Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803006639/ww6070sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803006639/ww6070Isup2.hkl |
CCDC reference: 209996
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).
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.
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.
C4H12N5+·NO3− | Z = 2 |
Mr = 192.20 | F(000) = 204 |
Triclinic, P1 | Dx = 1.418 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.204 (3) Å | Cell parameters from 2484 reflections |
b = 7.534 (3) Å | θ = 2.8–24.7° |
c = 8.821 (4) Å | µ = 0.12 mm−1 |
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 |
Bruker SMART 1K CCD area-detector diffractometer | 1559 independent reflections |
Radiation source: fine-focus sealed tube | 1181 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −5→8 |
Tmin = 0.965, Tmax = 0.988 | k = −7→8 |
1875 measured reflections | l = −10→10 |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | All 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 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C4H12N5+·NO3− | γ = 85.353 (6)° |
Mr = 192.20 | V = 450.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.204 (3) Å | Mo Kα radiation |
b = 7.534 (3) Å | µ = 0.12 mm−1 |
c = 8.821 (4) Å | T = 184 K |
α = 78.109 (5)° | 0.30 × 0.20 × 0.10 mm |
β = 73.979 (6)° |
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 = 0.988 | Rint = 0.022 |
1875 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.129 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.27 e Å−3 |
1559 reflections | Δρmin = −0.20 e Å−3 |
155 parameters |
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 | ||
C1 | 0.3203 (3) | 0.1619 (3) | 0.7195 (3) | 0.0232 (6) | |
C2 | 0.3318 (4) | 0.2505 (3) | 0.9550 (3) | 0.0236 (6) | |
C3 | 0.2488 (5) | 0.0584 (4) | 0.4995 (3) | 0.0315 (7) | |
C4 | 0.1365 (6) | −0.1112 (4) | 0.7791 (4) | 0.0477 (9) | |
N1 | 0.2468 (3) | 0.0374 (3) | 0.6676 (2) | 0.0251 (5) | |
N2 | 0.3802 (3) | 0.3163 (3) | 0.6177 (3) | 0.0290 (6) | |
N3 | 0.3490 (3) | 0.1233 (2) | 0.8670 (2) | 0.0262 (5) | |
N4 | 0.2262 (3) | 0.4036 (3) | 0.9364 (3) | 0.0309 (6) | |
N5 | 0.4182 (3) | 0.2203 (3) | 1.0727 (3) | 0.0342 (6) | |
N6 | 0.1893 (3) | 0.5910 (3) | 0.3001 (3) | 0.0316 (6) | |
O1 | 0.3340 (3) | 0.4826 (2) | 0.2927 (2) | 0.0312 (5) | |
O2 | 0.1352 (3) | 0.6691 (3) | 0.4143 (3) | 0.0542 (6) | |
O3 | 0.1053 (3) | 0.6168 (3) | 0.1917 (2) | 0.0534 (6) | |
H21 | 0.347 (4) | 0.357 (4) | 0.529 (4) | 0.051 (3)* | |
H22 | 0.451 (4) | 0.388 (4) | 0.646 (3) | 0.051 (3)* | |
H41 | 0.219 (4) | 0.468 (4) | 1.005 (4) | 0.051 (3)* | |
H42 | 0.151 (5) | 0.418 (4) | 0.868 (4) | 0.051 (3)* | |
H51 | 0.499 (4) | 0.123 (4) | 1.084 (3) | 0.051 (3)* | |
H52 | 0.401 (4) | 0.294 (4) | 1.138 (4) | 0.051 (3)* | |
H3A | 0.368 (5) | 0.110 (4) | 0.435 (4) | 0.051 (3)* | |
H4A | 0.006 (5) | −0.095 (4) | 0.782 (4) | 0.051 (3)* | |
H3B | 0.147 (4) | 0.141 (4) | 0.472 (3) | 0.051 (3)* | |
H4B | 0.170 (4) | −0.224 (4) | 0.745 (3) | 0.051 (3)* | |
H3C | 0.231 (4) | −0.060 (4) | 0.476 (3) | 0.051 (3)* | |
H4C | 0.146 (4) | −0.119 (4) | 0.885 (4) | 0.051 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0173 (13) | 0.0265 (13) | 0.0250 (13) | 0.0027 (11) | −0.0048 (11) | −0.0056 (10) |
C2 | 0.0249 (14) | 0.0258 (13) | 0.0191 (12) | −0.0013 (11) | −0.0055 (11) | −0.0025 (10) |
C3 | 0.0318 (17) | 0.0356 (16) | 0.0318 (15) | 0.0009 (13) | −0.0132 (13) | −0.0113 (12) |
C4 | 0.065 (2) | 0.0401 (18) | 0.0394 (18) | −0.0224 (18) | −0.0158 (18) | −0.0008 (14) |
N1 | 0.0258 (12) | 0.0255 (11) | 0.0256 (11) | −0.0022 (9) | −0.0083 (9) | −0.0059 (9) |
N2 | 0.0345 (14) | 0.0287 (12) | 0.0260 (12) | −0.0060 (10) | −0.0142 (11) | −0.0001 (9) |
N3 | 0.0320 (13) | 0.0250 (11) | 0.0242 (11) | 0.0030 (9) | −0.0126 (10) | −0.0052 (8) |
N4 | 0.0342 (14) | 0.0313 (13) | 0.0323 (13) | 0.0088 (10) | −0.0159 (11) | −0.0118 (10) |
N5 | 0.0455 (16) | 0.0329 (13) | 0.0322 (13) | 0.0131 (11) | −0.0219 (12) | −0.0141 (10) |
N6 | 0.0275 (13) | 0.0372 (13) | 0.0345 (13) | 0.0011 (11) | −0.0112 (11) | −0.0135 (10) |
O1 | 0.0291 (10) | 0.0319 (10) | 0.0367 (11) | 0.0084 (8) | −0.0137 (8) | −0.0126 (8) |
O2 | 0.0514 (14) | 0.0640 (14) | 0.0607 (14) | 0.0165 (11) | −0.0200 (12) | −0.0422 (12) |
O3 | 0.0410 (13) | 0.0811 (16) | 0.0530 (13) | 0.0201 (11) | −0.0317 (11) | −0.0286 (11) |
C1—N1 | 1.327 (3) | C4—H4B | 0.95 (3) |
C1—N2 | 1.335 (3) | C4—H4C | 0.95 (3) |
C1—N3 | 1.343 (3) | N2—H21 | 0.87 (3) |
C2—N5 | 1.324 (3) | N2—H22 | 0.89 (3) |
C2—N3 | 1.331 (3) | N4—H41 | 0.84 (3) |
C2—N4 | 1.336 (3) | N4—H42 | 0.90 (3) |
C3—N1 | 1.455 (3) | N5—H51 | 0.91 (3) |
C3—H3A | 0.95 (3) | N5—H52 | 0.85 (3) |
C3—H3B | 0.98 (3) | N6—O2 | 1.226 (3) |
C3—H3C | 0.98 (3) | N6—O3 | 1.241 (3) |
C4—N1 | 1.453 (4) | N6—O1 | 1.266 (3) |
C4—H4A | 0.93 (3) | ||
N1—C1—N2 | 118.7 (2) | H4B—C4—H4C | 111 (2) |
N1—C1—N3 | 119.4 (2) | C1—N1—C4 | 121.3 (2) |
N2—C1—N3 | 121.6 (2) | C1—N1—C3 | 121.2 (2) |
N5—C2—N3 | 118.1 (2) | C4—N1—C3 | 116.8 (2) |
N5—C2—N4 | 117.8 (2) | C1—N2—H21 | 125.2 (19) |
N3—C2—N4 | 124.1 (2) | C1—N2—H22 | 118.1 (19) |
N1—C3—H3A | 108.3 (17) | H21—N2—H22 | 117 (3) |
N1—C3—H3B | 112.5 (17) | C2—N3—C1 | 121.5 (2) |
H3A—C3—H3B | 107 (2) | C2—N4—H41 | 115 (2) |
N1—C3—H3C | 109.4 (16) | C2—N4—H42 | 118.8 (18) |
H3A—C3—H3C | 112 (2) | H41—N4—H42 | 125 (3) |
H3B—C3—H3C | 108 (2) | C2—N5—H51 | 120.1 (18) |
N1—C4—H4A | 110.5 (19) | C2—N5—H52 | 120 (2) |
N1—C4—H4B | 112.4 (18) | H51—N5—H52 | 119 (3) |
H4A—C4—H4B | 103 (3) | O2—N6—O3 | 121.2 (2) |
N1—C4—H4C | 111.9 (17) | O2—N6—O1 | 119.2 (2) |
H4A—C4—H4C | 107 (3) | O3—N6—O1 | 119.6 (2) |
N2—C1—N1—C4 | −164.5 (3) | N5—C2—N3—C1 | −159.1 (2) |
N3—C1—N1—C4 | 21.6 (4) | N4—C2—N3—C1 | 23.8 (4) |
N2—C1—N1—C3 | 6.3 (4) | N1—C1—N3—C2 | −147.5 (2) |
N3—C1—N1—C3 | −167.6 (2) | N2—C1—N3—C2 | 38.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H52···O1i | 0.85 (3) | 2.11 (3) | 2.962 (3) | 175 (3) |
N5—H51···N3ii | 0.91 (3) | 2.10 (3) | 3.003 (3) | 171 (3) |
N4—H41···O3i | 0.84 (3) | 2.12 (3) | 2.932 (3) | 162 (3) |
N2—H21···O1 | 0.87 (3) | 2.13 (3) | 2.980 (3) | 166 (3) |
N2—H22···O1iii | 0.89 (3) | 2.14 (3) | 3.009 (3) | 168 (3) |
N4—H42···O3iv | 0.90 (3) | 2.10 (3) | 2.936 (3) | 153 (3) |
N4—H42···N2 | 0.90 (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 formula | C4H12N5+·NO3− |
Mr | 192.20 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 450.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.965, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1875, 1559, 1181 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.129, 1.01 |
No. of reflections | 1559 |
No. of parameters | 155 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.27, −0.20 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2000), SHELXTL.
C1—N1 | 1.327 (3) | C2—N5 | 1.324 (3) |
C1—N2 | 1.335 (3) | C2—N3 | 1.331 (3) |
C1—N3 | 1.343 (3) | C2—N4 | 1.336 (3) |
N1—C1—N2 | 118.7 (2) | N3—C2—N4 | 124.1 (2) |
N1—C1—N3 | 119.4 (2) | C1—N1—C4 | 121.3 (2) |
N2—C1—N3 | 121.6 (2) | C1—N1—C3 | 121.2 (2) |
N5—C2—N3 | 118.1 (2) | C2—N3—C1 | 121.5 (2) |
N5—C2—N4 | 117.8 (2) | ||
N2—C1—N1—C4 | −164.5 (3) | N5—C2—N3—C1 | −159.1 (2) |
N3—C1—N1—C4 | 21.6 (4) | N4—C2—N3—C1 | 23.8 (4) |
N2—C1—N1—C3 | 6.3 (4) | N1—C1—N3—C2 | −147.5 (2) |
N3—C1—N1—C3 | −167.6 (2) | N2—C1—N3—C2 | 38.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H52···O1i | 0.85 (3) | 2.11 (3) | 2.962 (3) | 175 (3) |
N5—H51···N3ii | 0.91 (3) | 2.10 (3) | 3.003 (3) | 171 (3) |
N4—H41···O3i | 0.84 (3) | 2.12 (3) | 2.932 (3) | 162 (3) |
N2—H21···O1 | 0.87 (3) | 2.13 (3) | 2.980 (3) | 166 (3) |
N2—H22···O1iii | 0.89 (3) | 2.14 (3) | 3.009 (3) | 168 (3) |
N4—H42···O3iv | 0.90 (3) | 2.10 (3) | 2.936 (3) | 153 (3) |
N4—H42···N2 | 0.90 (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. |
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).