Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108007567/em3010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108007567/em3010Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108007567/em3010IIsup3.hkl |
CCDC references: 690172; 690173
The synthesis of N2,N6-bis(1,3-dimethylimidazolidin-2-ylidene)pyridine-2,6-diamine is described in the literature (Herres-Pawlis et al., 2005). For the preparation of (I), a solution of Mn(ClO4)2.6H2O (362 mg, 1 mmol) in MeCN (quantity?) was treated at room temperature with N2,N6-bis(1,3-dimethylimidazolidin-2-ylidene)pyridine-2,6-diamine (331 mg, 1.1 mmol). The clear solution was stirred for one hour, and diffusion of Et2O gave colourless crystals suitable for X-ray diffraction after three days. IR (KBr, ν, cm-1): 3486 (s), 2949 (w), 2871 (w), 1617 (m), 1585 (vs, C═N), 1536 (vs, C═ N), 1448 (s), 1417 (m), 1382 (s), 1294 (m), 1240 (w), 1166 (m), 960 (m), 838 (s), 557 (m). For the preparation of (II), a solution of FeCl2 (127 mg, 1 mmol) in CH2Cl2 (quantity?) was treated at room temperature with N2,N6-bis(1,3-dimethylimidazolidin-2-ylidene)pyridine-2,6-diamine (331 mg, 1.1 mmol) to yield a yellow solution. After 30 min at reflux, the solution was filtered and allowed to stand in air. After 2 days, red crystals suitable for X-ray diffraction were obtained. IR (KBr, ν, cm-1): 3423 (m), 2935 (w), 2875 (w), 1629 (m), 1596 (vs, C═N), 1562 (s, C═N), 1520 (vs), 1479 (s), 1446 (m), 1390 (s), 1361 (s), 1295 (m) 1250 (s), 1165 (s), 1049 (m), 960 (m), 877 (w), 785 (w), 673 (m), 569 (w).
Npy-bound H atoms were refined with N—H distance restraints of 0.88 (1) Å. All other H atoms were refined at idealized positions riding on their parent C atoms with Uiso(H) parameters of 1.2Ueq(C) or 1.5Ueq(CH3). All CH3 H atoms were allowed to rotate but not to tip. The disordered perchlorate anions of (I) were refined with an isotropic split model for O-atom positions O11/O12, O51/O52 and O61/O62, each with a site occupation factor of 0.5.
For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C15H24N7+·ClO4− | Z = 4 |
Mr = 401.86 | F(000) = 848 |
Triclinic, P1 | Dx = 1.435 Mg m−3 Dm = 0 Mg m−3 Dm measured by not measured |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4399 (11) Å | Cell parameters from 1687 reflections |
b = 12.0367 (13) Å | θ = 2.4–21.8° |
c = 16.6200 (18) Å | µ = 0.24 mm−1 |
α = 95.979 (2)° | T = 120 K |
β = 93.739 (2)° | Prism, colourless |
γ = 115.549 (2)° | 0.35 × 0.20 × 0.18 mm |
V = 1859.9 (3) Å3 |
Bruker SMART APEX diffractometer | 8994 independent reflections |
Radiation source: sealed tube | 3686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
ϕ and ω scans | θmax = 28.1°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −13→13 |
Tmin = 0.920, Tmax = 0.960 | k = −15→15 |
18737 measured reflections | l = −21→21 |
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)] = 0.064 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.83 | w = 1/[σ2(Fo2) + (0.0481P)2] where P = (Fo2 + 2Fc2)/3 |
8994 reflections | (Δ/σ)max < 0.001 |
499 parameters | Δρmax = 0.73 e Å−3 |
9 restraints | Δρmin = −0.45 e Å−3 |
C15H24N7+·ClO4− | γ = 115.549 (2)° |
Mr = 401.86 | V = 1859.9 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.4399 (11) Å | Mo Kα radiation |
b = 12.0367 (13) Å | µ = 0.24 mm−1 |
c = 16.6200 (18) Å | T = 120 K |
α = 95.979 (2)° | 0.35 × 0.20 × 0.18 mm |
β = 93.739 (2)° |
Bruker SMART APEX diffractometer | 8994 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 3686 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 0.960 | Rint = 0.093 |
18737 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 9 restraints |
wR(F2) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.83 | Δρmax = 0.73 e Å−3 |
8994 reflections | Δρmin = −0.45 e Å−3 |
499 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 | Occ. (<1) | |
N1 | 0.4193 (3) | 0.7986 (3) | 0.30531 (18) | 0.0298 (7) | |
N2 | 0.2195 (3) | 0.7556 (3) | 0.22891 (18) | 0.0361 (8) | |
N3 | 0.1938 (3) | 0.6525 (3) | 0.34145 (17) | 0.0257 (7) | |
N4 | 0.1482 (3) | 0.5201 (3) | 0.43559 (17) | 0.0233 (7) | |
H4 | 0.085 (3) | 0.547 (3) | 0.448 (2) | 0.031 (7)* | |
N5 | 0.0428 (3) | 0.3750 (3) | 0.51835 (18) | 0.0265 (7) | |
N7 | 0.1384 (3) | 0.2929 (3) | 0.61883 (18) | 0.0306 (8) | |
N6 | −0.0726 (3) | 0.1735 (2) | 0.55170 (18) | 0.0279 (7) | |
C1 | 0.5115 (4) | 0.8253 (3) | 0.3806 (2) | 0.0355 (10) | |
H10D | 0.4550 | 0.7809 | 0.4218 | 0.053* | |
H10E | 0.5563 | 0.9150 | 0.3997 | 0.053* | |
H10F | 0.5859 | 0.7979 | 0.3712 | 0.053* | |
C2 | 0.4649 (4) | 0.8748 (3) | 0.2406 (2) | 0.0352 (10) | |
H10I | 0.5195 | 0.8457 | 0.2046 | 0.042* | |
H10J | 0.5249 | 0.9633 | 0.2634 | 0.042* | |
C3 | 0.3254 (4) | 0.8573 (3) | 0.1949 (2) | 0.0394 (10) | |
H10G | 0.3111 | 0.9335 | 0.2049 | 0.047* | |
H10H | 0.3223 | 0.8350 | 0.1355 | 0.047* | |
C4 | 0.0690 (4) | 0.6979 (4) | 0.1986 (2) | 0.0385 (10) | |
H10A | 0.0161 | 0.6350 | 0.2323 | 0.058* | |
H10B | 0.0550 | 0.6582 | 0.1421 | 0.058* | |
H10C | 0.0336 | 0.7614 | 0.2008 | 0.058* | |
C5 | 0.2768 (4) | 0.7299 (3) | 0.2956 (2) | 0.0264 (8) | |
C6 | 0.2329 (4) | 0.5754 (3) | 0.3792 (2) | 0.0230 (8) | |
C7 | 0.3394 (4) | 0.5383 (3) | 0.3625 (2) | 0.0257 (8) | |
H10K | 0.4050 | 0.5766 | 0.3254 | 0.031* | |
C8 | 0.3470 (4) | 0.4450 (3) | 0.4009 (2) | 0.0298 (9) | |
H10L | 0.4193 | 0.4197 | 0.3897 | 0.036* | |
C9 | 0.2543 (4) | 0.3870 (3) | 0.4548 (2) | 0.0295 (9) | |
H10M | 0.2609 | 0.3215 | 0.4793 | 0.035* | |
C10 | 0.1504 (4) | 0.4263 (3) | 0.4730 (2) | 0.0240 (8) | |
C11 | 0.0397 (4) | 0.2857 (3) | 0.5609 (2) | 0.0241 (8) | |
C12 | −0.2082 (4) | 0.1369 (3) | 0.5029 (2) | 0.0355 (10) | |
H11D | −0.2056 | 0.2073 | 0.4771 | 0.053* | |
H11E | −0.2850 | 0.1116 | 0.5379 | 0.053* | |
H11F | −0.2258 | 0.0669 | 0.4608 | 0.053* | |
C13 | −0.0588 (4) | 0.1033 (3) | 0.6152 (2) | 0.0304 (9) | |
H11I | −0.0864 | 0.0155 | 0.5928 | 0.036* | |
H11J | −0.1176 | 0.1060 | 0.6591 | 0.036* | |
C14 | 0.1006 (4) | 0.1726 (3) | 0.6458 (2) | 0.0361 (10) | |
H11G | 0.1182 | 0.1810 | 0.7058 | 0.043* | |
H11H | 0.1544 | 0.1304 | 0.6207 | 0.043* | |
C15 | 0.2695 (4) | 0.4028 (3) | 0.6505 (3) | 0.0434 (11) | |
H11A | 0.3502 | 0.3961 | 0.6273 | 0.065* | |
H11B | 0.2845 | 0.4100 | 0.7100 | 0.065* | |
H11C | 0.2624 | 0.4768 | 0.6355 | 0.065* | |
N1B | 0.8872 (3) | 0.8037 (2) | 0.79216 (17) | 0.0256 (7) | |
N2B | 1.0488 (3) | 0.7664 (3) | 0.73194 (19) | 0.0370 (8) | |
N3B | 0.9617 (3) | 0.6540 (3) | 0.83672 (17) | 0.0241 (7) | |
N4B | 0.8704 (3) | 0.5182 (2) | 0.92639 (17) | 0.0210 (7) | |
H4B | 0.9621 (14) | 0.547 (3) | 0.9457 (19) | 0.031 (7)* | |
N5B | 0.8266 (3) | 0.3693 (2) | 1.00946 (17) | 0.0247 (7) | |
N6B | 0.7360 (3) | 0.1658 (2) | 1.04175 (17) | 0.0248 (7) | |
N7B | 0.6413 (3) | 0.2831 (2) | 1.09544 (17) | 0.0252 (7) | |
C1B | 0.8148 (4) | 0.8241 (3) | 0.8596 (2) | 0.0302 (9) | |
H20D | 0.8269 | 0.7798 | 0.9035 | 0.045* | |
H20E | 0.7127 | 0.7931 | 0.8410 | 0.045* | |
H20F | 0.8559 | 0.9134 | 0.8798 | 0.045* | |
C2B | 0.9248 (4) | 0.8871 (3) | 0.7314 (2) | 0.0326 (9) | |
H20I | 0.9636 | 0.9750 | 0.7571 | 0.039* | |
H20J | 0.8408 | 0.8677 | 0.6914 | 0.039* | |
C3B | 1.0391 (4) | 0.8621 (3) | 0.6907 (2) | 0.0341 (9) | |
H20G | 1.0093 | 0.8329 | 0.6316 | 0.041* | |
H20H | 1.1317 | 0.9377 | 0.6988 | 0.041* | |
C4B | 1.1335 (4) | 0.7043 (3) | 0.7069 (2) | 0.0370 (10) | |
H20A | 1.1239 | 0.6412 | 0.7420 | 0.056* | |
H20B | 1.2341 | 0.7652 | 0.7115 | 0.056* | |
H20C | 1.1003 | 0.6641 | 0.6502 | 0.056* | |
C5B | 0.9615 (4) | 0.7355 (3) | 0.7895 (2) | 0.0240 (8) | |
C6B | 0.8430 (4) | 0.5760 (3) | 0.8656 (2) | 0.0223 (8) | |
C7B | 0.7009 (4) | 0.5381 (3) | 0.8373 (2) | 0.0239 (8) | |
H20K | 0.6752 | 0.5774 | 0.7968 | 0.029* | |
C8B | 0.5974 (4) | 0.4427 (3) | 0.8687 (2) | 0.0268 (8) | |
H20L | 0.4999 | 0.4174 | 0.8492 | 0.032* | |
C9B | 0.6288 (4) | 0.3821 (3) | 0.9271 (2) | 0.0242 (8) | |
H20M | 0.5549 | 0.3148 | 0.9464 | 0.029* | |
C10B | 0.7720 (4) | 0.4219 (3) | 0.9572 (2) | 0.0218 (8) | |
C11B | 0.7369 (3) | 0.2783 (3) | 1.0469 (2) | 0.0222 (8) | |
C12B | 0.8414 (4) | 0.1344 (3) | 1.0064 (2) | 0.0283 (9) | |
H21A | 0.9021 | 0.2019 | 0.9780 | 0.043* | |
H21B | 0.7928 | 0.0573 | 0.9676 | 0.043* | |
H21C | 0.9007 | 0.1226 | 1.0497 | 0.043* | |
C13B | 0.6481 (4) | 0.0937 (3) | 1.0995 (2) | 0.0260 (8) | |
H21G | 0.7075 | 0.0960 | 1.1492 | 0.031* | |
H21H | 0.5885 | 0.0060 | 1.0748 | 0.031* | |
C14B | 0.5561 (4) | 0.1615 (3) | 1.1184 (2) | 0.0284 (9) | |
H21I | 0.4610 | 0.1192 | 1.0853 | 0.034* | |
H21J | 0.5433 | 0.1679 | 1.1769 | 0.034* | |
C15B | 0.6087 (4) | 0.3876 (3) | 1.1160 (2) | 0.0341 (9) | |
H21D | 0.6852 | 0.4635 | 1.1023 | 0.051* | |
H21E | 0.6013 | 0.3984 | 1.1745 | 0.051* | |
H21F | 0.5178 | 0.3716 | 1.0851 | 0.051* | |
Cl1 | 0.52136 (11) | 0.80821 (9) | 0.61828 (6) | 0.0374 (3) | |
O11 | 0.5772 (7) | 0.8296 (7) | 0.7004 (4) | 0.066 (2)* | 0.50 |
O12 | 0.5313 (6) | 0.7574 (5) | 0.6928 (3) | 0.0422 (15)* | 0.50 |
O2 | 0.4741 (4) | 0.9008 (3) | 0.6159 (3) | 0.0993 (14) | |
O3 | 0.4058 (3) | 0.6962 (3) | 0.5771 (2) | 0.0839 (11) | |
O4 | 0.6386 (3) | 0.8309 (3) | 0.57352 (17) | 0.0496 (8) | |
Cl2 | 0.21733 (10) | 0.18930 (9) | 0.90326 (6) | 0.0367 (3) | |
O51 | 0.2283 (6) | 0.3116 (5) | 0.9423 (3) | 0.0447 (14)* | 0.50 |
O61 | 0.2643 (6) | 0.2127 (6) | 0.8281 (3) | 0.0483 (15)* | 0.50 |
O52 | 0.2469 (8) | 0.3025 (7) | 0.8784 (5) | 0.092 (2)* | 0.50 |
O62 | 0.2388 (7) | 0.1222 (6) | 0.8275 (4) | 0.0695 (19)* | 0.50 |
O7 | 0.0740 (3) | 0.1098 (3) | 0.90689 (19) | 0.0625 (9) | |
O8 | 0.3122 (3) | 0.1735 (3) | 0.96106 (17) | 0.0539 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0260 (18) | 0.0259 (17) | 0.0300 (18) | 0.0035 (14) | 0.0028 (14) | 0.0084 (14) |
N2 | 0.0310 (19) | 0.048 (2) | 0.0316 (19) | 0.0152 (16) | 0.0068 (16) | 0.0220 (16) |
N3 | 0.0244 (17) | 0.0303 (17) | 0.0242 (17) | 0.0120 (14) | 0.0044 (14) | 0.0111 (14) |
N4 | 0.0192 (16) | 0.0247 (17) | 0.0298 (18) | 0.0120 (14) | 0.0034 (14) | 0.0093 (14) |
N5 | 0.0186 (16) | 0.0253 (17) | 0.0370 (19) | 0.0076 (13) | 0.0063 (14) | 0.0180 (15) |
N7 | 0.0242 (17) | 0.0237 (17) | 0.044 (2) | 0.0080 (14) | 0.0000 (15) | 0.0178 (15) |
N6 | 0.0234 (17) | 0.0218 (16) | 0.0332 (18) | 0.0041 (14) | −0.0009 (14) | 0.0109 (14) |
C1 | 0.027 (2) | 0.029 (2) | 0.043 (2) | 0.0063 (17) | −0.0011 (19) | 0.0036 (19) |
C2 | 0.038 (2) | 0.026 (2) | 0.037 (2) | 0.0090 (18) | 0.011 (2) | 0.0096 (18) |
C3 | 0.055 (3) | 0.032 (2) | 0.034 (2) | 0.018 (2) | 0.010 (2) | 0.0157 (19) |
C4 | 0.035 (2) | 0.048 (3) | 0.037 (2) | 0.022 (2) | −0.0036 (19) | 0.011 (2) |
C5 | 0.031 (2) | 0.024 (2) | 0.027 (2) | 0.0140 (18) | 0.0071 (18) | 0.0049 (17) |
C6 | 0.0223 (19) | 0.0204 (19) | 0.0203 (19) | 0.0038 (16) | 0.0026 (16) | 0.0034 (15) |
C7 | 0.024 (2) | 0.0217 (19) | 0.031 (2) | 0.0086 (16) | 0.0091 (17) | 0.0049 (16) |
C8 | 0.025 (2) | 0.026 (2) | 0.041 (2) | 0.0134 (17) | 0.0079 (18) | 0.0062 (18) |
C9 | 0.029 (2) | 0.026 (2) | 0.040 (2) | 0.0148 (17) | 0.0073 (18) | 0.0118 (18) |
C10 | 0.024 (2) | 0.0179 (19) | 0.029 (2) | 0.0072 (16) | −0.0006 (17) | 0.0071 (16) |
C11 | 0.024 (2) | 0.026 (2) | 0.026 (2) | 0.0133 (17) | 0.0032 (16) | 0.0085 (17) |
C12 | 0.029 (2) | 0.034 (2) | 0.037 (2) | 0.0078 (18) | −0.0021 (19) | 0.0062 (19) |
C13 | 0.030 (2) | 0.024 (2) | 0.036 (2) | 0.0095 (17) | 0.0052 (18) | 0.0137 (17) |
C14 | 0.032 (2) | 0.035 (2) | 0.046 (3) | 0.0155 (19) | 0.0022 (19) | 0.022 (2) |
C15 | 0.027 (2) | 0.034 (2) | 0.061 (3) | 0.0069 (19) | −0.010 (2) | 0.012 (2) |
N1B | 0.0298 (17) | 0.0235 (16) | 0.0265 (17) | 0.0122 (14) | 0.0070 (14) | 0.0120 (14) |
N2B | 0.042 (2) | 0.045 (2) | 0.042 (2) | 0.0288 (17) | 0.0232 (17) | 0.0309 (17) |
N3B | 0.0242 (17) | 0.0257 (16) | 0.0265 (17) | 0.0127 (14) | 0.0061 (14) | 0.0113 (14) |
N4B | 0.0163 (16) | 0.0226 (16) | 0.0233 (16) | 0.0066 (14) | 0.0035 (14) | 0.0088 (13) |
N5B | 0.0218 (16) | 0.0221 (16) | 0.0316 (18) | 0.0082 (13) | 0.0088 (14) | 0.0134 (14) |
N6B | 0.0253 (17) | 0.0211 (16) | 0.0304 (18) | 0.0105 (13) | 0.0075 (14) | 0.0097 (14) |
N7B | 0.0245 (17) | 0.0221 (16) | 0.0307 (18) | 0.0098 (13) | 0.0111 (14) | 0.0077 (13) |
C1B | 0.031 (2) | 0.022 (2) | 0.038 (2) | 0.0117 (17) | 0.0042 (18) | 0.0028 (17) |
C2B | 0.036 (2) | 0.030 (2) | 0.034 (2) | 0.0123 (18) | 0.0063 (19) | 0.0211 (18) |
C3B | 0.038 (2) | 0.033 (2) | 0.029 (2) | 0.0110 (18) | 0.0073 (19) | 0.0152 (18) |
C4B | 0.030 (2) | 0.043 (2) | 0.040 (2) | 0.0158 (19) | 0.0107 (19) | 0.013 (2) |
C5B | 0.022 (2) | 0.0221 (19) | 0.024 (2) | 0.0068 (16) | −0.0023 (16) | 0.0056 (16) |
C6B | 0.027 (2) | 0.0223 (19) | 0.0199 (19) | 0.0124 (16) | 0.0037 (16) | 0.0070 (16) |
C7B | 0.029 (2) | 0.025 (2) | 0.0222 (19) | 0.0154 (17) | −0.0008 (16) | 0.0094 (16) |
C8B | 0.023 (2) | 0.025 (2) | 0.031 (2) | 0.0103 (17) | −0.0006 (17) | 0.0039 (17) |
C9B | 0.0218 (19) | 0.0180 (18) | 0.030 (2) | 0.0053 (15) | 0.0041 (16) | 0.0047 (16) |
C10B | 0.0213 (19) | 0.0197 (19) | 0.026 (2) | 0.0088 (16) | 0.0079 (16) | 0.0070 (16) |
C11B | 0.0194 (19) | 0.023 (2) | 0.0207 (19) | 0.0061 (16) | −0.0003 (16) | 0.0034 (16) |
C12B | 0.032 (2) | 0.026 (2) | 0.032 (2) | 0.0162 (17) | 0.0061 (18) | 0.0073 (17) |
C13B | 0.029 (2) | 0.024 (2) | 0.026 (2) | 0.0101 (16) | 0.0037 (17) | 0.0114 (16) |
C14B | 0.023 (2) | 0.027 (2) | 0.029 (2) | 0.0035 (16) | 0.0084 (17) | 0.0129 (17) |
C15B | 0.036 (2) | 0.029 (2) | 0.041 (2) | 0.0167 (18) | 0.0125 (19) | 0.0054 (18) |
Cl1 | 0.0386 (6) | 0.0389 (6) | 0.0413 (6) | 0.0247 (5) | −0.0010 (5) | 0.0031 (5) |
O2 | 0.102 (3) | 0.077 (3) | 0.147 (4) | 0.077 (2) | −0.014 (3) | −0.013 (2) |
O3 | 0.057 (2) | 0.043 (2) | 0.122 (3) | −0.0012 (16) | 0.001 (2) | −0.003 (2) |
O4 | 0.0403 (17) | 0.064 (2) | 0.0505 (19) | 0.0247 (15) | 0.0160 (15) | 0.0192 (16) |
Cl2 | 0.0254 (5) | 0.0384 (6) | 0.0451 (6) | 0.0108 (4) | 0.0054 (5) | 0.0156 (5) |
O7 | 0.0199 (15) | 0.062 (2) | 0.089 (2) | −0.0001 (14) | 0.0080 (16) | 0.0232 (19) |
O8 | 0.0368 (17) | 0.065 (2) | 0.053 (2) | 0.0153 (15) | −0.0072 (15) | 0.0211 (16) |
N1—C5 | 1.342 (4) | N3B—C5B | 1.319 (4) |
N1—C1 | 1.445 (4) | N3B—C6B | 1.348 (4) |
N1—C2 | 1.455 (4) | N4B—C10B | 1.352 (4) |
N2—C5 | 1.352 (4) | N4B—C6B | 1.366 (4) |
N2—C4 | 1.445 (4) | N4B—H4B | 0.888 (10) |
N2—C3 | 1.449 (4) | N5B—C11B | 1.341 (4) |
N3—C5 | 1.318 (4) | N5B—C10B | 1.357 (4) |
N3—C6 | 1.355 (4) | N6B—C11B | 1.344 (4) |
N4—C10 | 1.352 (4) | N6B—C12B | 1.448 (4) |
N4—C6 | 1.354 (4) | N6B—C13B | 1.455 (4) |
N4—H4 | 0.881 (10) | N7B—C11B | 1.340 (4) |
N5—C11 | 1.337 (4) | N7B—C15B | 1.452 (4) |
N5—C10 | 1.350 (4) | N7B—C14B | 1.455 (4) |
N7—C11 | 1.331 (4) | C1B—H20D | 0.9800 |
N7—C15 | 1.449 (4) | C1B—H20E | 0.9800 |
N7—C14 | 1.456 (4) | C1B—H20F | 0.9800 |
N6—C11 | 1.338 (4) | C2B—C3B | 1.530 (5) |
N6—C12 | 1.447 (4) | C2B—H20I | 0.9900 |
N6—C13 | 1.456 (4) | C2B—H20J | 0.9900 |
C1—H10D | 0.9800 | C3B—H20G | 0.9900 |
C1—H10E | 0.9800 | C3B—H20H | 0.9900 |
C1—H10F | 0.9800 | C4B—H20A | 0.9800 |
C2—C3 | 1.517 (5) | C4B—H20B | 0.9800 |
C2—H10I | 0.9900 | C4B—H20C | 0.9800 |
C2—H10J | 0.9900 | C6B—C7B | 1.383 (4) |
C3—H10G | 0.9900 | C7B—C8B | 1.373 (4) |
C3—H10H | 0.9900 | C7B—H20K | 0.9500 |
C4—H10A | 0.9800 | C8B—C9B | 1.377 (5) |
C4—H10B | 0.9800 | C8B—H20L | 0.9500 |
C4—H10C | 0.9800 | C9B—C10B | 1.397 (4) |
C6—C7 | 1.398 (4) | C9B—H20M | 0.9500 |
C7—C8 | 1.377 (5) | C12B—H21A | 0.9800 |
C7—H10K | 0.9500 | C12B—H21B | 0.9800 |
C8—C9 | 1.373 (5) | C12B—H21C | 0.9800 |
C8—H10L | 0.9500 | C13B—C14B | 1.532 (4) |
C9—C10 | 1.395 (4) | C13B—H21G | 0.9900 |
C9—H10M | 0.9500 | C13B—H21H | 0.9900 |
C12—H11D | 0.9800 | C14B—H21I | 0.9900 |
C12—H11E | 0.9800 | C14B—H21J | 0.9900 |
C12—H11F | 0.9800 | C15B—H21D | 0.9800 |
C13—C14 | 1.525 (5) | C15B—H21E | 0.9800 |
C13—H11I | 0.9900 | C15B—H21F | 0.9800 |
C13—H11J | 0.9900 | Cl1—O11 | 1.400 (6) |
C14—H11G | 0.9900 | Cl1—O2 | 1.403 (3) |
C14—H11H | 0.9900 | Cl1—O4 | 1.414 (3) |
C15—H11A | 0.9800 | Cl1—O3 | 1.428 (3) |
C15—H11B | 0.9800 | Cl1—O12 | 1.454 (5) |
C15—H11C | 0.9800 | Cl2—O52 | 1.376 (7) |
N1B—C5B | 1.350 (4) | Cl2—O61 | 1.384 (5) |
N1B—C1B | 1.449 (4) | Cl2—O7 | 1.395 (3) |
N1B—C2B | 1.451 (4) | Cl2—O8 | 1.420 (3) |
N2B—C5B | 1.334 (4) | Cl2—O51 | 1.499 (5) |
N2B—C3B | 1.436 (4) | Cl2—O62 | 1.507 (6) |
N2B—C4B | 1.438 (4) | ||
C5—N1—C1 | 124.8 (3) | C11B—N6B—C12B | 124.9 (3) |
C5—N1—C2 | 111.4 (3) | C11B—N6B—C13B | 110.5 (3) |
C1—N1—C2 | 121.3 (3) | C12B—N6B—C13B | 121.5 (3) |
C5—N2—C4 | 124.9 (3) | C11B—N7B—C15B | 127.0 (3) |
C5—N2—C3 | 111.9 (3) | C11B—N7B—C14B | 110.9 (3) |
C4—N2—C3 | 123.0 (3) | C15B—N7B—C14B | 121.7 (3) |
C5—N3—C6 | 122.4 (3) | N1B—C1B—H20D | 109.5 |
C10—N4—C6 | 126.0 (3) | N1B—C1B—H20E | 109.5 |
C10—N4—H4 | 118 (2) | H20D—C1B—H20E | 109.5 |
C6—N4—H4 | 116 (2) | N1B—C1B—H20F | 109.5 |
C11—N5—C10 | 119.5 (3) | H20D—C1B—H20F | 109.5 |
C11—N7—C15 | 126.0 (3) | H20E—C1B—H20F | 109.5 |
C11—N7—C14 | 111.0 (3) | N1B—C2B—C3B | 103.5 (3) |
C15—N7—C14 | 123.0 (3) | N1B—C2B—H20I | 111.1 |
C11—N6—C12 | 125.8 (3) | C3B—C2B—H20I | 111.1 |
C11—N6—C13 | 110.6 (3) | N1B—C2B—H20J | 111.1 |
C12—N6—C13 | 121.3 (3) | C3B—C2B—H20J | 111.1 |
N1—C1—H10D | 109.5 | H20I—C2B—H20J | 109.0 |
N1—C1—H10E | 109.5 | N2B—C3B—C2B | 103.2 (3) |
H10D—C1—H10E | 109.5 | N2B—C3B—H20G | 111.1 |
N1—C1—H10F | 109.5 | C2B—C3B—H20G | 111.1 |
H10D—C1—H10F | 109.5 | N2B—C3B—H20H | 111.1 |
H10E—C1—H10F | 109.5 | C2B—C3B—H20H | 111.1 |
N1—C2—C3 | 103.6 (3) | H20G—C3B—H20H | 109.1 |
N1—C2—H10I | 111.0 | N2B—C4B—H20A | 109.5 |
C3—C2—H10I | 111.0 | N2B—C4B—H20B | 109.5 |
N1—C2—H10J | 111.0 | H20A—C4B—H20B | 109.5 |
C3—C2—H10J | 111.0 | N2B—C4B—H20C | 109.5 |
H10I—C2—H10J | 109.0 | H20A—C4B—H20C | 109.5 |
N2—C3—C2 | 102.7 (3) | H20B—C4B—H20C | 109.5 |
N2—C3—H10G | 111.2 | N3B—C5B—N2B | 120.9 (3) |
C2—C3—H10G | 111.2 | N3B—C5B—N1B | 129.1 (3) |
N2—C3—H10H | 111.2 | N2B—C5B—N1B | 109.9 (3) |
C2—C3—H10H | 111.2 | N3B—C6B—N4B | 113.5 (3) |
H10G—C3—H10H | 109.1 | N3B—C6B—C7B | 129.4 (3) |
N2—C4—H10A | 109.5 | N4B—C6B—C7B | 116.8 (3) |
N2—C4—H10B | 109.5 | C8B—C7B—C6B | 119.0 (3) |
H10A—C4—H10B | 109.5 | C8B—C7B—H20K | 120.5 |
N2—C4—H10C | 109.5 | C6B—C7B—H20K | 120.5 |
H10A—C4—H10C | 109.5 | C7B—C8B—C9B | 122.8 (3) |
H10B—C4—H10C | 109.5 | C7B—C8B—H20L | 118.6 |
N3—C5—N1 | 130.3 (3) | C9B—C8B—H20L | 118.6 |
N3—C5—N2 | 120.5 (3) | C8B—C9B—C10B | 118.4 (3) |
N1—C5—N2 | 109.1 (3) | C8B—C9B—H20M | 120.8 |
N4—C6—N3 | 114.2 (3) | C10B—C9B—H20M | 120.8 |
N4—C6—C7 | 116.9 (3) | N4B—C10B—N5B | 115.0 (3) |
N3—C6—C7 | 128.6 (3) | N4B—C10B—C9B | 117.0 (3) |
C8—C7—C6 | 118.5 (3) | N5B—C10B—C9B | 127.7 (3) |
C8—C7—H10K | 120.8 | N7B—C11B—N5B | 127.9 (3) |
C6—C7—H10K | 120.8 | N7B—C11B—N6B | 109.9 (3) |
C9—C8—C7 | 122.7 (3) | N5B—C11B—N6B | 122.2 (3) |
C9—C8—H10L | 118.7 | N6B—C12B—H21A | 109.5 |
C7—C8—H10L | 118.7 | N6B—C12B—H21B | 109.5 |
C8—C9—C10 | 118.7 (3) | H21A—C12B—H21B | 109.5 |
C8—C9—H10M | 120.6 | N6B—C12B—H21C | 109.5 |
C10—C9—H10M | 120.6 | H21A—C12B—H21C | 109.5 |
N5—C10—N4 | 115.0 (3) | H21B—C12B—H21C | 109.5 |
N5—C10—C9 | 127.7 (3) | N6B—C13B—C14B | 102.0 (3) |
N4—C10—C9 | 117.0 (3) | N6B—C13B—H21G | 111.4 |
N7—C11—N5 | 127.7 (3) | C14B—C13B—H21G | 111.4 |
N7—C11—N6 | 109.9 (3) | N6B—C13B—H21H | 111.4 |
N5—C11—N6 | 122.3 (3) | C14B—C13B—H21H | 111.4 |
N6—C12—H11D | 109.5 | H21G—C13B—H21H | 109.2 |
N6—C12—H11E | 109.5 | N7B—C14B—C13B | 101.8 (3) |
H11D—C12—H11E | 109.5 | N7B—C14B—H21I | 111.4 |
N6—C12—H11F | 109.5 | C13B—C14B—H21I | 111.4 |
H11D—C12—H11F | 109.5 | N7B—C14B—H21J | 111.4 |
H11E—C12—H11F | 109.5 | C13B—C14B—H21J | 111.4 |
N6—C13—C14 | 102.0 (3) | H21I—C14B—H21J | 109.3 |
N6—C13—H11I | 111.4 | N7B—C15B—H21D | 109.5 |
C14—C13—H11I | 111.4 | N7B—C15B—H21E | 109.5 |
N6—C13—H11J | 111.4 | H21D—C15B—H21E | 109.5 |
C14—C13—H11J | 111.4 | N7B—C15B—H21F | 109.5 |
H11I—C13—H11J | 109.2 | H21D—C15B—H21F | 109.5 |
N7—C14—C13 | 101.8 (3) | H21E—C15B—H21F | 109.5 |
N7—C14—H11G | 111.4 | O11—Cl1—O2 | 101.5 (3) |
C13—C14—H11G | 111.4 | O11—Cl1—O4 | 105.7 (3) |
N7—C14—H11H | 111.4 | O2—Cl1—O4 | 111.7 (2) |
C13—C14—H11H | 111.4 | O11—Cl1—O3 | 125.7 (3) |
H11G—C14—H11H | 109.3 | O2—Cl1—O3 | 105.6 (2) |
N7—C15—H11A | 109.5 | O4—Cl1—O3 | 106.4 (2) |
N7—C15—H11B | 109.5 | O2—Cl1—O12 | 121.6 (3) |
H11A—C15—H11B | 109.5 | O4—Cl1—O12 | 113.7 (2) |
N7—C15—H11C | 109.5 | O3—Cl1—O12 | 94.8 (3) |
H11A—C15—H11C | 109.5 | O52—Cl2—O7 | 117.1 (3) |
H11B—C15—H11C | 109.5 | O61—Cl2—O7 | 119.3 (3) |
C5B—N1B—C1B | 126.0 (3) | O52—Cl2—O8 | 122.3 (4) |
C5B—N1B—C2B | 110.9 (3) | O61—Cl2—O8 | 115.7 (3) |
C1B—N1B—C2B | 120.4 (3) | O7—Cl2—O8 | 112.83 (18) |
C5B—N2B—C3B | 112.4 (3) | O61—Cl2—O51 | 104.1 (3) |
C5B—N2B—C4B | 125.0 (3) | O7—Cl2—O51 | 101.8 (2) |
C3B—N2B—C4B | 122.3 (3) | O8—Cl2—O51 | 99.4 (3) |
C5B—N3B—C6B | 122.7 (3) | O52—Cl2—O62 | 100.0 (4) |
C10B—N4B—C6B | 125.9 (3) | O7—Cl2—O62 | 98.5 (3) |
C10B—N4B—H4B | 119 (2) | O8—Cl2—O62 | 99.3 (3) |
C6B—N4B—H4B | 115 (2) | O51—Cl2—O62 | 144.4 (3) |
C11B—N5B—C10B | 119.1 (3) | ||
C5—N1—C2—C3 | 8.0 (4) | C5B—N1B—C2B—C3B | −1.3 (4) |
C1—N1—C2—C3 | −154.7 (3) | C1B—N1B—C2B—C3B | 161.4 (3) |
C5—N2—C3—C2 | 11.0 (4) | C5B—N2B—C3B—C2B | −1.2 (4) |
C4—N2—C3—C2 | −174.4 (3) | C4B—N2B—C3B—C2B | 173.1 (3) |
N1—C2—C3—N2 | −10.8 (4) | N1B—C2B—C3B—N2B | 1.4 (4) |
C6—N3—C5—N1 | −38.5 (5) | C6B—N3B—C5B—N2B | −147.1 (3) |
C6—N3—C5—N2 | 145.3 (3) | C6B—N3B—C5B—N1B | 37.0 (5) |
C1—N1—C5—N3 | −15.9 (6) | C3B—N2B—C5B—N3B | −176.2 (3) |
C2—N1—C5—N3 | −177.9 (3) | C4B—N2B—C5B—N3B | 9.7 (5) |
C1—N1—C5—N2 | 160.6 (3) | C3B—N2B—C5B—N1B | 0.4 (4) |
C2—N1—C5—N2 | −1.4 (4) | C4B—N2B—C5B—N1B | −173.7 (3) |
C4—N2—C5—N3 | −4.1 (5) | C1B—N1B—C5B—N3B | 15.3 (6) |
C3—N2—C5—N3 | 170.4 (3) | C2B—N1B—C5B—N3B | 176.9 (3) |
C4—N2—C5—N1 | 179.0 (3) | C1B—N1B—C5B—N2B | −160.9 (3) |
C3—N2—C5—N1 | −6.5 (4) | C2B—N1B—C5B—N2B | 0.6 (4) |
C10—N4—C6—N3 | 169.6 (3) | C5B—N3B—C6B—N4B | −166.9 (3) |
C10—N4—C6—C7 | −5.0 (5) | C5B—N3B—C6B—C7B | 20.3 (5) |
C5—N3—C6—N4 | 168.0 (3) | C10B—N4B—C6B—N3B | −168.9 (3) |
C5—N3—C6—C7 | −18.1 (5) | C10B—N4B—C6B—C7B | 4.8 (5) |
N4—C6—C7—C8 | 3.1 (5) | N3B—C6B—C7B—C8B | 169.9 (3) |
N3—C6—C7—C8 | −170.7 (3) | N4B—C6B—C7B—C8B | −2.7 (5) |
C6—C7—C8—C9 | 0.0 (5) | C6B—C7B—C8B—C9B | −0.4 (5) |
C7—C8—C9—C10 | −1.6 (5) | C7B—C8B—C9B—C10B | 1.8 (5) |
C11—N5—C10—N4 | −176.7 (3) | C6B—N4B—C10B—N5B | 171.5 (3) |
C11—N5—C10—C9 | 9.3 (5) | C6B—N4B—C10B—C9B | −3.4 (5) |
C6—N4—C10—N5 | −171.1 (3) | C11B—N5B—C10B—N4B | 175.9 (3) |
C6—N4—C10—C9 | 3.5 (5) | C11B—N5B—C10B—C9B | −9.9 (5) |
C8—C9—C10—N5 | 173.8 (3) | C8B—C9B—C10B—N4B | 0.0 (5) |
C8—C9—C10—N4 | 0.0 (5) | C8B—C9B—C10B—N5B | −174.2 (3) |
C15—N7—C11—N5 | 2.7 (6) | C15B—N7B—C11B—N5B | 2.7 (6) |
C14—N7—C11—N5 | −175.3 (3) | C14B—N7B—C11B—N5B | 175.1 (3) |
C15—N7—C11—N6 | −174.8 (3) | C15B—N7B—C11B—N6B | −179.4 (3) |
C14—N7—C11—N6 | 7.2 (4) | C14B—N7B—C11B—N6B | −7.0 (4) |
C10—N5—C11—N7 | 59.1 (5) | C10B—N5B—C11B—N7B | −58.2 (5) |
C10—N5—C11—N6 | −123.7 (4) | C10B—N5B—C11B—N6B | 124.1 (3) |
C12—N6—C11—N7 | 170.9 (3) | C12B—N6B—C11B—N7B | −168.8 (3) |
C13—N6—C11—N7 | 8.0 (4) | C13B—N6B—C11B—N7B | −8.5 (4) |
C12—N6—C11—N5 | −6.8 (5) | C12B—N6B—C11B—N5B | 9.2 (5) |
C13—N6—C11—N5 | −169.6 (3) | C13B—N6B—C11B—N5B | 169.6 (3) |
C11—N6—C13—C14 | −18.6 (4) | C11B—N6B—C13B—C14B | 19.0 (4) |
C12—N6—C13—C14 | 177.6 (3) | C12B—N6B—C13B—C14B | −179.8 (3) |
C11—N7—C14—C13 | −18.1 (4) | C11B—N7B—C14B—C13B | 18.2 (4) |
C15—N7—C14—C13 | 163.8 (3) | C15B—N7B—C14B—C13B | −169.0 (3) |
N6—C13—C14—N7 | 20.9 (4) | N6B—C13B—C14B—N7B | −21.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N5i | 0.88 (1) | 2.01 (1) | 2.885 (4) | 175 (3) |
N4B—H4B···N5Bii | 0.89 (1) | 2.04 (1) | 2.922 (4) | 174 (3) |
C1—H10E···O2iii | 0.98 | 2.41 | 3.229 (5) | 141 |
C2—H10J···O2iii | 0.99 | 2.45 | 3.219 (5) | 134 |
C1B—H20F···O7iv | 0.98 | 2.44 | 3.301 (4) | 146 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y+2, −z+1; (iv) x+1, y+1, z. |
(C15H24N7)2[Fe2Cl6O] | F(000) = 976 |
Mr = 945.22 | Dx = 1.503 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1781 reflections |
a = 10.5673 (8) Å | θ = 2.2–28.3° |
b = 10.9286 (8) Å | µ = 1.12 mm−1 |
c = 18.3329 (14) Å | T = 120 K |
β = 99.438 (2)° | Prism, red |
V = 2088.5 (3) Å3 | 0.43 × 0.25 × 0.20 mm |
Z = 2 |
Bruker SMART APEX diffractometer | 5142 independent reflections |
Radiation source: sealed tube | 3929 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ϕ and ω scans | θmax = 28.2°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −14→14 |
Tmin = 0.644, Tmax = 0.807 | k = −14→14 |
20962 measured reflections | l = −24→24 |
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)] = 0.045 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0646P)2] where P = (Fo2 + 2Fc2)/3 |
5142 reflections | (Δ/σ)max < 0.001 |
249 parameters | Δρmax = 0.96 e Å−3 |
1 restraint | Δρmin = −0.72 e Å−3 |
(C15H24N7)2[Fe2Cl6O] | V = 2088.5 (3) Å3 |
Mr = 945.22 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.5673 (8) Å | µ = 1.12 mm−1 |
b = 10.9286 (8) Å | T = 120 K |
c = 18.3329 (14) Å | 0.43 × 0.25 × 0.20 mm |
β = 99.438 (2)° |
Bruker SMART APEX diffractometer | 5142 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 3929 reflections with I > 2σ(I) |
Tmin = 0.644, Tmax = 0.807 | Rint = 0.066 |
20962 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 1 restraint |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.96 e Å−3 |
5142 reflections | Δρmin = −0.72 e Å−3 |
249 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 | ||
Fe1 | 0.10796 (3) | −0.07833 (3) | 0.456159 (17) | 0.02885 (11) | |
Cl1 | 0.13940 (7) | −0.27077 (6) | 0.49480 (4) | 0.0526 (2) | |
Cl2 | 0.03929 (7) | −0.07802 (7) | 0.33459 (3) | 0.04969 (19) | |
Cl3 | 0.29055 (6) | 0.02168 (6) | 0.48206 (4) | 0.04693 (18) | |
O1 | 0.0000 | 0.0000 | 0.5000 | 0.0813 (11) | |
N1 | 0.31587 (19) | 0.70020 (19) | 0.76065 (11) | 0.0363 (5) | |
N2 | 0.5183 (2) | 0.6560 (2) | 0.80379 (10) | 0.0383 (5) | |
N3 | 0.44032 (17) | 0.58018 (17) | 0.68759 (10) | 0.0279 (4) | |
N4 | 0.38268 (16) | 0.49413 (16) | 0.57400 (9) | 0.0216 (4) | |
H4 | 0.4539 (16) | 0.528 (2) | 0.5661 (15) | 0.046 (8)* | |
N5 | 0.37760 (16) | 0.39960 (16) | 0.46291 (9) | 0.0248 (4) | |
N6 | 0.38638 (16) | 0.23645 (16) | 0.38284 (10) | 0.0264 (4) | |
N7 | 0.20585 (17) | 0.33867 (18) | 0.36675 (10) | 0.0317 (4) | |
C1 | 0.2135 (2) | 0.7462 (2) | 0.70542 (15) | 0.0410 (6) | |
H1A | 0.2229 | 0.7133 | 0.6569 | 0.061* | |
H1B | 0.2176 | 0.8357 | 0.7041 | 0.061* | |
H1C | 0.1307 | 0.7208 | 0.7178 | 0.061* | |
C2 | 0.3481 (3) | 0.7679 (3) | 0.83068 (14) | 0.0481 (7) | |
H2A | 0.2794 | 0.7599 | 0.8612 | 0.058* | |
H2B | 0.3629 | 0.8557 | 0.8218 | 0.058* | |
C3 | 0.4701 (3) | 0.7055 (3) | 0.86695 (13) | 0.0465 (7) | |
H3A | 0.5311 | 0.7648 | 0.8943 | 0.056* | |
H3B | 0.4521 | 0.6400 | 0.9011 | 0.056* | |
C4 | 0.6344 (3) | 0.5822 (2) | 0.81291 (14) | 0.0436 (6) | |
H4A | 0.6558 | 0.5625 | 0.7642 | 0.065* | |
H4B | 0.6203 | 0.5062 | 0.8389 | 0.065* | |
H4C | 0.7052 | 0.6280 | 0.8418 | 0.065* | |
C5 | 0.4204 (2) | 0.6408 (2) | 0.74617 (11) | 0.0291 (5) | |
C6 | 0.34876 (19) | 0.51945 (19) | 0.64142 (11) | 0.0228 (4) | |
C7 | 0.2344 (2) | 0.4686 (2) | 0.65571 (11) | 0.0259 (4) | |
H7A | 0.2035 | 0.4869 | 0.7003 | 0.031* | |
C8 | 0.1669 (2) | 0.3912 (2) | 0.60412 (12) | 0.0271 (5) | |
H8A | 0.0896 | 0.3559 | 0.6144 | 0.033* | |
C9 | 0.20649 (19) | 0.36267 (19) | 0.53832 (11) | 0.0251 (4) | |
H9A | 0.1591 | 0.3068 | 0.5047 | 0.030* | |
C10 | 0.31875 (19) | 0.41802 (18) | 0.52187 (11) | 0.0226 (4) | |
C11 | 0.32300 (18) | 0.32753 (19) | 0.40762 (10) | 0.0225 (4) | |
C12 | 0.5111 (2) | 0.1920 (2) | 0.41635 (13) | 0.0316 (5) | |
H12A | 0.5457 | 0.2446 | 0.4582 | 0.047* | |
H12B | 0.5691 | 0.1934 | 0.3797 | 0.047* | |
H12C | 0.5033 | 0.1081 | 0.4338 | 0.047* | |
C13 | 0.3120 (2) | 0.1764 (2) | 0.31942 (11) | 0.0299 (5) | |
H13A | 0.3047 | 0.0874 | 0.3282 | 0.036* | |
H13B | 0.3507 | 0.1892 | 0.2744 | 0.036* | |
C14 | 0.1808 (2) | 0.2396 (2) | 0.31276 (13) | 0.0332 (5) | |
H14A | 0.1528 | 0.2719 | 0.2623 | 0.040* | |
H14B | 0.1146 | 0.1829 | 0.3254 | 0.040* | |
C15 | 0.1156 (2) | 0.4368 (2) | 0.37111 (14) | 0.0352 (5) | |
H15A | 0.1578 | 0.5023 | 0.4026 | 0.053* | |
H15B | 0.0425 | 0.4056 | 0.3923 | 0.053* | |
H15C | 0.0851 | 0.4689 | 0.3214 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.02239 (17) | 0.0393 (2) | 0.02508 (18) | 0.00218 (13) | 0.00447 (12) | −0.00348 (13) |
Cl1 | 0.0575 (4) | 0.0451 (4) | 0.0497 (4) | −0.0166 (3) | −0.0072 (3) | 0.0111 (3) |
Cl2 | 0.0573 (4) | 0.0568 (4) | 0.0293 (3) | −0.0050 (3) | −0.0098 (3) | −0.0033 (3) |
Cl3 | 0.0424 (4) | 0.0499 (4) | 0.0435 (4) | −0.0162 (3) | −0.0076 (3) | 0.0106 (3) |
O1 | 0.0544 (19) | 0.124 (3) | 0.072 (2) | 0.0340 (19) | 0.0291 (17) | −0.024 (2) |
N1 | 0.0397 (11) | 0.0408 (11) | 0.0305 (10) | −0.0076 (9) | 0.0119 (9) | −0.0133 (9) |
N2 | 0.0440 (12) | 0.0483 (13) | 0.0215 (9) | −0.0148 (10) | 0.0020 (8) | −0.0084 (9) |
N3 | 0.0267 (9) | 0.0375 (11) | 0.0187 (8) | −0.0052 (8) | 0.0011 (7) | −0.0055 (7) |
N4 | 0.0185 (8) | 0.0273 (9) | 0.0187 (8) | −0.0021 (7) | 0.0017 (7) | −0.0030 (7) |
N5 | 0.0189 (8) | 0.0340 (10) | 0.0209 (9) | −0.0017 (7) | 0.0011 (7) | −0.0071 (7) |
N6 | 0.0253 (9) | 0.0272 (9) | 0.0251 (9) | 0.0007 (7) | −0.0003 (7) | −0.0051 (7) |
N7 | 0.0246 (9) | 0.0387 (11) | 0.0286 (9) | 0.0040 (8) | −0.0056 (7) | −0.0117 (8) |
C1 | 0.0397 (14) | 0.0380 (14) | 0.0490 (15) | −0.0007 (11) | 0.0184 (12) | −0.0062 (11) |
C2 | 0.0663 (18) | 0.0471 (16) | 0.0368 (14) | −0.0173 (14) | 0.0257 (13) | −0.0188 (12) |
C3 | 0.0649 (18) | 0.0504 (16) | 0.0252 (12) | −0.0228 (14) | 0.0105 (12) | −0.0124 (11) |
C4 | 0.0431 (15) | 0.0523 (17) | 0.0308 (13) | −0.0112 (12) | −0.0073 (11) | 0.0044 (11) |
C5 | 0.0326 (11) | 0.0339 (12) | 0.0216 (10) | −0.0128 (9) | 0.0070 (9) | −0.0025 (9) |
C6 | 0.0242 (10) | 0.0260 (11) | 0.0171 (9) | 0.0016 (8) | −0.0004 (8) | −0.0003 (8) |
C7 | 0.0273 (11) | 0.0302 (11) | 0.0205 (10) | −0.0006 (9) | 0.0047 (8) | 0.0011 (8) |
C8 | 0.0224 (10) | 0.0316 (12) | 0.0273 (11) | −0.0013 (9) | 0.0036 (8) | 0.0041 (9) |
C9 | 0.0224 (10) | 0.0273 (11) | 0.0243 (10) | −0.0042 (8) | −0.0002 (8) | −0.0020 (8) |
C10 | 0.0197 (10) | 0.0268 (11) | 0.0200 (9) | 0.0038 (8) | −0.0006 (8) | −0.0014 (8) |
C11 | 0.0211 (10) | 0.0262 (11) | 0.0196 (9) | −0.0018 (8) | 0.0014 (8) | −0.0015 (8) |
C12 | 0.0270 (11) | 0.0317 (12) | 0.0355 (12) | 0.0053 (9) | 0.0031 (9) | −0.0017 (10) |
C13 | 0.0368 (12) | 0.0291 (12) | 0.0229 (10) | −0.0028 (9) | 0.0017 (9) | −0.0053 (9) |
C14 | 0.0357 (13) | 0.0319 (12) | 0.0283 (11) | −0.0036 (10) | −0.0056 (9) | −0.0073 (9) |
C15 | 0.0293 (12) | 0.0378 (13) | 0.0346 (13) | 0.0081 (10) | −0.0066 (10) | −0.0043 (10) |
Fe1—O1 | 1.7266 (3) | C2—C3 | 1.512 (4) |
Fe1—Cl3 | 2.2005 (7) | C2—H2A | 0.9900 |
Fe1—Cl1 | 2.2267 (8) | C2—H2B | 0.9900 |
Fe1—Cl2 | 2.2278 (7) | C3—H3A | 0.9900 |
O1—Fe1i | 1.7266 (3) | C3—H3B | 0.9900 |
N1—C5 | 1.345 (3) | C4—H4A | 0.9800 |
N1—C1 | 1.445 (3) | C4—H4B | 0.9800 |
N1—C2 | 1.472 (3) | C4—H4C | 0.9800 |
N2—C5 | 1.362 (3) | C6—C7 | 1.394 (3) |
N2—C3 | 1.444 (3) | C7—C8 | 1.377 (3) |
N2—C4 | 1.455 (3) | C7—H7A | 0.9500 |
N3—C5 | 1.308 (3) | C8—C9 | 1.376 (3) |
N3—C6 | 1.351 (3) | C8—H8A | 0.9500 |
N4—C10 | 1.360 (3) | C9—C10 | 1.408 (3) |
N4—C6 | 1.370 (2) | C9—H9A | 0.9500 |
N4—H4 | 0.871 (10) | C12—H12A | 0.9800 |
N5—C11 | 1.337 (2) | C12—H12B | 0.9800 |
N5—C10 | 1.348 (3) | C12—H12C | 0.9800 |
N6—C11 | 1.321 (3) | C13—C14 | 1.536 (3) |
N6—C12 | 1.444 (3) | C13—H13A | 0.9900 |
N6—C13 | 1.449 (3) | C13—H13B | 0.9900 |
N7—C11 | 1.343 (3) | C14—H14A | 0.9900 |
N7—C15 | 1.446 (3) | C14—H14B | 0.9900 |
N7—C14 | 1.461 (3) | C15—H15A | 0.9800 |
C1—H1A | 0.9800 | C15—H15B | 0.9800 |
C1—H1B | 0.9800 | C15—H15C | 0.9800 |
C1—H1C | 0.9800 | ||
O1—Fe1—Cl3 | 106.03 (3) | H4B—C4—H4C | 109.5 |
O1—Fe1—Cl1 | 113.31 (3) | N3—C5—N1 | 130.9 (2) |
Cl3—Fe1—Cl1 | 108.71 (3) | N3—C5—N2 | 119.7 (2) |
O1—Fe1—Cl2 | 109.46 (2) | N1—C5—N2 | 109.37 (19) |
Cl3—Fe1—Cl2 | 110.20 (3) | N3—C6—N4 | 113.45 (17) |
Cl1—Fe1—Cl2 | 109.08 (3) | N3—C6—C7 | 129.23 (18) |
Fe1—O1—Fe1i | 180.0 | N4—C6—C7 | 116.87 (18) |
C5—N1—C1 | 125.05 (19) | C8—C7—C6 | 118.90 (19) |
C5—N1—C2 | 109.5 (2) | C8—C7—H7A | 120.6 |
C1—N1—C2 | 118.4 (2) | C6—C7—H7A | 120.6 |
C5—N2—C3 | 110.2 (2) | C9—C8—C7 | 122.93 (19) |
C5—N2—C4 | 122.7 (2) | C9—C8—H8A | 118.5 |
C3—N2—C4 | 121.1 (2) | C7—C8—H8A | 118.5 |
C5—N3—C6 | 124.65 (19) | C8—C9—C10 | 118.59 (19) |
C10—N4—C6 | 125.73 (17) | C8—C9—H9A | 120.7 |
C10—N4—H4 | 119.0 (19) | C10—C9—H9A | 120.7 |
C6—N4—H4 | 115.2 (19) | N5—C10—N4 | 114.43 (17) |
C11—N5—C10 | 119.83 (17) | N5—C10—C9 | 128.57 (19) |
C11—N6—C12 | 125.86 (18) | N4—C10—C9 | 116.83 (18) |
C11—N6—C13 | 112.24 (17) | N6—C11—N5 | 121.62 (18) |
C12—N6—C13 | 121.74 (18) | N6—C11—N7 | 110.44 (17) |
C11—N7—C15 | 126.33 (18) | N5—C11—N7 | 127.80 (19) |
C11—N7—C14 | 111.01 (17) | N6—C12—H12A | 109.5 |
C15—N7—C14 | 122.60 (18) | N6—C12—H12B | 109.5 |
N1—C1—H1A | 109.5 | H12A—C12—H12B | 109.5 |
N1—C1—H1B | 109.5 | N6—C12—H12C | 109.5 |
H1A—C1—H1B | 109.5 | H12A—C12—H12C | 109.5 |
N1—C1—H1C | 109.5 | H12B—C12—H12C | 109.5 |
H1A—C1—H1C | 109.5 | N6—C13—C14 | 102.91 (17) |
H1B—C1—H1C | 109.5 | N6—C13—H13A | 111.2 |
N1—C2—C3 | 102.5 (2) | C14—C13—H13A | 111.2 |
N1—C2—H2A | 111.3 | N6—C13—H13B | 111.2 |
C3—C2—H2A | 111.3 | C14—C13—H13B | 111.2 |
N1—C2—H2B | 111.3 | H13A—C13—H13B | 109.1 |
C3—C2—H2B | 111.3 | N7—C14—C13 | 102.63 (17) |
H2A—C2—H2B | 109.2 | N7—C14—H14A | 111.2 |
N2—C3—C2 | 101.7 (2) | C13—C14—H14A | 111.2 |
N2—C3—H3A | 111.4 | N7—C14—H14B | 111.2 |
C2—C3—H3A | 111.4 | C13—C14—H14B | 111.2 |
N2—C3—H3B | 111.4 | H14A—C14—H14B | 109.2 |
C2—C3—H3B | 111.4 | N7—C15—H15A | 109.5 |
H3A—C3—H3B | 109.3 | N7—C15—H15B | 109.5 |
N2—C4—H4A | 109.5 | H15A—C15—H15B | 109.5 |
N2—C4—H4B | 109.5 | N7—C15—H15C | 109.5 |
H4A—C4—H4B | 109.5 | H15A—C15—H15C | 109.5 |
N2—C4—H4C | 109.5 | H15B—C15—H15C | 109.5 |
H4A—C4—H4C | 109.5 | ||
C5—N1—C2—C3 | −18.7 (3) | C7—C8—C9—C10 | −2.1 (3) |
C1—N1—C2—C3 | −170.9 (2) | C11—N5—C10—N4 | −179.22 (18) |
C5—N2—C3—C2 | −23.9 (3) | C11—N5—C10—C9 | 5.7 (3) |
C4—N2—C3—C2 | −177.3 (2) | C6—N4—C10—N5 | −174.28 (19) |
N1—C2—C3—N2 | 24.5 (2) | C6—N4—C10—C9 | 1.4 (3) |
C6—N3—C5—N1 | −30.1 (4) | C8—C9—C10—N5 | 176.8 (2) |
C6—N3—C5—N2 | 153.4 (2) | C8—C9—C10—N4 | 1.8 (3) |
C1—N1—C5—N3 | −22.4 (4) | C12—N6—C11—N5 | 8.9 (3) |
C2—N1—C5—N3 | −172.3 (2) | C13—N6—C11—N5 | −175.75 (19) |
C1—N1—C5—N2 | 154.4 (2) | C12—N6—C11—N7 | −175.1 (2) |
C2—N1—C5—N2 | 4.4 (3) | C13—N6—C11—N7 | 0.2 (3) |
C3—N2—C5—N3 | −169.8 (2) | C10—N5—C11—N6 | −127.9 (2) |
C4—N2—C5—N3 | −16.8 (3) | C10—N5—C11—N7 | 56.8 (3) |
C3—N2—C5—N1 | 13.1 (3) | C15—N7—C11—N6 | −171.7 (2) |
C4—N2—C5—N1 | 166.0 (2) | C14—N7—C11—N6 | 5.6 (3) |
C5—N3—C6—N4 | 162.0 (2) | C15—N7—C11—N5 | 4.0 (4) |
C5—N3—C6—C7 | −26.0 (4) | C14—N7—C11—N5 | −178.7 (2) |
C10—N4—C6—N3 | 168.84 (19) | C11—N6—C13—C14 | −5.5 (2) |
C10—N4—C6—C7 | −4.2 (3) | C12—N6—C13—C14 | 170.1 (2) |
N3—C6—C7—C8 | −168.0 (2) | C11—N7—C14—C13 | −8.6 (2) |
N4—C6—C7—C8 | 3.8 (3) | C15—N7—C14—C13 | 168.8 (2) |
C6—C7—C8—C9 | −0.8 (3) | N6—C13—C14—N7 | 8.0 (2) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N5ii | 0.87 (1) | 2.10 (1) | 2.964 (2) | 174 (3) |
C1—H1A···Cl1iii | 0.98 | 2.96 | 3.816 (3) | 146 |
C1—H1C···Cl2iv | 0.98 | 2.94 | 3.716 (3) | 137 |
C12—H12C···Cl3v | 0.98 | 2.83 | 3.469 (2) | 123 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z; (iv) x, −y+1/2, z+1/2; (v) −x+1, −y, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C15H24N7+·ClO4− | (C15H24N7)2[Fe2Cl6O] |
Mr | 401.86 | 945.22 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 10.4399 (11), 12.0367 (13), 16.6200 (18) | 10.5673 (8), 10.9286 (8), 18.3329 (14) |
α, β, γ (°) | 95.979 (2), 93.739 (2), 115.549 (2) | 90, 99.438 (2), 90 |
V (Å3) | 1859.9 (3) | 2088.5 (3) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.24 | 1.12 |
Crystal size (mm) | 0.35 × 0.20 × 0.18 | 0.43 × 0.25 × 0.20 |
Data collection | ||
Diffractometer | Bruker SMART APEX diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.920, 0.960 | 0.644, 0.807 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18737, 8994, 3686 | 20962, 5142, 3929 |
Rint | 0.093 | 0.066 |
(sin θ/λ)max (Å−1) | 0.662 | 0.665 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.147, 0.83 | 0.045, 0.113, 0.99 |
No. of reflections | 8994 | 5142 |
No. of parameters | 499 | 249 |
No. of restraints | 9 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.73, −0.45 | 0.96, −0.72 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).
N1—C5 | 1.342 (4) | N1B—C5B | 1.350 (4) |
N2—C5 | 1.352 (4) | N2B—C5B | 1.334 (4) |
N3—C5 | 1.318 (4) | N3B—C5B | 1.319 (4) |
N3—C6 | 1.355 (4) | N3B—C6B | 1.348 (4) |
N4—C10 | 1.352 (4) | N4B—C10B | 1.352 (4) |
N4—C6 | 1.354 (4) | N4B—C6B | 1.366 (4) |
N5—C11 | 1.337 (4) | N5B—C11B | 1.341 (4) |
N5—C10 | 1.350 (4) | N5B—C10B | 1.357 (4) |
N7—C11 | 1.331 (4) | N6B—C11B | 1.344 (4) |
N6—C11 | 1.338 (4) | N7B—C11B | 1.340 (4) |
N3—C5—N1 | 130.3 (3) | N3B—C5B—N2B | 120.9 (3) |
N3—C5—N2 | 120.5 (3) | N3B—C5B—N1B | 129.1 (3) |
N1—C5—N2 | 109.1 (3) | N2B—C5B—N1B | 109.9 (3) |
N7—C11—N5 | 127.7 (3) | N7B—C11B—N5B | 127.9 (3) |
N7—C11—N6 | 109.9 (3) | N7B—C11B—N6B | 109.9 (3) |
N5—C11—N6 | 122.3 (3) | N5B—C11B—N6B | 122.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N5i | 0.881 (10) | 2.007 (11) | 2.885 (4) | 175 (3) |
N4B—H4B···N5Bii | 0.888 (10) | 2.037 (11) | 2.922 (4) | 174 (3) |
C1—H10E···O2iii | 0.98 | 2.41 | 3.229 (5) | 141.0 |
C2—H10J···O2iii | 0.99 | 2.45 | 3.219 (5) | 134.3 |
C1B—H20F···O7iv | 0.98 | 2.44 | 3.301 (4) | 145.7 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y+2, −z+1; (iv) x+1, y+1, z. |
N1—C5 | 1.345 (3) | N4—C6 | 1.370 (2) |
N2—C5 | 1.362 (3) | N5—C11 | 1.337 (2) |
N3—C5 | 1.308 (3) | N5—C10 | 1.348 (3) |
N3—C6 | 1.351 (3) | N6—C11 | 1.321 (3) |
N4—C10 | 1.360 (3) | N7—C11 | 1.343 (3) |
N3—C5—N1 | 130.9 (2) | N6—C11—N5 | 121.62 (18) |
N3—C5—N2 | 119.7 (2) | N6—C11—N7 | 110.44 (17) |
N1—C5—N2 | 109.37 (19) | N5—C11—N7 | 127.80 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N5i | 0.871 (10) | 2.096 (10) | 2.964 (2) | 174 (3) |
C1—H1A···Cl1ii | 0.98 | 2.96 | 3.816 (3) | 146.3 |
C1—H1C···Cl2iii | 0.98 | 2.94 | 3.716 (3) | 137.1 |
C12—H12C···Cl3iv | 0.98 | 2.83 | 3.469 (2) | 123.2 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z; (iii) x, −y+1/2, z+1/2; (iv) −x+1, −y, −z+1. |
The development of discrete dimeric, trimeric and other higher-order ensembles is a significant field of research with possible applications in materials chemistry and nanotechnology. Furthermore, base pairs must be considered as playing a salient role in such critical areas as genetic coding, biological information storage and protein synthesis (Sessler et al., 2007). During synthesis of biomimetic complexes using iron and manganese salts, as well as ligands containing two guanidine (gua) N-donor functions and one pyridine N atom [N2,N6-bis(1,3-dimethylimidazolidin-2-ylidene)pyridine-2,6-diamine; Herres-Pawlis et al., 2005; Neuba et al., 2008], we synthesized the title compounds, (I) and (II), with an interesting base-pair arrangement in the crystal structure.
The Cgua–N formal single bonds in (I), with a mean bond length of 1.340 (4) Å, have the same length as the double bonds C5═N3 and C11═N5 [average 1.327 (4) Å]. In (II), the corresponding Cgua—N and C═N bonds have average lengths of 1.343 (3) and 1.323 (3) Å, respectively. Thus, the guanidyl double bonds in (I) and (II) are clearly delocalized over the three C—N bonds.
Similar delocalization of the guanidyl double bonds is known from the protonated form of bis(tetramethylguanidino)biphenyl (Pruszynski et al., 1992), but with a protonated Ngua atom instead. 2-Cyanoguanidine with C–N bonds in the range 1.3327–1.3441 Å (Hirshfeld & Hope, 1980) also shows delocalization, but this is due to the cyano groups attached to the imine N atom. Localized C═N bond lengths in nonprotonated bisguanidine ligands range from 1.276 Å in N,N'-bis(dipiperidin-1-ylmethylene)propane-1,3-diamine (Herres et al., 2004) to 1.302 Å in 2',2'-(2,2'-dithiodiphenylene)bis(1,1,3,3-tetramethylguanidine) (Neuba et al., 2007b). Cgua—N single bond lengths vary from 1.362 Å in N,N'-bis(1,3-dimethylimidazolindin-2-ylidene)-2,2'-dithiodianiline (Neuba et al., 2007a) to 1.407 Å in N,N'-bis(dipiperidin-1-ylmethylene)propane-1,3-diamine (Herres et al., 2004).
Furthermore, the Cgua—Ngua bond lengths in (I) and (II) are similar to the Ngua—Cpy and Cpy—Npy distances. The pyridine ring and both guanidine units lie in a plane, showing that the guanidine delocalization is extended over the pyridine ring. In consequence, the protonation occurs at the Npy atom and not the Ngua atom, which indicates that the basicity of the Npy atom is increased compared with that of the Ngua atom. Normally, the Ngua position is found to be more basic. In this special case, the protonation leads to a pyridinium species, which is stabilized by mesomeric effects from both guanidyl units.
The exocyclic N—Cgua—N angles show, for both structures, the same significant differences of 5.5–11.2° within each pair, but the angle sum at the Cgua atom in both (I) and (II) is 360°. Other geometric parameters of C═N, Cgua—N, Ngua—Cpy and Cpy—Npy for (I) and (II) are nearly identical (see Tables 1 and 3).
The crystal packing for both compounds (Figs. 1–4) is dominated by pairs of intermolecular hydrogen-bond interactions between the protonated pyridine atom N4 and the nonprotonated guanidine atom N5gua of a centrosymmetrically related neighbouring molecule, stabilizing the structure with Ngua···H interactions of 2.007 (11) and 2.037 (11) Å in (I) and 2.096 (10) Å in (II). Additionally, these dimers form weak C—H···O and C—H···Cl bridges to the respective anions in (I) and (II). Thus the packing pattern of (II) shows infinite –dimer–anion–dimer– chains along [010]. For geometric details see Tables 2 and 4.
Similarly generated dimers incorporating Npy+–H and C═N functions are reported for 2-hydroxy(5-{[4- (2-pyridinylamino)sulfonyl]phenyl}azo)benzoic acid–N,N-dimethylformamide–water (1/0.5/n) (van der Sluis & Spek, 1990), 2-(nitroamino)pyridine (Angelova et al., 1998) and ethyl 3-[4,5-dimethoxy-2-(4-methyl-2- pyridylsulphamoyl)phenyl]propionate (Eliopoulos et al., 1983). The hydrogen-bond lengths in these structures range from 1.839 to 1.950 Å.
Similar dimers formed via N—H···N hydrogen bonds are reported for 2-(4-bromophenyl)-1,2-dihydropyrimido[1,2-a]benzimidazol-4(3H)-one and 4-(4-methylphenyl)-3,4-dihydropyrimido[1,2-a]benzimidazol-2(1H)-one (Low, Cobo, Insuasty et al., 2002). Here, the hydrogen bonds are formed between an aliphatic N—H and a C═N group with N···H distances from 1.98 to 2.30 Å. Similar geometries are observed in 2,2-dimethyl-1,2,3,4-tetrahydrobenzimidazo[3,2-a]pyrimid-4-one, with a hydrogen-bond length of 2.18 Å (Bird et al., 1991), and 2-phenyl-5-p-tolyl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline, 5-(4-bromophenyl)-2-phenyl-1,5,6,10b-tetrahydropyrazolo[1,5-c]quinazoline and 2-(4-chlorophenyl)-5-phenyl-1,5,6,10b- tetrahydropyrazolo[1,5-c]quinazoline, with an average N···H distance of 2.23 Å (Low, Cobo, Nogueras et al., 2002).