 27.6°, θ_min = 1.8°
T_min = 0.586, T_max = 0.866	h = −7→7
20448 measured reflections	k = −29→29
3163 independent reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.065	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.196	w = 1/[σ²(F_o²) + (0.0937P)² + 1.0476P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3163 reflections	Δρ_max = 0.25 e Å⁻³
213 parameters	Δρ_min = −0.32 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
C4	−0.3894 (5)	0.67552 (12)	0.7844 (2)	0.0424 (6)
H4A	−0.558043	0.685231	0.796735	0.051*
H4B	−0.392828	0.639390	0.738318	0.051*
C5	−0.2733 (5)	0.72557 (12)	0.7240 (2)	0.0427 (6)
C2	−0.0405 (4)	0.70851 (10)	0.9023 (2)	0.0350 (5)
C3	−0.2620 (5)	0.62719 (12)	0.9871 (2)	0.0483 (6)
H3B	−0.129434	0.630486	1.053120	0.072*
H3C	−0.262564	0.588098	0.954290	0.072*
H3A	−0.419004	0.634623	1.013773	0.072*
N8	0.9177 (6)	1.01956 (13)	0.7037 (3)	0.0736 (8)
C11	0.7730 (4)	0.87486 (11)	0.9151 (2)	0.0393 (5)
H11	0.743572	0.843176	0.963179	0.047*
C6	0.6068 (4)	0.88805 (10)	0.8141 (2)	0.0375 (5)
C8	0.8648 (5)	0.96901 (11)	0.7773 (2)	0.0472 (6)
C10	0.9834 (4)	0.90935 (11)	0.9437 (2)	0.0414 (6)
C7	0.6512 (5)	0.93614 (11)	0.7447 (2)	0.0437 (6)
H6	0.538901	0.946056	0.677449	0.052*
C9	1.0353 (5)	0.95663 (12)	0.8765 (2)	0.0473 (6)
H8	1.178680	0.979244	0.896870	0.057*
N3	−0.2244 (4)	0.66995 (9)	0.89681 (17)	0.0392 (5)
N1	−0.0656 (4)	0.74201 (10)	0.80206 (19)	0.0413 (5)
N2	0.1457 (4)	0.71462 (10)	0.98893 (19)	0.0463 (5)
H2A	0.156560	0.692065	1.050385	0.069*
H2B	0.257351	0.741190	0.984511	0.069*
C12	0.3804 (5)	0.84969 (12)	0.7774 (2)	0.0441 (6)
N10	1.1616 (4)	0.89413 (11)	1.0507 (2)	0.0552 (6)
O5	−0.3441 (4)	0.74696 (10)	0.62776 (17)	0.0607 (6)
O1	0.3484 (4)	0.80812 (10)	0.8451 (2)	0.0662 (6)
O2	0.2439 (4)	0.86212 (10)	0.68288 (18)	0.0627 (6)
O6	1.3477 (4)	0.92497 (11)	1.0742 (2)	0.0732 (7)
O7	1.1140 (5)	0.85160 (13)	1.1091 (2)	0.0908 (9)
O3	0.7738 (7)	1.02949 (15)	0.6138 (3)	0.1128 (12)
O4	1.1050 (7)	1.04788 (15)	0.7360 (3)	0.1269 (14)
H1	0.036 (7)	0.7666 (16)	0.799 (3)	0.076 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C4	0.0374 (12)	0.0478 (14)	0.0387 (13)	−0.0006 (10)	−0.0048 (10)	−0.0040 (11)
C5	0.0398 (13)	0.0499 (14)	0.0366 (13)	0.0072 (11)	0.0001 (10)	−0.0009 (11)
C2	0.0346 (11)	0.0369 (12)	0.0328 (11)	0.0018 (9)	0.0026 (9)	−0.0035 (9)
C3	0.0509 (15)	0.0497 (15)	0.0431 (14)	−0.0087 (12)	0.0028 (11)	0.0045 (12)
N8	0.088 (2)	0.0612 (17)	0.0709 (19)	−0.0125 (16)	0.0086 (16)	0.0176 (14)
C11	0.0400 (13)	0.0404 (12)	0.0362 (12)	0.0012 (10)	0.0020 (10)	−0.0023 (10)
C6	0.0370 (12)	0.0401 (12)	0.0345 (12)	−0.0001 (10)	0.0028 (9)	−0.0058 (10)
C8	0.0566 (16)	0.0379 (13)	0.0481 (15)	−0.0018 (11)	0.0106 (12)	−0.0002 (11)
C10	0.0375 (12)	0.0447 (13)	0.0388 (13)	0.0045 (10)	−0.0042 (10)	−0.0078 (10)
C7	0.0483 (14)	0.0448 (13)	0.0358 (12)	0.0058 (11)	−0.0012 (10)	−0.0015 (11)
C9	0.0420 (14)	0.0453 (14)	0.0532 (15)	−0.0038 (11)	0.0034 (12)	−0.0111 (12)
N3	0.0401 (11)	0.0426 (11)	0.0327 (10)	−0.0057 (9)	−0.0020 (8)	−0.0009 (8)
N1	0.0398 (11)	0.0429 (12)	0.0397 (11)	−0.0031 (9)	0.0011 (9)	0.0031 (9)
N2	0.0422 (11)	0.0560 (13)	0.0371 (11)	−0.0083 (10)	−0.0054 (9)	−0.0006 (10)
C12	0.0378 (13)	0.0503 (15)	0.0436 (14)	−0.0010 (11)	0.0036 (11)	−0.0110 (12)
N10	0.0452 (13)	0.0611 (15)	0.0534 (14)	−0.0011 (11)	−0.0113 (11)	−0.0053 (12)
O5	0.0587 (13)	0.0767 (14)	0.0428 (11)	0.0066 (10)	−0.0048 (9)	0.0150 (10)
O1	0.0575 (13)	0.0698 (14)	0.0686 (14)	−0.0231 (11)	0.0015 (11)	0.0062 (11)
O2	0.0508 (12)	0.0755 (14)	0.0546 (12)	−0.0006 (10)	−0.0151 (9)	−0.0134 (10)
O6	0.0506 (12)	0.0799 (15)	0.0798 (16)	−0.0069 (11)	−0.0200 (11)	−0.0083 (12)
O7	0.0811 (18)	0.103 (2)	0.0752 (17)	−0.0186 (15)	−0.0296 (14)	0.0361 (16)
O3	0.120 (3)	0.109 (2)	0.101 (2)	−0.0165 (19)	−0.0119 (19)	0.0592 (19)
O4	0.142 (3)	0.107 (2)	0.123 (3)	−0.075 (2)	−0.010 (2)	0.041 (2)

Geometric parameters (Å, º) top

C4—N3	1.450 (3)	C11—C6	1.381 (3)
C4—C5	1.511 (4)	C11—H11	0.9300
C4—H4A	0.9700	C6—C7	1.386 (4)
C4—H4B	0.9700	C6—C12	1.509 (3)
C5—O5	1.204 (3)	C8—C9	1.374 (4)
C5—N1	1.375 (3)	C8—C7	1.378 (4)
C2—N2	1.306 (3)	C10—C9	1.369 (4)
C2—N3	1.319 (3)	C10—N10	1.475 (3)
C2—N1	1.358 (3)	C7—H6	0.9300
C3—N3	1.447 (3)	C9—H8	0.9300
C3—H3B	0.9600	N1—H1	0.79 (4)
C3—H3C	0.9600	N2—H2A	0.8600
C3—H3A	0.9600	N2—H2B	0.8600
N8—O3	1.209 (4)	C12—O2	1.241 (3)
N8—O4	1.210 (4)	C12—O1	1.244 (3)
N8—C8	1.471 (4)	N10—O7	1.219 (3)
C11—C10	1.379 (3)	N10—O6	1.223 (3)

N3—C4—C5	102.84 (19)	C9—C8—C7	122.9 (3)
N3—C4—H4A	111.2	C9—C8—N8	117.4 (3)
C5—C4—H4A	111.2	C7—C8—N8	119.7 (3)
N3—C4—H4B	111.2	C9—C10—C11	122.9 (2)
C5—C4—H4B	111.2	C9—C10—N10	118.6 (2)
H4A—C4—H4B	109.1	C11—C10—N10	118.5 (2)
O5—C5—N1	126.5 (3)	C8—C7—C6	118.8 (2)
O5—C5—C4	128.1 (2)	C8—C7—H6	120.6
N1—C5—C4	105.4 (2)	C6—C7—H6	120.6
N2—C2—N3	126.7 (2)	C10—C9—C8	116.6 (2)
N2—C2—N1	122.8 (2)	C10—C9—H8	121.7
N3—C2—N1	110.5 (2)	C8—C9—H8	121.7
N3—C3—H3B	109.5	C2—N3—C3	126.6 (2)
N3—C3—H3C	109.5	C2—N3—C4	110.2 (2)
H3B—C3—H3C	109.5	C3—N3—C4	123.3 (2)
N3—C3—H3A	109.5	C2—N1—C5	111.0 (2)
H3B—C3—H3A	109.5	C2—N1—H1	117 (3)
H3C—C3—H3A	109.5	C5—N1—H1	132 (3)
O3—N8—O4	124.2 (3)	C2—N2—H2A	120.0
O3—N8—C8	118.0 (3)	C2—N2—H2B	120.0
O4—N8—C8	117.8 (3)	H2A—N2—H2B	120.0
C10—C11—C6	119.0 (2)	O2—C12—O1	125.9 (3)
C10—C11—H11	120.5	O2—C12—C6	117.5 (3)
C6—C11—H11	120.5	O1—C12—C6	116.6 (2)
C11—C6—C7	119.7 (2)	O7—N10—O6	124.6 (3)
C11—C6—C12	120.4 (2)	O7—N10—C10	117.9 (2)
C7—C6—C12	119.9 (2)	O6—N10—C10	117.5 (3)

N3—C4—C5—O5	−179.6 (3)	N2—C2—N3—C3	1.7 (4)
N3—C4—C5—N1	0.7 (3)	N1—C2—N3—C3	−179.4 (2)
C10—C11—C6—C7	−1.3 (4)	N2—C2—N3—C4	−177.8 (2)
C10—C11—C6—C12	177.4 (2)	N1—C2—N3—C4	1.1 (3)
O3—N8—C8—C9	177.2 (3)	C5—C4—N3—C2	−1.1 (3)
O4—N8—C8—C9	−1.4 (5)	C5—C4—N3—C3	179.4 (2)
O3—N8—C8—C7	−2.4 (5)	N2—C2—N1—C5	178.4 (2)
O4—N8—C8—C7	179.0 (4)	N3—C2—N1—C5	−0.6 (3)
C6—C11—C10—C9	0.3 (4)	O5—C5—N1—C2	−179.8 (3)
C6—C11—C10—N10	−179.0 (2)	C4—C5—N1—C2	−0.1 (3)
C9—C8—C7—C6	−0.7 (4)	C11—C6—C12—O2	−176.7 (2)
N8—C8—C7—C6	178.9 (2)	C7—C6—C12—O2	2.0 (4)
C11—C6—C7—C8	1.4 (4)	C11—C6—C12—O1	3.0 (4)
C12—C6—C7—C8	−177.3 (2)	C7—C6—C12—O1	−178.3 (2)
C11—C10—C9—C8	0.4 (4)	C9—C10—N10—O7	−179.4 (3)
N10—C10—C9—C8	179.7 (2)	C11—C10—N10—O7	0.0 (4)
C7—C8—C9—C10	−0.2 (4)	C9—C10—N10—O6	0.2 (4)
N8—C8—C9—C10	−179.8 (2)	C11—C10—N10—O6	179.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.79 (4)	1.94 (4)	2.679 (3)	157 (3)
N2—H2B···O1	0.86	2.30	2.983 (3)	137
N2—H2B···O5ⁱ	0.86	2.51	3.093 (3)	125
N2—H2A···O2ⁱⁱ	0.86	1.94	2.794 (3)	169
C3—H3B···O2ⁱⁱ	0.96	2.32	3.268 (3)	168
C4—H4B···O4ⁱⁱⁱ	0.97	2.58	3.299 (4)	131

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

Comparison of the supramolecular interactions and the types of primary and secondary motifs of creatinine salts top

Creatinine salts	Protonation at	Unit cell (Å, °) and space group	Centro/Noncentrosymmetric	Primary interaction between	Graph-set motif	Motif type	Secondary interaction between	Graph-set motif	Motif type	Supramolecular architecture
Creatininium chloride	N1	Monoclinic, P2₁/n; a = 8.4617 (2), b = 7.7073 (2), c = 10.2215 (3), β = 98.369 (2)	Centrosymmetric	Pair of N—H···Cl	R₄²(8)	III	C—H···Cl	R₂¹(7), R₄²(12)	XVIII and XIX	Chain
Creatininium bromide	N1	Monoclinic, P2₁/n a = 8.7252 (4), b = 7.7772 (4), c = 10.7406 (5), β = 97.969 (1)°	Centrosymmetric	Pair of N—H···Br	R₄²(8)	III	C—H···Br	R₂¹(7), R₄²(12)	XVIII and XIX	Chain
Creatininium nitrate	N1	Orthorhombic, Pbca; a = 16.6509 (3), b = 9.7336 (2), c = 8.9989 (3)	Centrosymmetric	N—H···O	R₄⁴(16)	X				Chain
Creatininium phosphite	N1	Monoclinic, P2₁/c; a = 8.8083 (11), b = 6.6316 (9), c = 15.068 (2), β = 99.539 (4)	Centrosymmetric	Pair of N—H···O Fork-like dimer, Pair of N—H···O	R₂²(8)	III	O—H···O Fork-like dimer b/w acid	R₂²(8), R₄²(8)	XIII and XIV	Chain
Creatinium perchlorate	N1	Monoclinic, P2₁/c; a = 5.8023 (3), b = 20.7782 (13), c = 7.3250 (4), β = 107.947 (4)	Centrosymmetric	Pair of N—H···O	R₂¹(6)	V	N—H···O	R₂⁴(8)	XX
Bis(creatininium) sulfate	N1	Monoclinic, P2₁/c; a = 12.469 (6), b = 7.560 (3), c = 14.382 (9), β = 97.347 (11)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	IV	N—H···O	C₂²(7)	XXV	Grid
Creatininium benzenesulfonate	N1	Monoclinic, P2₁; a = 7.0344 (12), b = 11.4987 (18), c = 7.8380 (11), β = 102.477 (4)	Noncentrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	IV	C—H···N			Zigzag chain
Creatininium 2-chloroacetate	N1	Monoclinic, P2₁/n; a = 5.7993 (8), b = 13.934 (2), c = 11.2205 (16), β = 95.326 (2)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	N—H···O	R₄²(8)	XIV	Sheet
Creatininium cinnamate	N1	Monoclinic, P2₁/c; a = 9.1680 (8), b = 11.3391 (11), c = 12.7070 (12), β = 104.578 (2)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	N—H···O	C₂²(6)	XXVI	Linear chain
Creatininium benzoate	N1	Monoclinic, P2₁/c; a = 8.5574 (5), b = 6.2094 (4), c = 22.0169 (14), β = 99.904 (1)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	C—H···O, N—H···O	R₂¹(7)	XXII	Zigzag chain
Creatininium benzoate	N1	Orthorhombic, SG?; a = 6.9095 (5), b = 10.2699 (7), c = 16.4105 (11)	Noncentrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	C—H···O, N—H···O	R₂¹(7)	XXII	Zigzag chain
Creatininium 4-nitrobenzoate	N1	Orthorhombic, SG?; a = 5.747 (3), b = 9.092 (2), c = 24.148 (6)	Noncentrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I				Chain
Creatininium 3,5-dinitrobenzoate	N1	Monoclinic, P2₁/c; a = 5.4175 (8), b = 22.634 (3), c = 11.3668 (16)	Centrosymmetric	Pair of N—H···O	R₂¹(6)	VII	C—H···O and N—H···O	R₂¹(7)	IX	Chain
Creatininium 3-aminobenzoate	N1	Monoclinic, P2₁; a = 7.9887 (4), b = 6.6098 (3), c = 11.4753 (6), β = 102.080 (2)	Noncentrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	N—H···O, C—H···O	R₂¹(7)	IX	Chain
Creatininium hydrogen oxalate monohydrate	N1	Orthorhombic, Pnma; a = 9.1728 (7), b = 6.3520 (5), c = 16.6567 (12)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	Pair of O—H···O b/w anions	R₁²(7)	XV	Sheet
Creatininium succinate	N1	Orthorhombic, F2dd; a = 5.534 (3), b = 14.278 (1), c = 40.131 (2)	Noncentrosymmetric
Bis(creatininium) fumarate fumaric acid	N2	Monoclinic, P2₁/c; a = 5.902 (2), b = 21.833 (9), c = 7.7752 (6)	Centrosymmetric	Pair of N—H···O	R₂¹(6)	VII	Pair of O—H···O	R₁²(4)	XXI
Creatininium hydrogen maleate	N14	Monoclinic, P2₁/n; a = 5.6271 (4) b = 24.8915 (17), c = 7.7752 (6), β = 108.69 (2)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	Anion intramolecular O—H···O; N—H···O b/w cation and anion	S(7), R₆⁴(16)	XV
Creatininium L-tartrate monohydrate	N1	Orthorhombic, P2₁2₁2₁	Noncentrosymmetric	N—H···O and O—H···O	R₃²(8)	VIII
Creatininium phthalate	N1	Triclinic, P1; a = 7.7322 (7), b = 9.9601 (9), c = 10.0821 (9), α = 107.173 (1), β = 11.892 (1), γ = 103.843 (1)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	N—H···O, C—H···O	R₂¹(7), R₆⁴(16), S(7)	XXII and XVI	Sheet
Bis(creatininium) 3-nitrophthalate monohydrate	N1	Monoclinic, P2₁/c; a = 7.6682 (3), b = 16.5504 (6), c = 16.2358 (7), β = 93.775 (1)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I and II	O—H···O and pair of C—H···O, N—H···O and O—H···O
Creatininium salicylate	N1	Monoclinic, P2₁/n; a = 7.6782 (10), b = 12.4991 (16), c = 12.4268 (16), β = 101.005 (2)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	Intramolecular O—H···O in anion	S(7)	XVI	Chain
Creatinine diphenic acid monohydrate	N1	Monoclinic, P2₁/c; a = 15.673, b = 7.2975, c = 17.120, β = 115.878	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	O—H···O
Creatinine pyrazine-2,3-dicarboxylic acid	N1	Monoclinic, Pc; a = 3.9677 (6), b = 11.567 (2), c = 13.290 (2), β = 94.53 (1)	Noncentrosymmetric	Pair of N—H···O	R₂²(8)	I	N—H···O	R₂¹(6)	XVII	Chain
Creatininium gallate trihydrate	N1	Monoclinic, P2₁/c; a = 6.6373 (1); b = 15.7350 (2); c = 14.1111 (1); β = 96.156 (1)	Centrosymmetric	Pair of N—H···O Fork-like dimer	R₂²(8)	I	O—H···O and C—H···O			Chain
Creatininium 5-(2,4-dinitrophenyl)-1,3-dimethylbarbiturate monohydrate	N1	Monoclinic, P2₁/n; a = 12.6926 (3), b = 7.3093 (2), c = 20.6213 (5), β = 100.420 (4)	Centrosymmetric	N—H···O hydrogen bond	R₂¹(7)	IX	O—H···O and N—H···O between anions	R₆⁶(24)	XXIV	Sheet

Percentage (%) of noncovalent interactions in the supramolecular packing of salts (I)–(III) analyzed by Hirshfeld surface analysis top

Salt (I)
All···All	100%	N···H/H···N	5.8
Br···H/H···Br	32.7	C···H/H···C	4.0
O···H/H···O	19.3	H···H	31.0

Salt (II)
All···All	100	N···H/H···N	4.8
O···H/H···O	28.9	H···H	41.8%
C···H/H···C	16.9	C···C	2.4

Salt (III)
All···All	100	N···H/H···N	4.2
O···H/H···O	51.4	H···H	13.2
C···H/H···C	10.3

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Synthesis, crystal structure determination and Hirshfeld surface analysis of three new salt forms of creatinine with hydro­bromic acid, 3-amino­benzoic acid and 3,5-di­nitro­benzoic acid

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Synthesis, crystal structure determination and Hirshfeld surface analysis of three new salt forms of creatinine with hydrobromic acid, 3-aminobenzoic acid and 3,5-dinitrobenzoic acid