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The cation in the title compound, C4H12N5+·NO3, is protonated at one imino group, and through this an intramolecular N—H...N hydrogen bond is formed, which stabilizes the conformation of the cation in the structure. The dihedral angle between the two guanidine groups is 51.7 (1)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803006639/ww6070sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803006639/ww6070Isup2.hkl
Contains datablock I

CCDC reference: 209996

Key indicators

  • Single-crystal X-ray study
  • T = 184 K
  • Mean [sigma](O-N) = 0.003 Å
  • R factor = 0.054
  • wR factor = 0.129
  • Data-to-parameter ratio = 10.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Metformin is an antihyperglycemic agent which improves glucose tolerance in type-2 diabetic patients, lowering both basal and postprandial plasma glucose levels. There are some benefits for these diabetic patients who use it in order to control their plasma glucose levels. From pharmacological studies, metformin acts by improving peripheral sensitivity to insulin, inhibiting gastrointestinal absorption of glucose, and decreasing hepatic glucose production. Researchers indicate that metformin alone does not produce hypoglycemia in either diabetic or nondiabetic individuals (Davidson & Peters, 1997; Jackson et al., 1987; Klip et al., 1990). In previous reports, we studied that the structures of metformin formed the complexes with Zn2+, Cu2+ and Ni2+ (Zhu et al., 2002, 2002a,b). Magnesium, a ubiquitous element that plays a fundamental role in many cellular reactions, is involved in more than 300 enzymatic reactions in which food is catabolized and new chemical products are formed, such as glycogen breakdown, fat oxidation, protein synthesis, ATP synthesis, and the second messenger system (Lukaski, 2000). In order to obtain the information regarding interaction between metformin and magnesium ions, magnesium(II) nitrate is employed in our current research. However, the title compound, (I), is obtained instead of the Mg2+ complex. Compared with (C4H12N5)[TlBr4] (He et al., 2002) and C4H12N5+·Cl (Hariharan et al., 1989), the anion of (I) is NO3 here.

Selected geometric parameters are listed in Table 1, and a perspective view of the structure is shown in Fig. 1. In the structure of (I), the two guanidine groups form two planes with a 51.7 (1)° planar angle. Atoms C1 and C2 are −0.042 (3) and −0.019 (3) Å out of planes N1/N2/N3/C1 and N3/N4/N5/C2, respectively. The C—N bond distances of (I) in the range of 1.324 (3)–1.336 (3) Å are shorter than a single and longer than the double bond, indicating a delocalization of π-electron density across the biguanide group. In other words, the position of the single and double bond is not strictly located inside the molecule. 1,1-Dimethylbiguanide as a form of cation appears in several compounds, such as (C4H12N5)[ZnCl3] (Zhu et al., 2002), and previously mentioned. Compared with the cation form of these compounds, a notable difference can be drawn from the packing diagrams. As shown in Fig. 2, two molecules are connected by two N5—H···N3 hydrogen bonds, forming an elongated hexagon. The hydrogen bonding information is given in Table 2 and a packing diagram is shown in Fig. 3. In addition, the molecules in the crystal are held together by van der Waals forces by a number of intermolecular N—H···O interactions. A weak N—H···N intramolecular hydrogen bond stabilizes the cation conformation (Fig. 1).

Experimental top

Crystals of (I) were grown from an aqueous solution of magnesium(II) nitrate hexahydrate (100.0 mmol) and N-dimethylbiguanide hydrochloride (100.0 mmol). The solution was left at room temperature and crystals formed after a few days. The elemental analysis result was in agreement with the structural composition of (I).

Refinement top

H atoms attached to C and N atoms were located in difference Fourier maps and refined with a global Uiso value. The C—H and N—H distances were in the ranges 0.93 (3)–0.98 (3) and 0.84 (3)–0.91 (3) Å, respectively.

Computing details top

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

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of (I), with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radii. Dotted lines represent hydrogen bonds.
[Figure 2] Fig. 2. The crystal structure of (I) as a dimer formed via hydrogen bonds. Dotted lines represent hydrogen bonds.
[Figure 3] Fig. 3. A packing diagram of the structure of the title compound.
N,N-dimethylbiguanidium nitrate top
Crystal data top
C4H12N5+·NO3Z = 2
Mr = 192.20F(000) = 204
Triclinic, P1Dx = 1.418 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.204 (3) ÅCell parameters from 2484 reflections
b = 7.534 (3) Åθ = 2.8–24.7°
c = 8.821 (4) ŵ = 0.12 mm1
α = 78.109 (5)°T = 184 K
β = 73.979 (6)°Block, colorless
γ = 85.353 (6)°0.30 × 0.20 × 0.10 mm
V = 450.1 (3) Å3
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1559 independent reflections
Radiation source: fine-focus sealed tube1181 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
h = 58
Tmin = 0.965, Tmax = 0.988k = 78
1875 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129All H-atom parameters refined
S = 1.01 w = 1/[σ2(Fo2) + (0.0627P)2]
where P = (Fo2 + 2Fc2)/3
1559 reflections(Δ/σ)max = 0.002
155 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C4H12N5+·NO3γ = 85.353 (6)°
Mr = 192.20V = 450.1 (3) Å3
Triclinic, P1Z = 2
a = 7.204 (3) ÅMo Kα radiation
b = 7.534 (3) ŵ = 0.12 mm1
c = 8.821 (4) ÅT = 184 K
α = 78.109 (5)°0.30 × 0.20 × 0.10 mm
β = 73.979 (6)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
1559 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)
1181 reflections with I > 2σ(I)
Tmin = 0.965, Tmax = 0.988Rint = 0.022
1875 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.129All H-atom parameters refined
S = 1.01Δρmax = 0.27 e Å3
1559 reflectionsΔρmin = 0.20 e Å3
155 parameters
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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3203 (3)0.1619 (3)0.7195 (3)0.0232 (6)
C20.3318 (4)0.2505 (3)0.9550 (3)0.0236 (6)
C30.2488 (5)0.0584 (4)0.4995 (3)0.0315 (7)
C40.1365 (6)0.1112 (4)0.7791 (4)0.0477 (9)
N10.2468 (3)0.0374 (3)0.6676 (2)0.0251 (5)
N20.3802 (3)0.3163 (3)0.6177 (3)0.0290 (6)
N30.3490 (3)0.1233 (2)0.8670 (2)0.0262 (5)
N40.2262 (3)0.4036 (3)0.9364 (3)0.0309 (6)
N50.4182 (3)0.2203 (3)1.0727 (3)0.0342 (6)
N60.1893 (3)0.5910 (3)0.3001 (3)0.0316 (6)
O10.3340 (3)0.4826 (2)0.2927 (2)0.0312 (5)
O20.1352 (3)0.6691 (3)0.4143 (3)0.0542 (6)
O30.1053 (3)0.6168 (3)0.1917 (2)0.0534 (6)
H210.347 (4)0.357 (4)0.529 (4)0.051 (3)*
H220.451 (4)0.388 (4)0.646 (3)0.051 (3)*
H410.219 (4)0.468 (4)1.005 (4)0.051 (3)*
H420.151 (5)0.418 (4)0.868 (4)0.051 (3)*
H510.499 (4)0.123 (4)1.084 (3)0.051 (3)*
H520.401 (4)0.294 (4)1.138 (4)0.051 (3)*
H3A0.368 (5)0.110 (4)0.435 (4)0.051 (3)*
H4A0.006 (5)0.095 (4)0.782 (4)0.051 (3)*
H3B0.147 (4)0.141 (4)0.472 (3)0.051 (3)*
H4B0.170 (4)0.224 (4)0.745 (3)0.051 (3)*
H3C0.231 (4)0.060 (4)0.476 (3)0.051 (3)*
H4C0.146 (4)0.119 (4)0.885 (4)0.051 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0173 (13)0.0265 (13)0.0250 (13)0.0027 (11)0.0048 (11)0.0056 (10)
C20.0249 (14)0.0258 (13)0.0191 (12)0.0013 (11)0.0055 (11)0.0025 (10)
C30.0318 (17)0.0356 (16)0.0318 (15)0.0009 (13)0.0132 (13)0.0113 (12)
C40.065 (2)0.0401 (18)0.0394 (18)0.0224 (18)0.0158 (18)0.0008 (14)
N10.0258 (12)0.0255 (11)0.0256 (11)0.0022 (9)0.0083 (9)0.0059 (9)
N20.0345 (14)0.0287 (12)0.0260 (12)0.0060 (10)0.0142 (11)0.0001 (9)
N30.0320 (13)0.0250 (11)0.0242 (11)0.0030 (9)0.0126 (10)0.0052 (8)
N40.0342 (14)0.0313 (13)0.0323 (13)0.0088 (10)0.0159 (11)0.0118 (10)
N50.0455 (16)0.0329 (13)0.0322 (13)0.0131 (11)0.0219 (12)0.0141 (10)
N60.0275 (13)0.0372 (13)0.0345 (13)0.0011 (11)0.0112 (11)0.0135 (10)
O10.0291 (10)0.0319 (10)0.0367 (11)0.0084 (8)0.0137 (8)0.0126 (8)
O20.0514 (14)0.0640 (14)0.0607 (14)0.0165 (11)0.0200 (12)0.0422 (12)
O30.0410 (13)0.0811 (16)0.0530 (13)0.0201 (11)0.0317 (11)0.0286 (11)
Geometric parameters (Å, º) top
C1—N11.327 (3)C4—H4B0.95 (3)
C1—N21.335 (3)C4—H4C0.95 (3)
C1—N31.343 (3)N2—H210.87 (3)
C2—N51.324 (3)N2—H220.89 (3)
C2—N31.331 (3)N4—H410.84 (3)
C2—N41.336 (3)N4—H420.90 (3)
C3—N11.455 (3)N5—H510.91 (3)
C3—H3A0.95 (3)N5—H520.85 (3)
C3—H3B0.98 (3)N6—O21.226 (3)
C3—H3C0.98 (3)N6—O31.241 (3)
C4—N11.453 (4)N6—O11.266 (3)
C4—H4A0.93 (3)
N1—C1—N2118.7 (2)H4B—C4—H4C111 (2)
N1—C1—N3119.4 (2)C1—N1—C4121.3 (2)
N2—C1—N3121.6 (2)C1—N1—C3121.2 (2)
N5—C2—N3118.1 (2)C4—N1—C3116.8 (2)
N5—C2—N4117.8 (2)C1—N2—H21125.2 (19)
N3—C2—N4124.1 (2)C1—N2—H22118.1 (19)
N1—C3—H3A108.3 (17)H21—N2—H22117 (3)
N1—C3—H3B112.5 (17)C2—N3—C1121.5 (2)
H3A—C3—H3B107 (2)C2—N4—H41115 (2)
N1—C3—H3C109.4 (16)C2—N4—H42118.8 (18)
H3A—C3—H3C112 (2)H41—N4—H42125 (3)
H3B—C3—H3C108 (2)C2—N5—H51120.1 (18)
N1—C4—H4A110.5 (19)C2—N5—H52120 (2)
N1—C4—H4B112.4 (18)H51—N5—H52119 (3)
H4A—C4—H4B103 (3)O2—N6—O3121.2 (2)
N1—C4—H4C111.9 (17)O2—N6—O1119.2 (2)
H4A—C4—H4C107 (3)O3—N6—O1119.6 (2)
N2—C1—N1—C4164.5 (3)N5—C2—N3—C1159.1 (2)
N3—C1—N1—C421.6 (4)N4—C2—N3—C123.8 (4)
N2—C1—N1—C36.3 (4)N1—C1—N3—C2147.5 (2)
N3—C1—N1—C3167.6 (2)N2—C1—N3—C238.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H52···O1i0.85 (3)2.11 (3)2.962 (3)175 (3)
N5—H51···N3ii0.91 (3)2.10 (3)3.003 (3)171 (3)
N4—H41···O3i0.84 (3)2.12 (3)2.932 (3)162 (3)
N2—H21···O10.87 (3)2.13 (3)2.980 (3)166 (3)
N2—H22···O1iii0.89 (3)2.14 (3)3.009 (3)168 (3)
N4—H42···O3iv0.90 (3)2.10 (3)2.936 (3)153 (3)
N4—H42···N20.90 (3)2.58 (3)2.913 (3)103 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+2; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC4H12N5+·NO3
Mr192.20
Crystal system, space groupTriclinic, P1
Temperature (K)184
a, b, c (Å)7.204 (3), 7.534 (3), 8.821 (4)
α, β, γ (°)78.109 (5), 73.979 (6), 85.353 (6)
V3)450.1 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.965, 0.988
No. of measured, independent and
observed [I > 2σ(I)] reflections
1875, 1559, 1181
Rint0.022
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.129, 1.01
No. of reflections1559
No. of parameters155
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.27, 0.20

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2000), SHELXTL.

Selected geometric parameters (Å, º) top
C1—N11.327 (3)C2—N51.324 (3)
C1—N21.335 (3)C2—N31.331 (3)
C1—N31.343 (3)C2—N41.336 (3)
N1—C1—N2118.7 (2)N3—C2—N4124.1 (2)
N1—C1—N3119.4 (2)C1—N1—C4121.3 (2)
N2—C1—N3121.6 (2)C1—N1—C3121.2 (2)
N5—C2—N3118.1 (2)C2—N3—C1121.5 (2)
N5—C2—N4117.8 (2)
N2—C1—N1—C4164.5 (3)N5—C2—N3—C1159.1 (2)
N3—C1—N1—C421.6 (4)N4—C2—N3—C123.8 (4)
N2—C1—N1—C36.3 (4)N1—C1—N3—C2147.5 (2)
N3—C1—N1—C3167.6 (2)N2—C1—N3—C238.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N5—H52···O1i0.85 (3)2.11 (3)2.962 (3)175 (3)
N5—H51···N3ii0.91 (3)2.10 (3)3.003 (3)171 (3)
N4—H41···O3i0.84 (3)2.12 (3)2.932 (3)162 (3)
N2—H21···O10.87 (3)2.13 (3)2.980 (3)166 (3)
N2—H22···O1iii0.89 (3)2.14 (3)3.009 (3)168 (3)
N4—H42···O3iv0.90 (3)2.10 (3)2.936 (3)153 (3)
N4—H42···N20.90 (3)2.58 (3)2.913 (3)103 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+2; (iii) x+1, y+1, z+1; (iv) x, y+1, z+1.
 

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