2-Phenyl-biguanidinium hydrogen succinate methanol monosolvate.

In the crystal of the title compound, C(8)H(12)N(5) (+)·C(4)H(5)O(4) (-)·CH(3)OH, the hydrogen succinate anions form infinite [010] chains via short, almost symmetrical, O⋯H⋯O hydrogen bonds. The 2-phenyl-biguanidium cations inter-connect these chains into layers lying parallel to the bc plane by way of N-H⋯O links. These planes only weakly inter-act in the direction of the a axis via C-H⋯π contacts between offset phenyl rings, leaving as much as 17% of the unit-cell volume accessible for the solvent. However, the methanol solvent mol-ecules could not be resolved due to extensive disorder and their assumed presence was removed from the overall scattering by the PLATON SQUEEZE procedure.

Related literature

Biguanides forms stable complexes, see: Marchi et al. (1999 ▶); Ray (1961 ▶); Anderson et al. (1995 ▶) and also have applications in medicine, see: Sirtori & Pasik (1994 ▶); Clement & Girreser (1999 ▶); Thompson et al. (1999 ▶); Ross et al. (2004 ▶); Woo et al. (1999 ▶); Watkins et al. (1987 ▶); Morain et al. (1994 ▶); Shapiro et al. (1959a ▶,b ▶). Ionic crystal structures containing biguanide cations are formed by relatively strong hydrogen bonds, see: Martin et al. (1996 ▶); Martin & Pinkerton (1996 ▶); Pinkerton et al. (1978 ▶); Matulková et al. (2008 ▶, 2010 ▶). For the SQUEEZE method used to solve the structure, see: van der Sluis & Spek (1990 ▶).

Experimental

Crystal data

C8H12N5 +·C4H5O4 −·CH4O

M = 327.35

Monoclinic,

a = 10.3280 (3) Å

b = 6.4590 (1) Å

c = 24.6770 (6) Å

β = 94.0480 (13)°

V = 1642.06 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.45 × 0.4 × 0.18 mm

Data collection

Nonius KappaCCD diffractometer

18123 measured reflections

3568 independent reflections

2613 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.174

S = 1.07

3568 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.23 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶) and DENZO (Otwinowski & Minor, 1997 ▶); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) ▶; molecular graphics: PLATON (Spek, 2009) ▶; software used to prepare material for publication: SHELXL97 ▶.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681004585X/hb5725sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004585X/hb5725Isup2.hkl

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

C8H12N5+·C4H5O4−·CH4O	F(000) = 696
Mr = 327.35	Dx = 1.324 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3693 reflections
a = 10.3280 (3) Å	θ = 1–27.1°
b = 6.4590 (1) Å	µ = 0.10 mm−1
c = 24.6770 (6) Å	T = 293 K
β = 94.0480 (13)°	Plate, colourless
V = 1642.06 (7) Å3	0.45 × 0.4 × 0.18 mm
Z = 4

Nonius KappaCCD diffractometer	2613 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
horizontally mounted graphite crystal	θmax = 27.1°, θmin = 1.7°
Detector resolution: 9.091 pixels mm-1	h = −13→13
ω and π scans to fill the Ewald sphere	k = −8→8
18123 measured reflections	l = −31→31
3568 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056	H-atom parameters constrained
wR(F2) = 0.174	w = 1/[σ2(Fo2) + (0.1087P)2 + 0.1338P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
3568 reflections	Δρmax = 0.25 e Å−3
191 parameters	Δρmin = −0.23 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.055 (7)

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
N1	0.20697 (15)	−0.1226 (2)	0.77926 (5)	0.0515 (4)
H1	0.1757	−0.1468	0.7435	0.062*
N2	0.07708 (16)	−0.3948 (2)	0.79668 (5)	0.0570 (4)
H2A	0.0599	−0.4106	0.7620	0.068*
H2B	0.0280	−0.4630	0.8208	0.068*
N3	0.18707 (15)	−0.2116 (2)	0.86872 (5)	0.0514 (4)
N4	0.16449 (16)	−0.2862 (2)	0.95713 (5)	0.0537 (4)
H4A	0.1524	−0.1453	0.9625	0.064*
H4B	0.1638	−0.3785	0.9874	0.064*
N5	0.18754 (16)	−0.5585 (2)	0.90047 (5)	0.0575 (4)
H5A	0.2005	−0.6075	0.8702	0.069*
H5B	0.1909	−0.6467	0.9288	0.069*
C1	0.15804 (17)	−0.2481 (2)	0.81647 (6)	0.0464 (4)
C2	0.17836 (16)	−0.3547 (2)	0.90737 (6)	0.0448 (4)
O1	−0.16551 (14)	−0.15632 (17)	1.00242 (4)	0.0577 (4)
O2	−0.16362 (15)	−0.43722 (16)	0.95237 (5)	0.0616 (4)
H2	−0.1523	−0.4961	0.9068	0.074*
O3	−0.10001 (17)	0.1366 (2)	0.81889 (5)	0.0738 (5)
O4	−0.13315 (14)	0.42420 (17)	0.86173 (4)	0.0598 (4)
C3	0.29311 (18)	0.0463 (2)	0.78891 (6)	0.0519 (4)
C4	0.3920 (2)	0.0464 (3)	0.82884 (8)	0.0687 (6)
H4	0.4044	−0.0663	0.8521	0.082*
C5	0.4738 (3)	0.2177 (5)	0.83414 (11)	0.0929 (9)
H5	0.5407	0.2191	0.8614	0.112*
C6	0.4578 (3)	0.3832 (4)	0.80008 (14)	0.0964 (10)
H6	0.5130	0.4967	0.8042	0.116*
C7	0.3612 (3)	0.3805 (4)	0.76041 (14)	0.0911 (9)
H7	0.3508	0.4928	0.7369	0.109*
C8	0.2768 (2)	0.2135 (3)	0.75394 (9)	0.0694 (6)
H8	0.2103	0.2139	0.7265	0.083*
C9	−0.16134 (17)	−0.2385 (2)	0.95785 (6)	0.0464 (4)
C10	−0.15527 (19)	−0.1185 (2)	0.90552 (6)	0.0488 (4)
H10A	−0.0830	−0.1701	0.8864	0.059*
H10B	−0.2341	−0.1447	0.8828	0.059*
C11	−0.13977 (19)	0.1122 (2)	0.91303 (6)	0.0462 (4)
H11A	−0.2155	0.1663	0.9293	0.055*
H11B	−0.0647	0.1387	0.9379	0.055*
C12	−0.12325 (17)	0.2254 (2)	0.86057 (6)	0.0462 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0785 (10)	0.0498 (8)	0.0273 (6)	−0.0067 (6)	0.0109 (6)	0.0028 (5)
N2	0.0825 (11)	0.0601 (9)	0.0291 (7)	−0.0165 (7)	0.0088 (6)	−0.0007 (6)
N3	0.0828 (10)	0.0438 (7)	0.0288 (7)	−0.0077 (7)	0.0109 (6)	0.0018 (5)
N4	0.0905 (11)	0.0458 (8)	0.0258 (6)	−0.0013 (7)	0.0104 (6)	0.0035 (5)
N5	0.0926 (12)	0.0439 (8)	0.0368 (7)	0.0057 (7)	0.0099 (7)	0.0031 (6)
C1	0.0672 (10)	0.0430 (8)	0.0302 (7)	0.0002 (7)	0.0121 (7)	0.0014 (6)
C2	0.0593 (10)	0.0457 (8)	0.0300 (7)	−0.0025 (7)	0.0065 (6)	0.0021 (6)
O1	0.1019 (10)	0.0397 (6)	0.0324 (6)	−0.0008 (6)	0.0104 (6)	0.0029 (4)
O2	0.1145 (11)	0.0315 (6)	0.0402 (6)	−0.0014 (6)	0.0168 (6)	0.0058 (4)
O3	0.1439 (14)	0.0514 (7)	0.0279 (6)	−0.0011 (7)	0.0179 (7)	0.0000 (5)
O4	0.1054 (10)	0.0345 (6)	0.0410 (6)	−0.0023 (6)	0.0155 (6)	0.0084 (4)
C3	0.0733 (11)	0.0461 (9)	0.0391 (8)	−0.0031 (8)	0.0240 (8)	−0.0013 (6)
C4	0.0815 (14)	0.0792 (14)	0.0468 (10)	−0.0154 (10)	0.0140 (10)	0.0015 (9)
C5	0.0854 (16)	0.119 (2)	0.0775 (16)	−0.0400 (15)	0.0293 (13)	−0.0254 (15)
C6	0.105 (2)	0.0770 (16)	0.114 (2)	−0.0389 (14)	0.0597 (19)	−0.0213 (15)
C7	0.110 (2)	0.0545 (12)	0.116 (2)	−0.0070 (12)	0.0548 (19)	0.0143 (13)
C8	0.0849 (14)	0.0561 (11)	0.0711 (13)	0.0021 (9)	0.0319 (11)	0.0170 (9)
C9	0.0715 (11)	0.0329 (7)	0.0357 (8)	0.0001 (7)	0.0097 (7)	0.0041 (6)
C10	0.0817 (12)	0.0329 (8)	0.0325 (7)	−0.0001 (7)	0.0086 (7)	0.0027 (5)
C11	0.0779 (11)	0.0335 (7)	0.0281 (7)	−0.0031 (7)	0.0087 (7)	0.0026 (5)
C12	0.0741 (11)	0.0366 (8)	0.0281 (7)	−0.0040 (7)	0.0050 (7)	0.0029 (5)

N1—C1	1.3495 (19)	C3—C4	1.368 (3)
N1—C3	1.417 (2)	C3—C8	1.385 (2)
N1—H1	0.9313	C4—C5	1.393 (3)
N2—C1	1.333 (2)	C4—H4	0.9300
N2—H2A	0.8679	C5—C6	1.363 (4)
N2—H2B	0.9206	C5—H5	0.9300
N3—C1	1.3242 (19)	C6—C7	1.348 (5)
N3—C2	1.3358 (19)	C6—H6	0.9300
N4—C2	1.3223 (18)	C7—C8	1.389 (4)
N4—H4A	0.9291	C7—H7	0.9300
N4—H4B	0.9561	C8—H8	0.9300
N5—C2	1.331 (2)	C9—C10	1.511 (2)
N5—H5A	0.8301	C10—C11	1.509 (2)
N5—H5B	0.9016	C10—H10A	0.9700
O1—C9	1.2245 (18)	C10—H10B	0.9700
O2—C9	1.2909 (19)	C11—C12	1.5069 (19)
O2—H2	1.2016	C11—H11A	0.9700
O3—C12	1.2164 (18)	C11—H11B	0.9700
O4—C12	1.2884 (19)
C1—N1—C3	127.49 (14)	C4—C5—H5	119.4
C1—N1—H1	115.0	C7—C6—C5	119.3 (2)
C3—N1—H1	117.4	C7—C6—H6	120.3
C1—N2—H2A	121.6	C5—C6—H6	120.3
C1—N2—H2B	117.6	C6—C7—C8	121.3 (2)
H2A—N2—H2B	119.8	C6—C7—H7	119.4
C1—N3—C2	123.36 (14)	C8—C7—H7	119.4
C2—N4—H4A	119.0	C3—C8—C7	119.1 (2)
C2—N4—H4B	121.6	C3—C8—H8	120.4
H4A—N4—H4B	119.4	C7—C8—H8	120.4
C2—N5—H5A	120.7	O1—C9—O2	121.57 (13)
C2—N5—H5B	121.7	O1—C9—C10	123.48 (13)
H5A—N5—H5B	117.2	O2—C9—C10	114.95 (13)
N3—C1—N2	125.19 (14)	C11—C10—C9	114.32 (12)
N3—C1—N1	119.06 (15)	C11—C10—H10A	108.7
N2—C1—N1	115.64 (14)	C9—C10—H10A	108.7
N4—C2—N5	117.58 (14)	C11—C10—H10B	108.7
N4—C2—N3	116.65 (14)	C9—C10—H10B	108.7
N5—C2—N3	125.71 (13)	H10A—C10—H10B	107.6
C9—O2—H2	114.2	C12—C11—C10	113.04 (12)
C4—C3—C8	119.99 (19)	C12—C11—H11A	109.0
C4—C3—N1	123.32 (16)	C10—C11—H11A	109.0
C8—C3—N1	116.63 (18)	C12—C11—H11B	109.0
C3—C4—C5	119.0 (2)	C10—C11—H11B	109.0
C3—C4—H4	120.5	H11A—C11—H11B	107.8
C5—C4—H4	120.5	O3—C12—O4	120.62 (13)
C6—C5—C4	121.2 (3)	O3—C12—C11	122.59 (14)
C6—C5—H5	119.4	O4—C12—C11	116.78 (12)

Cg1 is the centroidof the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3i	0.93	2.18	3.021 (2)	149
N1—H1···O4i	0.93	2.64	3.5217 (17)	158
N2—H2A···O3i	0.87	2.09	2.8855 (17)	152
N2—H2B···O4ii	0.92	2.14	3.0248 (19)	162
N4—H4A···O1iii	0.93	2.13	3.0273 (18)	161
N4—H4B···O2iv	0.96	1.90	2.8605 (16)	180
N5—H5B···O1iv	0.90	2.15	3.0440 (17)	170
O2—H2···O4ii	1.20	1.25	2.4500 (16)	173
C6—H6···Cg1v	0.93	3.10	3.676 (2)	122

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroidof the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3i	0.93	2.18	3.021 (2)	149
N1—H1⋯O4i	0.93	2.64	3.5217 (17)	158
N2—H2A⋯O3i	0.87	2.09	2.8855 (17)	152
N2—H2B⋯O4ii	0.92	2.14	3.0248 (19)	162
N4—H4A⋯O1iii	0.93	2.13	3.0273 (18)	161
N4—H4B⋯O2iv	0.96	1.90	2.8605 (16)	180
N5—H5B⋯O1iv	0.90	2.15	3.0440 (17)	170
O2—H2⋯O4ii	1.20	1.25	2.4500 (16)	173
C6—H6⋯Cg1v	0.93	3.10	3.676 (2)	122

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