Crystal structure of bis-{2-[amino(iminium-yl)meth-yl]-1,1-di-methyl-guanidine} carbonate methanol disolvate.

In the title solvated mol-ecular salt, 2C4H12N5 (+)·CO3 (2-)·2CH3OH, the complete carbonate ion is generated by crystallographic twofold symmetry, with the C atom and one O atom lying on the rotation axis. The cation is twisted about the central C-N bond [C-N-C-N = -137.7 (6)°]. In the crystal, the components are linked by N-H⋯O, N-H⋯N and O-H⋯O hydrogen bonds, generating a three-dimensional supra-molecular network.

Related literature

For background to and medical applications of metformin (systematic name: N,N-di­methyl­imidodicarbonimidic di­amide), see: Castagnolo et al. (2011 ▸); De Jager et al. (2005 ▸); Pérez-Fernández et al. (2013 ▸); Yardımcı & Özaltın (2005 ▸); Xi et al. (2008 ▸); Li et al. (2005 ▸). For a related structure, see: Huang et al. (2008 ▸).

Experimental

Crystal data

2C4H12N5 +·CO3 2−·2CH4O

M = 384.46

Monoclinic,

a = 13.5726 (12) Å

b = 10.5634 (8) Å

c = 13.9825 (13) Å

β = 90.386 (1)°

V = 2004.7 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 298 K

0.40 × 0.32 × 0.29 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▸) T min = 0.961, T max = 0.971

4837 measured reflections

1749 independent reflections

947 reflections with I > 2σ(I)

R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.083

wR(F 2) = 0.280

S = 1.02

1749 reflections

123 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.64 e Å−3

Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2000 ▸); cell refinement: SAINT (Bruker, 2000 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015016771/hb7495sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016771/hb7495Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015016771/hb7495Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015016771/hb7495fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015016771/hb7495fig2.tif

Part of the crystal structure with the hydrogen bonds drawn as dashed lines.

CCDC reference: 1422939

Additional supporting information: crystallographic information; 3D view; checkCIF report

2C4H12N5+·CO32−·2CH4O	F(000) = 832
Mr = 384.46	Dx = 1.274 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.5726 (12) Å	Cell parameters from 1052 reflections
b = 10.5634 (8) Å	θ = 2.8–22.8°
c = 13.9825 (13) Å	µ = 0.10 mm−1
β = 90.386 (1)°	T = 298 K
V = 2004.7 (3) Å3	Block, colourless
Z = 4	0.40 × 0.32 × 0.29 mm

Bruker APEXII CCD diffractometer	947 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.065
φ and ω scans	θmax = 25.1°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→15
Tmin = 0.961, Tmax = 0.971	k = −12→11
4837 measured reflections	l = −16→16
1749 independent reflections

Refinement on F2	6 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.083	H-atom parameters constrained
wR(F2) = 0.280	w = 1/[σ2(Fo2) + (0.1395P)2 + 3.7847P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
1749 reflections	Δρmax = 0.64 e Å−3
123 parameters	Δρmin = −0.29 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.

	x	y	z	Uiso*/Ueq
N1	0.9937 (3)	0.6120 (4)	0.3964 (3)	0.0764 (14)
H1A	1.0180	0.6664	0.3574	0.092*
H1B	1.0312	0.5752	0.4377	0.092*
N2	0.8445 (3)	0.6436 (4)	0.3289 (3)	0.0651 (12)
H2A	0.8709	0.6975	0.2908	0.078*
H2B	0.7824	0.6279	0.3250	0.078*
N3	0.8641 (3)	0.5040 (4)	0.4562 (3)	0.0753 (14)
N4	0.7163 (3)	0.4414 (5)	0.5183 (3)	0.0787 (14)
N5	0.7482 (3)	0.3984 (4)	0.3619 (3)	0.0663 (12)
H5A	0.6934	0.3578	0.3579	0.080*
H5B	0.7857	0.4044	0.3128	0.080*
O1	0.43093 (19)	0.6744 (3)	0.7084 (2)	0.0513 (9)
O2	0.5000	0.4941 (4)	0.7500	0.0802 (17)
O3	0.3680 (3)	0.3385 (6)	0.6850 (5)	0.143 (2)
H3	0.4110	0.3854	0.7063	0.214*
C1	0.8990 (3)	0.5850 (5)	0.3931 (3)	0.0584 (12)
C2	0.7748 (3)	0.4516 (5)	0.4435 (3)	0.0627 (14)
C3	0.6269 (4)	0.3681 (7)	0.5153 (4)	0.095 (2)
H3A	0.5800	0.4085	0.4737	0.143*
H3B	0.6001	0.3621	0.5785	0.143*
H3C	0.6410	0.2847	0.4917	0.143*
C4	0.7393 (6)	0.5018 (9)	0.6077 (5)	0.127 (3)
H4A	0.8000	0.5476	0.6020	0.191*
H4B	0.7458	0.4389	0.6568	0.191*
H4C	0.6873	0.5594	0.6240	0.191*
C5	0.3996 (9)	0.2845 (15)	0.6049 (14)	0.279 (10)
H5D	0.3442	0.2644	0.5646	0.419*
H5E	0.4349	0.2084	0.6203	0.419*
H5F	0.4424	0.3419	0.5719	0.419*
C6	0.5000	0.6130 (5)	0.7500	0.0422 (13)

	U11	U22	U33	U12	U13	U23
N1	0.055 (2)	0.092 (3)	0.082 (3)	−0.035 (2)	−0.022 (2)	0.034 (2)
N2	0.050 (2)	0.079 (3)	0.067 (3)	−0.0205 (19)	−0.0089 (19)	0.017 (2)
N3	0.065 (3)	0.104 (3)	0.056 (2)	−0.049 (2)	−0.0220 (19)	0.023 (2)
N4	0.076 (3)	0.108 (4)	0.051 (3)	−0.041 (3)	0.000 (2)	−0.003 (2)
N5	0.058 (2)	0.093 (3)	0.047 (2)	−0.034 (2)	−0.0063 (17)	0.000 (2)
O1	0.0389 (15)	0.0469 (17)	0.068 (2)	−0.0007 (12)	−0.0176 (13)	−0.0020 (14)
O2	0.060 (3)	0.037 (3)	0.144 (5)	0.000	−0.032 (3)	0.000
O3	0.063 (3)	0.135 (4)	0.230 (7)	−0.016 (3)	0.011 (3)	−0.097 (4)
C1	0.051 (3)	0.076 (3)	0.048 (2)	−0.024 (2)	−0.009 (2)	0.006 (2)
C2	0.059 (3)	0.079 (3)	0.050 (3)	−0.032 (2)	−0.012 (2)	0.015 (2)
C3	0.076 (4)	0.133 (5)	0.077 (4)	−0.048 (4)	0.007 (3)	0.010 (4)
C4	0.140 (6)	0.180 (8)	0.062 (4)	−0.046 (6)	0.006 (4)	−0.028 (5)
C5	0.153 (9)	0.254 (15)	0.43 (2)	−0.090 (10)	0.122 (12)	−0.223 (16)
C6	0.029 (3)	0.039 (3)	0.059 (4)	0.000	−0.007 (2)	0.000

N1—C1	1.317 (6)	C6—O1	1.276 (4)
N1—H1A	0.8600	C6—O2	1.257 (7)
N1—H1B	0.8600	O3—C5	1.330 (13)
N2—C1	1.314 (6)	O3—H3	0.8200
N2—H2A	0.8600	C3—H3A	0.9600
N2—H2B	0.8600	C3—H3B	0.9600
N3—C1	1.319 (6)	C3—H3C	0.9600
N3—C2	1.344 (5)	C4—H4A	0.9600
N4—C2	1.321 (6)	C4—H4B	0.9600
N4—C4	1.436 (8)	C4—H4C	0.9600
N4—C3	1.440 (6)	C5—H5D	0.9600
N5—C2	1.320 (6)	C5—H5E	0.9600
N5—H5A	0.8600	C5—H5F	0.9600
N5—H5B	0.8600	C6—O1i	1.276 (4)
C1—N1—H1A	120.0	N4—C3—H3B	109.5
C1—N1—H1B	120.0	H3A—C3—H3B	109.5
H1A—N1—H1B	120.0	N4—C3—H3C	109.5
C1—N2—H2A	120.0	H3A—C3—H3C	109.5
C1—N2—H2B	120.0	H3B—C3—H3C	109.5
H2A—N2—H2B	120.0	N4—C4—H4A	109.5
C1—N3—C2	120.4 (4)	N4—C4—H4B	109.5
C2—N4—C4	121.7 (5)	H4A—C4—H4B	109.5
C2—N4—C3	122.1 (4)	N4—C4—H4C	109.5
C4—N4—C3	116.2 (5)	H4A—C4—H4C	109.5
C2—N5—H5A	120.0	H4B—C4—H4C	109.5
C2—N5—H5B	120.0	O3—C5—H5D	109.5
H5A—N5—H5B	120.0	O3—C5—H5E	109.5
C5—O3—H3	109.5	H5D—C5—H5E	109.5
N2—C1—N1	117.9 (4)	O3—C5—H5F	109.5
N2—C1—N3	124.0 (4)	H5D—C5—H5F	109.5
N1—C1—N3	118.1 (4)	H5E—C5—H5F	109.5
N5—C2—N4	119.2 (4)	O2—C6—O1i	120.5 (2)
N5—C2—N3	122.0 (4)	O2—C6—O1	120.5 (2)
N4—C2—N3	118.4 (4)	O1i—C6—O1	119.0 (5)
N4—C3—H3A	109.5
C2—N3—C1—N2	17.2 (8)	C4—N4—C2—N3	9.8 (9)
C2—N3—C1—N1	−165.0 (5)	C3—N4—C2—N3	−169.3 (6)
C4—N4—C2—N5	−177.3 (7)	C1—N3—C2—N5	49.6 (8)
C3—N4—C2—N5	3.6 (9)	C1—N3—C2—N4	−137.7 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ii	0.86	2.04	2.883 (5)	166
N1—H1B···N3iii	0.86	2.21	3.069 (6)	175
N2—H2A···O1iv	0.86	1.96	2.818 (5)	178
N2—H2B···O3v	0.86	2.08	2.896 (6)	159
N5—H5A···O1v	0.86	1.95	2.728 (4)	150
O3—H3···O2	0.82	1.77	2.591 (5)	177

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1AO1i	0.86	2.04	2.883(5)	166
N1H1BN3ii	0.86	2.21	3.069(6)	175
N2H2AO1iii	0.86	1.96	2.818(5)	178
N2H2BO3iv	0.86	2.08	2.896(6)	159
N5H5AO1iv	0.86	1.95	2.728(4)	150
O3H3O2	0.82	1.77	2.591(5)	177

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