Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106029532/fa3022sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106029532/fa3022Isup2.hkl |
CCDC reference: 621292
the addition of equimolar quantities of 1,9-diethyladenine iodide (Itaya et al., 1972) and Re2(CH3COO)2Cl4·2H2O (Chakravarty et al., 1986) in ethanol resulted in a purple precipitate. The precipitate was treated with 0.2 molar equivalents of Re2(CH3CH2COO)4Cl2 (Brignole & Cotton, 1971) in acetonitrile. The resulting purple solid was removed by filtration and slow evaporation of the filtrate gave red crystals of the starting material [Should this be (I)?] suitable for X-ray diffraction.
Displacement ellipsoids did not show any abnormalities. H atoms were positioned geometrically after each cycle. All H atoms were included in the refinement in calculated positions as riding models, with N—H = 0.88 Å, and C—H = 0.95 for Ar—H, 0.99 for CH2, and 0.98 Å for CH3, and with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(C) for methyl H. [Please check added text]
Data collection: SMART (Siemens, 1993); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).
3C9H14N5+·I3−·2I− | F(000) = 2296 |
Mr = 1211.26 | Dx = 2.020 Mg m−3 |
MonoclinicP21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5476 reflections |
a = 12.3570 (9) Å | θ = 2.4–27.2° |
b = 10.3185 (7) Å | µ = 3.95 mm−1 |
c = 31.305 (2) Å | T = 100 K |
β = 93.876 (1)° | Prism, red |
V = 3982.4 (5) Å3 | 0.25 × 0.20 × 0.18 mm |
Z = 4 |
Brruker SMART CCD area-detector diffractometer | 8826 independent reflections |
Radiation source: fine-focus sealed tube | 7819 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
φ and ω scans | θmax = 27.5°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −15→15 |
Tmin = 0.439, Tmax = 0.537 | k = −13→13 |
31380 measured reflections | l = −39→39 |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0218P)2 + 5.0719P] where P = (Fo2 + 2Fc2)/3 |
8826 reflections | (Δ/σ)max = 0.022 |
424 parameters | Δρmax = 0.95 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
3C9H14N5+·I3−·2I− | V = 3982.4 (5) Å3 |
Mr = 1211.26 | Z = 4 |
MonoclinicP21/c | Mo Kα radiation |
a = 12.3570 (9) Å | µ = 3.95 mm−1 |
b = 10.3185 (7) Å | T = 100 K |
c = 31.305 (2) Å | 0.25 × 0.20 × 0.18 mm |
β = 93.876 (1)° |
Brruker SMART CCD area-detector diffractometer | 8826 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 7819 reflections with I > 2σ(I) |
Tmin = 0.439, Tmax = 0.537 | Rint = 0.031 |
31380 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.95 e Å−3 |
8826 reflections | Δρmin = −0.59 e Å−3 |
424 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 | ||
N1A | 0.4065 (2) | 0.6966 (2) | 0.84301 (8) | 0.0173 (5) | |
C2A | 0.4862 (3) | 0.7811 (3) | 0.83158 (10) | 0.0221 (7) | |
H2A | 0.5191 | 0.8341 | 0.8536 | 0.026* | |
N3A | 0.5203 (2) | 0.7949 (3) | 0.79351 (8) | 0.0206 (6) | |
C4A | 0.4671 (2) | 0.7171 (3) | 0.76460 (10) | 0.0159 (6) | |
C5A | 0.3841 (2) | 0.6319 (3) | 0.77174 (10) | 0.0139 (6) | |
C6A | 0.3513 (2) | 0.6187 (3) | 0.81361 (10) | 0.0153 (6) | |
N6A | 0.2759 (2) | 0.5377 (2) | 0.82461 (8) | 0.0165 (5) | |
H6A1 | 0.2598 | 0.5325 | 0.8515 | 0.020* | |
H6A2 | 0.2416 | 0.4887 | 0.8051 | 0.020* | |
N7A | 0.3484 (2) | 0.5706 (2) | 0.73440 (8) | 0.0154 (5) | |
C8A | 0.4107 (2) | 0.6188 (3) | 0.70597 (10) | 0.0171 (6) | |
H8A | 0.4051 | 0.5943 | 0.6767 | 0.021* | |
N9A | 0.4843 (2) | 0.7076 (2) | 0.72242 (8) | 0.0149 (5) | |
C13A | 0.3869 (3) | 0.6904 (3) | 0.88911 (10) | 0.0217 (7) | |
H13A | 0.3091 | 0.6730 | 0.8923 | 0.026* | |
H14A | 0.4049 | 0.7750 | 0.9026 | 0.026* | |
C15A | 0.4543 (3) | 0.5855 (4) | 0.91158 (11) | 0.0295 (8) | |
H15A | 0.4397 | 0.5836 | 0.9419 | 0.044* | |
H16A | 0.5314 | 0.6033 | 0.9088 | 0.044* | |
H17A | 0.4356 | 0.5014 | 0.8985 | 0.044* | |
C20A | 0.5663 (3) | 0.7826 (3) | 0.70081 (10) | 0.0196 (7) | |
H20A | 0.6379 | 0.7716 | 0.7166 | 0.024* | |
H21A | 0.5472 | 0.8757 | 0.7014 | 0.024* | |
C22A | 0.5740 (3) | 0.7402 (3) | 0.65525 (11) | 0.0266 (8) | |
H22A | 0.6292 | 0.7921 | 0.6420 | 0.040* | |
H23A | 0.5037 | 0.7525 | 0.6394 | 0.040* | |
H24A | 0.5943 | 0.6484 | 0.6546 | 0.040* | |
N1B | 0.3080 (2) | 0.4613 (2) | 0.46298 (8) | 0.0151 (5) | |
C2B | 0.3821 (2) | 0.5604 (3) | 0.46873 (10) | 0.0170 (6) | |
H2B | 0.4530 | 0.5448 | 0.4598 | 0.020* | |
N3B | 0.36430 (19) | 0.6728 (2) | 0.48513 (8) | 0.0168 (5) | |
C4B | 0.2623 (2) | 0.6849 (3) | 0.49724 (9) | 0.0160 (6) | |
C5B | 0.1805 (2) | 0.5946 (3) | 0.49265 (9) | 0.0151 (6) | |
C6B | 0.2033 (2) | 0.4743 (3) | 0.47443 (10) | 0.0159 (6) | |
N6B | 0.1323 (2) | 0.3795 (2) | 0.46865 (8) | 0.0192 (6) | |
H6B1 | 0.1517 | 0.3058 | 0.4572 | 0.023* | |
H6B2 | 0.0656 | 0.3898 | 0.4762 | 0.023* | |
N7B | 0.0880 (2) | 0.6400 (3) | 0.50999 (8) | 0.0183 (6) | |
C8B | 0.1160 (2) | 0.7559 (3) | 0.52410 (10) | 0.0195 (7) | |
H8B | 0.0679 | 0.8118 | 0.5377 | 0.023* | |
N9B | 0.2204 (2) | 0.7885 (2) | 0.51742 (8) | 0.0185 (6) | |
C13B | 0.3462 (3) | 0.3371 (3) | 0.44561 (10) | 0.0200 (7) | |
H13B | 0.4123 | 0.3530 | 0.4302 | 0.024* | |
H14B | 0.2898 | 0.3020 | 0.4248 | 0.024* | |
C15B | 0.3712 (3) | 0.2383 (3) | 0.48069 (11) | 0.0248 (7) | |
H15B | 0.3963 | 0.1577 | 0.4681 | 0.037* | |
H16B | 0.3054 | 0.2211 | 0.4956 | 0.037* | |
H17B | 0.4279 | 0.2722 | 0.5011 | 0.037* | |
C20B | 0.2806 (3) | 0.9070 (3) | 0.53013 (12) | 0.0266 (8) | |
H20B | 0.3098 | 0.9463 | 0.5045 | 0.032* | |
H21B | 0.3427 | 0.8837 | 0.5503 | 0.032* | |
C22B | 0.2115 (3) | 1.0050 (3) | 0.55094 (11) | 0.0275 (8) | |
H22B | 0.2552 | 1.0818 | 0.5587 | 0.041* | |
H23B | 0.1837 | 0.9674 | 0.5768 | 0.041* | |
H24B | 0.1506 | 1.0298 | 0.5309 | 0.041* | |
N1C | 0.0798 (2) | 0.2378 (2) | 0.66445 (8) | 0.0179 (6) | |
C2C | −0.0083 (3) | 0.1661 (3) | 0.67542 (11) | 0.0244 (7) | |
H2C | −0.0465 | 0.1194 | 0.6530 | 0.029* | |
N3C | −0.0442 (2) | 0.1561 (3) | 0.71316 (9) | 0.0248 (6) | |
C4C | 0.0159 (2) | 0.2254 (3) | 0.74275 (10) | 0.0182 (7) | |
C5C | 0.1046 (2) | 0.3011 (3) | 0.73582 (10) | 0.0145 (6) | |
C6C | 0.1399 (2) | 0.3098 (3) | 0.69439 (10) | 0.0160 (6) | |
N6C | 0.22291 (19) | 0.3800 (2) | 0.68407 (8) | 0.0168 (5) | |
H6C1 | 0.2412 | 0.3818 | 0.6574 | 0.020* | |
H6C2 | 0.2602 | 0.4253 | 0.7038 | 0.020* | |
N7C | 0.1468 (2) | 0.3541 (2) | 0.77378 (8) | 0.0174 (5) | |
C8C | 0.0829 (2) | 0.3099 (3) | 0.80245 (11) | 0.0199 (7) | |
H8C | 0.0922 | 0.3305 | 0.8320 | 0.024* | |
N9C | 0.0016 (2) | 0.2314 (3) | 0.78555 (8) | 0.0192 (6) | |
C13C | 0.1081 (3) | 0.2329 (3) | 0.61925 (10) | 0.0246 (7) | |
H13C | 0.0848 | 0.1484 | 0.6068 | 0.029* | |
H14C | 0.1879 | 0.2387 | 0.6183 | 0.029* | |
C15C | 0.0560 (3) | 0.3407 (4) | 0.59232 (11) | 0.0323 (9) | |
H15C | 0.0773 | 0.3330 | 0.5628 | 0.048* | |
H16C | 0.0800 | 0.4247 | 0.6041 | 0.048* | |
H17C | −0.0231 | 0.3343 | 0.5926 | 0.048* | |
C20C | −0.0820 (3) | 0.1618 (4) | 0.80749 (11) | 0.0326 (9) | |
H20C | −0.0666 | 0.0677 | 0.8066 | 0.039* | |
H21C | −0.1533 | 0.1767 | 0.7919 | 0.039* | |
C22C | −0.0883 (3) | 0.2026 (4) | 0.85325 (12) | 0.0306 (8) | |
H22C | −0.1452 | 0.1528 | 0.8662 | 0.046* | |
H23C | −0.1056 | 0.2952 | 0.8544 | 0.046* | |
H24C | −0.0185 | 0.1865 | 0.8691 | 0.046* | |
I43 | 0.248646 (17) | 0.97569 (2) | 0.760819 (8) | 0.02560 (6) | |
I44 | 0.18962 (2) | 0.96314 (2) | 0.849434 (8) | 0.03517 (7) | |
I45 | 0.31148 (2) | 0.98887 (2) | 0.673068 (8) | 0.03473 (7) | |
I46 | 0.652104 (17) | 0.98231 (2) | 0.912337 (7) | 0.02143 (6) | |
I47 | 0.134898 (17) | 0.45351 (2) | 0.921727 (7) | 0.01976 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0211 (13) | 0.0192 (13) | 0.0115 (13) | −0.0029 (11) | 0.0009 (11) | −0.0045 (10) |
C2A | 0.0283 (18) | 0.0221 (17) | 0.0155 (16) | −0.0075 (14) | −0.0005 (14) | −0.0062 (13) |
N3A | 0.0223 (14) | 0.0215 (14) | 0.0178 (14) | −0.0089 (11) | −0.0015 (12) | −0.0019 (11) |
C4A | 0.0169 (15) | 0.0158 (15) | 0.0154 (16) | 0.0017 (12) | 0.0035 (13) | 0.0004 (12) |
C5A | 0.0110 (13) | 0.0149 (14) | 0.0153 (15) | 0.0011 (11) | −0.0018 (12) | −0.0004 (12) |
C6A | 0.0132 (14) | 0.0139 (14) | 0.0184 (16) | 0.0027 (11) | −0.0009 (12) | −0.0002 (12) |
N6A | 0.0166 (13) | 0.0199 (13) | 0.0130 (13) | −0.0031 (10) | 0.0009 (11) | −0.0027 (10) |
N7A | 0.0169 (13) | 0.0154 (12) | 0.0141 (13) | −0.0011 (10) | 0.0019 (11) | −0.0017 (10) |
C8A | 0.0201 (15) | 0.0181 (15) | 0.0129 (15) | −0.0005 (12) | −0.0006 (13) | −0.0022 (12) |
N9A | 0.0145 (12) | 0.0146 (12) | 0.0161 (13) | −0.0020 (10) | 0.0035 (11) | −0.0002 (10) |
C13A | 0.0296 (18) | 0.0226 (16) | 0.0131 (16) | −0.0085 (14) | 0.0024 (14) | −0.0067 (13) |
C15A | 0.034 (2) | 0.041 (2) | 0.0135 (17) | 0.0001 (17) | 0.0010 (15) | 0.0014 (15) |
C20A | 0.0188 (16) | 0.0193 (16) | 0.0213 (17) | −0.0067 (13) | 0.0051 (14) | 0.0033 (13) |
C22A | 0.0316 (19) | 0.0249 (18) | 0.0246 (19) | −0.0068 (15) | 0.0116 (16) | 0.0001 (15) |
N1B | 0.0137 (12) | 0.0174 (13) | 0.0144 (13) | 0.0001 (10) | 0.0013 (10) | −0.0002 (10) |
C2B | 0.0143 (14) | 0.0233 (16) | 0.0136 (15) | −0.0008 (12) | 0.0031 (12) | 0.0053 (13) |
N3B | 0.0129 (12) | 0.0199 (13) | 0.0178 (14) | 0.0005 (10) | 0.0022 (11) | 0.0045 (11) |
C4B | 0.0164 (15) | 0.0203 (15) | 0.0111 (15) | 0.0015 (12) | −0.0015 (12) | 0.0028 (12) |
C5B | 0.0130 (14) | 0.0192 (15) | 0.0129 (15) | −0.0006 (12) | 0.0002 (12) | 0.0018 (12) |
C6B | 0.0150 (14) | 0.0220 (16) | 0.0106 (14) | 0.0015 (12) | 0.0001 (12) | 0.0030 (12) |
N6B | 0.0138 (12) | 0.0206 (14) | 0.0238 (15) | −0.0019 (11) | 0.0049 (11) | −0.0076 (11) |
N7B | 0.0139 (12) | 0.0242 (14) | 0.0168 (14) | 0.0024 (11) | 0.0004 (11) | −0.0023 (11) |
C8B | 0.0151 (15) | 0.0238 (16) | 0.0199 (17) | 0.0006 (13) | 0.0030 (13) | −0.0031 (13) |
N9B | 0.0170 (13) | 0.0183 (13) | 0.0205 (14) | 0.0004 (10) | 0.0033 (11) | −0.0034 (11) |
C13B | 0.0163 (15) | 0.0233 (16) | 0.0215 (17) | −0.0004 (13) | 0.0088 (13) | −0.0084 (13) |
C15B | 0.0193 (16) | 0.0217 (17) | 0.033 (2) | 0.0025 (13) | −0.0016 (15) | −0.0037 (15) |
C20B | 0.0227 (17) | 0.0201 (17) | 0.037 (2) | −0.0046 (14) | 0.0029 (16) | −0.0054 (15) |
C22B | 0.0325 (19) | 0.0263 (18) | 0.0244 (19) | −0.0052 (15) | 0.0071 (16) | −0.0063 (15) |
N1C | 0.0187 (13) | 0.0172 (13) | 0.0173 (14) | −0.0034 (10) | −0.0032 (11) | −0.0048 (11) |
C2C | 0.0240 (17) | 0.0229 (17) | 0.0254 (19) | −0.0101 (14) | −0.0064 (15) | −0.0069 (14) |
N3C | 0.0231 (15) | 0.0252 (15) | 0.0254 (16) | −0.0104 (12) | −0.0035 (13) | −0.0015 (12) |
C4C | 0.0190 (16) | 0.0172 (15) | 0.0178 (16) | −0.0031 (12) | −0.0037 (13) | 0.0013 (13) |
C5C | 0.0146 (14) | 0.0125 (14) | 0.0159 (16) | 0.0013 (11) | −0.0025 (12) | 0.0005 (12) |
C6C | 0.0139 (14) | 0.0141 (14) | 0.0194 (16) | 0.0044 (12) | −0.0037 (13) | −0.0032 (12) |
N6C | 0.0158 (13) | 0.0210 (13) | 0.0135 (13) | −0.0027 (10) | −0.0001 (11) | −0.0045 (11) |
N7C | 0.0160 (13) | 0.0177 (13) | 0.0186 (14) | −0.0014 (10) | 0.0011 (11) | −0.0012 (11) |
C8C | 0.0185 (16) | 0.0212 (16) | 0.0198 (17) | −0.0047 (13) | −0.0005 (14) | 0.0003 (13) |
N9C | 0.0196 (13) | 0.0202 (14) | 0.0177 (14) | −0.0081 (11) | 0.0003 (12) | 0.0032 (11) |
C13C | 0.0261 (18) | 0.0288 (18) | 0.0185 (17) | −0.0060 (14) | −0.0013 (14) | −0.0120 (14) |
C15C | 0.0263 (19) | 0.053 (2) | 0.0173 (18) | 0.0018 (17) | 0.0006 (15) | 0.0003 (17) |
C20C | 0.0296 (19) | 0.043 (2) | 0.025 (2) | −0.0217 (17) | 0.0031 (16) | 0.0035 (17) |
C22C | 0.0274 (19) | 0.033 (2) | 0.033 (2) | −0.0062 (16) | 0.0119 (16) | 0.0045 (16) |
I43 | 0.02348 (11) | 0.01799 (11) | 0.03477 (14) | 0.00156 (8) | −0.00224 (10) | 0.00062 (9) |
I44 | 0.03507 (14) | 0.03477 (14) | 0.03601 (15) | −0.00137 (11) | 0.00493 (11) | 0.00021 (11) |
I45 | 0.03723 (14) | 0.03208 (13) | 0.03464 (15) | 0.00698 (11) | 0.00062 (11) | 0.00412 (11) |
I46 | 0.01742 (10) | 0.03375 (12) | 0.01321 (10) | −0.00525 (9) | 0.00158 (8) | −0.00501 (8) |
I47 | 0.01974 (10) | 0.02323 (11) | 0.01622 (11) | 0.00090 (8) | 0.00063 (8) | 0.00575 (8) |
N1A—C6A | 1.369 (4) | N9B—C20B | 1.472 (4) |
N1A—C13A | 1.481 (4) | C13B—C15B | 1.515 (5) |
C2A—N1A | 1.380 (4) | C13B—H13B | 0.9900 |
C2A—H2A | 0.9500 | C13B—H14B | 0.9900 |
N3A—C2A | 1.299 (4) | C15B—H15B | 0.9800 |
C4A—N3A | 1.347 (4) | C15B—H16B | 0.9800 |
C4A—N9A | 1.355 (4) | C15B—H17B | 0.9800 |
C5A—N7A | 1.376 (4) | C20B—C22B | 1.500 (5) |
C5A—C4A | 1.380 (4) | C20B—H20B | 0.9900 |
C5A—C6A | 1.405 (4) | C20B—H21B | 0.9900 |
C6A—N6A | 1.314 (4) | C22B—H22B | 0.9800 |
N6A—H6A1 | 0.8800 | C22B—H23B | 0.9800 |
N6A—H6A2 | 0.8800 | C22B—H24B | 0.9800 |
C8A—N7A | 1.313 (4) | N1C—C6C | 1.374 (4) |
C8A—H8A | 0.9500 | N1C—C13C | 1.481 (4) |
N9A—C8A | 1.367 (4) | C2C—N1C | 1.379 (4) |
N9A—C20A | 1.475 (4) | C2C—H2C | 0.9500 |
C13A—C15A | 1.510 (5) | N3C—C2C | 1.294 (4) |
C13A—h13a | 0.9900 | C4C—N3C | 1.352 (4) |
C13A—H14A | 0.9900 | C4C—N9C | 1.364 (4) |
C15A—H15A | 0.9800 | C5C—C4C | 1.376 (4) |
C15A—H16A | 0.9800 | C5C—N7C | 1.378 (4) |
C15A—H17A | 0.9800 | C5C—C6C | 1.399 (4) |
C20A—C22A | 1.501 (4) | C6C—N6C | 1.314 (4) |
C20A—H20A | 0.9900 | N6C—H6C1 | 0.8800 |
C20A—H21A | 0.9900 | N6C—H6C2 | 0.8800 |
C22A—H22A | 0.9800 | C8C—N7C | 1.317 (4) |
C22A—H23A | 0.9800 | C8C—H8C | 0.9500 |
C22A—H24A | 0.9800 | N9C—C8C | 1.368 (4) |
N1B—C6B | 1.373 (4) | N9C—C20C | 1.467 (4) |
N1B—C13B | 1.481 (4) | C13C—C15C | 1.513 (5) |
C2B—N1B | 1.376 (4) | C13C—H13C | 0.9900 |
N3B—C2B | 1.293 (4) | C13C—H14C | 0.9900 |
C4B—N3B | 1.346 (4) | C15C—H15C | 0.9800 |
C4B—N9B | 1.362 (4) | C15C—H16C | 0.9800 |
C5B—C4B | 1.376 (4) | C15C—H17C | 0.9800 |
C5B—N7B | 1.380 (4) | C20C—C22C | 1.500 (5) |
C5B—C6B | 1.402 (4) | C20C—H20C | 0.9900 |
C6B—N6B | 1.318 (4) | C20C—H21C | 0.9900 |
N6B—H6B1 | 0.8800 | C22C—H22C | 0.9800 |
N6B—H6B2 | 0.8800 | C22C—H23C | 0.9800 |
C8B—N7B | 1.313 (4) | C22C—H24C | 0.9800 |
C8B—H8B | 0.9500 | i43—i45 | 2.9079 (4) |
N9B—C8B | 1.363 (4) | i43—i44 | 2.9186 (4) |
N1A—C2A—H2A | 117.0 | C8B—N7B—C5B | 103.6 (3) |
N1A—C6A—C5A | 114.0 (3) | N9B—C4B—C5B | 106.3 (3) |
N1A—C13A—C15A | 111.3 (3) | N9B—C8B—H8B | 123.1 |
N1A—C13A—H13a | 109.4 | N9B—C20B—C22B | 112.7 (3) |
N1A—C13A—H14A | 109.4 | N9B—C20B—H20B | 109.1 |
C2A—N3A—C4A | 112.1 (3) | N9B—C20B—H21B | 109.1 |
C2A—N1A—C13A | 116.6 (2) | H13B—C13B—H14B | 107.9 |
N3A—C2A—N1A | 126.1 (3) | C13B—C15B—H15B | 109.5 |
N3A—C2A—H2A | 117.0 | C13B—C15B—H16B | 109.5 |
N3A—C4A—N9A | 126.6 (3) | C13B—C15B—H17B | 109.5 |
N3A—C4A—C5A | 127.2 (3) | H15B—C15B—H16B | 109.5 |
C4A—C5A—C6A | 118.6 (3) | C15B—C13B—H13B | 109.3 |
C4A—N9A—C8A | 105.8 (2) | C15B—C13B—H14B | 109.3 |
C4A—N9A—C20A | 124.5 (3) | H15B—C15B—H17B | 109.5 |
C6A—N1A—C2A | 121.9 (3) | H16B—C15B—H17B | 109.5 |
C6A—N1A—C13A | 121.5 (3) | C20B—C22B—H24B | 109.5 |
C6A—N6A—H6A1 | 120.0 | H20B—C20B—H21B | 107.8 |
C6A—N6A—H6A2 | 120.0 | C20B—C22B—H22B | 109.5 |
H6A1—N6A—H6A2 | 120.0 | C20B—C22B—H23B | 109.5 |
N6A—C6A—N1A | 121.8 (3) | C22B—C20B—H21B | 109.1 |
N6A—C6A—C5A | 124.1 (3) | C22B—C20B—H20B | 109.1 |
N7A—C5A—C4A | 110.8 (3) | H22B—C22B—H23B | 109.5 |
N7A—C5A—C6A | 130.7 (3) | H22B—C22B—H24B | 109.5 |
N7A—C8A—N9A | 113.8 (3) | H23B—C22B—H24B | 109.5 |
N7A—C8A—H8A | 123.1 | N1C—C2C—H2C | 116.7 |
C8A—N9A—C20A | 129.7 (3) | N1C—C6C—C5C | 114.2 (3) |
C8A—N7A—C5A | 103.4 (2) | N1C—C13C—C15C | 112.8 (3) |
N9A—C4A—C5A | 106.2 (3) | N1C—C13C—H13C | 109.0 |
N9A—C8A—H8A | 123.1 | N1C—C13C—H14C | 109.0 |
N9A—C20A—C22A | 111.9 (3) | C2C—N3C—C4C | 112.2 (3) |
N9A—C20A—H20A | 109.2 | C2C—N1C—C13C | 117.5 (3) |
N9A—C20A—H21A | 109.2 | N3C—C2C—N1C | 126.5 (3) |
H13A—C13A—H14A | 108.0 | N3C—C2C—H2C | 116.7 |
C13A—C15A—H15A | 109.5 | N3C—C4C—N9C | 126.5 (3) |
C13A—C15A—H16A | 109.5 | N3C—C4C—C5C | 126.8 (3) |
C13A—C15A—H17A | 109.5 | C4C—C5C—N7C | 110.4 (3) |
C15A—C13A—h13a | 109.4 | C4C—C5C—C6C | 119.0 (3) |
C15A—C13A—H14A | 109.4 | C4C—N9C—C8C | 105.5 (2) |
H15A—C15A—H17A | 109.5 | C4C—N9C—C20C | 125.4 (3) |
H15A—C15A—H16A | 109.5 | C6C—N1C—C2C | 121.3 (3) |
H16A—C15A—H17A | 109.5 | C6C—N1C—C13C | 121.2 (3) |
H20A—C20A—H21A | 107.9 | N6C—C6C—N1C | 121.7 (3) |
C20A—C22A—H22A | 109.5 | N6C—C6C—C5C | 124.1 (3) |
C20A—C22A—H23A | 109.5 | C6C—N6C—H6C1 | 120.0 |
C20A—C22A—H24A | 109.5 | C6C—N6C—H6C2 | 120.0 |
C22A—C20A—H20A | 109.2 | H6C1—N6C—H6C2 | 120.0 |
C22A—C20A—H21A | 109.2 | N7C—C5C—C6C | 130.6 (3) |
H22A—C22A—H23A | 109.5 | N7C—C8C—N9C | 113.6 (3) |
H22A—C22A—H24A | 109.5 | N7C—C8C—H8C | 123.2 |
H23A—C22A—H24A | 109.5 | C8C—N7C—C5C | 103.9 (3) |
N1B—C2B—H2B | 117.0 | C8C—N9C—C20C | 129.1 (3) |
N1B—C6B—C5B | 114.3 (3) | N9C—C4C—C5C | 106.6 (3) |
N1B—C13B—C15B | 111.7 (3) | N9C—C8C—H8C | 123.2 |
N1B—C13B—H13B | 109.3 | N9C—C20C—C22C | 113.2 (3) |
N1B—C13B—H14B | 109.3 | N9C—C20C—H20C | 108.9 |
C2B—N1B—C13B | 117.7 (2) | N9C—C20C—H21C | 108.9 |
C2B—N3B—C4B | 112.5 (3) | H13C—C13C—H14C | 107.8 |
N3B—C2B—N1B | 126.0 (3) | C13C—C15C—H15C | 109.5 |
N3B—C2B—H2B | 117.0 | C13C—C15C—H16C | 109.5 |
N3B—C4B—N9B | 126.6 (3) | C13C—C15C—H17C | 109.5 |
N3B—C4B—C5B | 127.1 (3) | C15C—C13C—H13C | 109.0 |
C4B—C5B—N7B | 110.6 (3) | C15C—C13C—H14C | 109.0 |
C4B—C5B—C6B | 118.4 (3) | H15C—C15C—H16C | 109.5 |
C4B—N9B—C8B | 105.7 (3) | H15C—C15C—H17C | 109.5 |
C4B—N9B—C20B | 125.2 (3) | H16C—C15C—H17C | 109.5 |
C6B—N1B—C2B | 121.6 (3) | H20C—C20C—H21C | 107.8 |
C6B—N1B—C13B | 120.6 (2) | C20C—C22C—H22C | 109.5 |
N6B—C6B—N1B | 121.5 (3) | C20C—C22C—H23C | 109.5 |
N6B—C6B—C5B | 124.2 (3) | C20C—C22C—H24C | 109.5 |
C6B—N6B—H6B1 | 120.0 | C22C—C20C—H21C | 108.9 |
C6B—N6B—H6B2 | 120.0 | H22C—C22C—H23C | 109.5 |
H6B1—N6B—H6B2 | 120.0 | H22C—C22C—H24C | 109.5 |
N7B—C5B—C6B | 130.9 (3) | C22C—C20C—H20C | 108.9 |
N7B—C8B—N9B | 113.8 (3) | H23C—C22C—H24C | 109.5 |
N7B—C8B—H8B | 123.1 | i45—i43—i44 | 178.980 (11) |
C8B—N9B—C20B | 129.0 (3) | ||
C2A—N1A—C13A—C15A | −92.1 (3) | C5B—C4B—N3B—C2B | −2.0 (5) |
C2A—N1A—C6A—N6A | 179.6 (3) | C6B—C5B—C4B—N3B | 1.7 (5) |
C2A—N1A—C6A—C5A | 0.8 (4) | C6B—C5B—C4B—N9B | −177.0 (3) |
N3A—C4A—N9A—C8A | −179.1 (3) | C6B—C5B—N7B—C8B | 176.6 (3) |
N3A—C4A—N9A—C20A | 0.1 (5) | C6B—N1B—C13B—C15B | −78.2 (4) |
N3A—C2A—N1A—C6A | −2.1 (5) | N7B—C5B—C4B—N3B | 178.3 (3) |
N3A—C2A—N1A—C13A | 175.4 (3) | N7B—C5B—C4B—N9B | −0.4 (3) |
C4A—N9A—C8A—N7A | −0.4 (4) | N7B—C5B—C6B—N6B | 3.6 (5) |
C4A—N9A—C20A—C22A | 173.8 (3) | N7B—C5B—C6B—N1B | −175.9 (3) |
C4A—C5A—N7A—C8A | 0.6 (3) | C8B—N9B—C20B—C22B | −3.8 (5) |
C4A—N3A—C2A—N1A | 1.2 (5) | N9B—C4B—N3B—C2B | 176.4 (3) |
C4A—C5A—C6A—N6A | −177.6 (3) | N9B—C8B—N7B—C5B | −0.4 (4) |
C4A—C5A—C6A—N1A | 1.1 (4) | C13B—N1B—C6B—N6B | −3.0 (4) |
C5A—C4A—N9A—C8A | 0.7 (3) | C13B—N1B—C6B—C5B | 176.5 (3) |
C5A—C4A—N9A—C20A | 179.9 (3) | C20B—N9B—C8B—N7B | −177.6 (3) |
C5A—C4A—N3A—C2A | 1.0 (5) | C2C—N1C—C6C—N6C | −178.9 (3) |
C6A—C5A—C4A—N3A | −2.2 (5) | C2C—N1C—C13C—C15C | 92.9 (4) |
C6A—C5A—C4A—N9A | 178.1 (3) | C2C—N1C—C6C—C5C | 1.0 (4) |
C6A—C5A—N7A—C8A | −178.1 (3) | N3C—C4C—N9C—C8C | 178.4 (3) |
C6A—N1A—C13A—C15A | 85.4 (4) | N3C—C4C—N9C—C20C | 0.7 (5) |
N7A—C5A—C4A—N3A | 179.0 (3) | N3C—C2C—N1C—C6C | −0.6 (5) |
N7A—C5A—C4A—N9A | −0.8 (3) | N3C—C2C—N1C—C13C | 178.6 (3) |
N7A—C5A—C6A—N6A | 1.0 (5) | C4C—N9C—C20C—C22C | −171.4 (3) |
N7A—C5A—C6A—N1A | 179.7 (3) | C4C—N9C—C8C—N7C | 0.2 (4) |
C8A—N9A—C20A—C22A | −7.3 (5) | C4C—C5C—N7C—C8C | −0.2 (3) |
N9A—C4A—N3A—C2A | −179.3 (3) | C4C—N3C—C2C—N1C | −0.4 (5) |
N9A—C8A—N7A—C5A | −0.1 (3) | C4C—C5C—C6C—N6C | 179.3 (3) |
C13A—N1A—C6A—N6A | 2.2 (4) | C4C—C5C—C6C—N1C | −0.5 (4) |
C13A—N1A—C6A—C5A | −176.6 (3) | C5C—C4C—N9C—C8C | −0.4 (3) |
C20A—N9A—C8A—N7A | −179.5 (3) | C5C—C4C—N9C—C20C | −178.0 (3) |
C2B—N1B—C13B—C15B | 99.2 (3) | C5C—C4C—N3C—C2C | 0.9 (5) |
C2B—N1B—C6B—N6B | 179.6 (3) | C6C—C5C—C4C—N3C | −0.4 (5) |
C2B—N1B—C6B—C5B | −0.9 (4) | C6C—C5C—C4C—N9C | 178.3 (3) |
N3B—C4B—N9B—C20B | −0.6 (5) | C6C—C5C—N7C—C8C | −177.8 (3) |
N3B—C4B—N9B—C8B | −178.6 (3) | C6C—N1C—C13C—C15C | −88.0 (4) |
N3B—C2B—N1B—C6B | 0.5 (5) | N7C—C5C—C4C—N3C | −178.3 (3) |
N3B—C2B—N1B—C13B | −176.9 (3) | N7C—C5C—C4C—N9C | 0.4 (3) |
C4B—N9B—C8B—N7B | 0.2 (4) | N7C—C5C—C6C—N6C | −3.3 (5) |
C4B—C5B—N7B—C8B | 0.5 (3) | N7C—C5C—C6C—N1C | 176.9 (3) |
C4B—N9B—C20B—C22B | 178.8 (3) | C8C—N9C—C20C—C22C | 11.5 (5) |
C4B—N3B—C2B—N1B | 0.8 (4) | N9C—C4C—N3C—C2C | −177.6 (3) |
C4B—C5B—C6B—N6B | 179.4 (3) | N9C—C8C—N7C—C5C | 0.0 (4) |
C4B—C5B—C6B—N1B | −0.1 (4) | C13C—N1C—C6C—N6C | 2.0 (4) |
C5B—C4B—N9B—C8B | 0.1 (3) | C13C—N1C—C6C—C5C | −178.1 (3) |
C5B—C4B—N9B—C20B | 178.1 (3) | C20C—N9C—C8C—N7C | 177.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N6C—H6C2···N7A | 0.88 | 2.05 | 2.902 (3) | 162 |
N6B—H6B1···I47i | 0.88 | 2.90 | 3.738 (3) | 160 |
N6C—H6C1···I46ii | 0.88 | 2.82 | 3.638 (3) | 155 |
N6A—H6A1···I47 | 0.88 | 2.89 | 3.708 (3) | 156 |
N6B—H6B2···N7Biii | 0.88 | 2.00 | 2.854 (3) | 164 |
N6A—H6A2···N7C | 0.88 | 2.03 | 2.885 (4) | 165 |
C8A—H8A···I46ii | 0.95 | 3.05 | 3.989 (3) | 168 |
C2A—H2A···I46 | 0.95 | 2.83 | 3.769 (3) | 170 |
C2B—H2B···I46iv | 0.95 | 2.97 | 3.903 (3) | 167 |
C2C—H2C···I47v | 0.95 | 3.04 | 3.983 (3) | 171 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x, −y+1, −z+1; (iv) x, −y+3/2, z−1/2; (v) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | 3C9H14N5+·I3−·2I− |
Mr | 1211.26 |
Crystal system, space group | MonoclinicP21/c |
Temperature (K) | 100 |
a, b, c (Å) | 12.3570 (9), 10.3185 (7), 31.305 (2) |
β (°) | 93.876 (1) |
V (Å3) | 3982.4 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.95 |
Crystal size (mm) | 0.25 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Brruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.439, 0.537 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31380, 8826, 7819 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.062, 1.04 |
No. of reflections | 8826 |
No. of parameters | 424 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.95, −0.59 |
Computer programs: SMART (Siemens, 1993), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1996), CRYSTALS (Betteridge et al., 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N6C—H6C2···N7A | 0.88 | 2.05 | 2.902 (3) | 162.2 |
N6B—H6B1···I47i | 0.88 | 2.90 | 3.738 (3) | 159.8 |
N6C—H6C1···I46ii | 0.88 | 2.82 | 3.638 (3) | 154.8 |
N6A—H6A1···I47 | 0.88 | 2.89 | 3.708 (3) | 155.9 |
N6B—H6B2···N7Biii | 0.88 | 2.00 | 2.854 (3) | 163.9 |
N6A—H6A2···N7C | 0.88 | 2.03 | 2.885 (4) | 164.9 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x, −y+1, −z+1. |
Purine No. | A | B | C |
N1—C2 | 1.380 (4) | 1.376 (4) | 1.379 (4) |
C2—N3 | 1.299 (4) | 1.293 (4) | 1.294 (4) |
N3—N4 | 1.347 (4) | 1.346 (4) | 1.352 (4) |
C4—C5 | 1.380 (4) | 1.376 (4) | 1.376 (4) |
C5—C6 | 1.405 (4) | 1.402 (4) | 1.399 (4) |
C6—N6 | 1.314 (4) | 1.318 (4) | 1.314 (4) |
C6—N1 | 1.369 (4) | 1.373 (4) | 1.374 (4) |
C5—N7 | 1.376 (4) | 1.380 (4) | 1.378 (4) |
N7—C8 | 1.313 (4) | 1.313 (4) | 1.317 (4) |
C8—N9 | 1.367 (4) | 1.363 (4) | 1.368 (4) |
N9—C4 | 1.355 (4) | 1.362 (4) | 1.364 (4) |
N1–C2–N3 | 126.1 (3) | 126.0 (3) | 126.5 (3) |
C2–N3–C4 | 112.1 (3) | 112.5 (3) | 112.2 (3) |
N3–C4–C5 | 127.2 (3) | 127.1 (3) | 126.8 (3) |
C4–C5–C6 | 118.6 (3) | 118.4 (3) | 119.0 (3) |
C5–C6–N1 | 114.0 (3) | 114.3 (3) | 114.2 (3) |
C6–N1–C2 | 121.9 (3) | 121.6 (3) | 121.3 (3) |
N6–C6–N1 | 121.8 (3) | 121.5 (3) | 121.7 (3) |
C4–C5–N7 | 110.8 (3) | 110.6 (3) | 110.4 (3) |
C5–N7–C8 | 103.4 (2) | 103.6 (3) | 103.9 (3) |
N7–C8–N9 | 113.8 (3) | 113.8 (3) | 113.6 (3) |
C8–N9–C4 | 105.8 (2) | 105.7 (3) | 105.5 (2) |
N9–C4–C5 | 106.2 (3) | 106.3 (3) | 106.6 (3) |
Derivatized nucleobases have long been studied, due to the biological activity of the many compounds that contain them. Nucleoside analogues and substituted nucleobases are used as antiviral and anticancer therapeutic agents (Galmarini et al., 2002; Mitsuya et al., 1990). Additionally, modified nucleobases, including those with N1 alkylation, are present in natural systems such as tRNA (McCloskey & Nishimura, 1977; Rich, 1977). As a result, a detailed understanding of the structures and reactivity of nucleobase derivatives remains an important topic of research.
The title compound, (I), has three independent cations, A, B and C, in the asymmetric unit. Fig. 1 shows the independent components of (I) with the atom-numbering scheme. Selected bond distances and angles for the three cations are presented in Table 1, using the standard purine numbering scheme shown in the scheme.
The amine tautomeric form dominates for N9-substituted adenine derivatives under normal conditions, with <0.01% of the imine form in 9-ethyladenine and adenosine (Lippert et al., 1992). However, alkylation of the 1 position leads to imine stabilization (Dreyfus et al., 1977). Notable parameters to support imine formation in (I) are the shortening of the C6—N6 bond distance [1.314 (4), 1.318 (4) and 1.314 (4) Å in cations A, B and C, respectively] compared with 9-MeAH [1.329 (2) Å; Reference?] and the lengthening of the C6—N1 bond [1.369 (4), 1.373 (4) and 1.374 (4) Å in cations A, B and C, respectively] compared with 1.357 (2) Å obtained from the crystal structure of 9-MeAH (Kistenmacher & Rossi, 1977; Clowney et al., 1996). Although the differences are just at the limit of statistical significance, the clear trend supports the bonding description of the nucleobase derivative as being the imine form. The enhanced internal C6—N1—C2 angle [121.9 (3), 121.6 (3) and 121.3 (3)° for cations A, B and C, respectively] clearly shows the effects of a substituent on N1, compared with 118.7 (1)° for 9-MeAH. As expected, comparison between the purine parameters of the three cations of (I) shows that the three cations have the same dimensions within experimental error. Also, comparison of the geometric values for the cations of (I) with those for the cations of 1,9-dimethyladeninium chloride shows that the parameters of the purine ring are all within calculated error (Chiang et al., 1979).
The three unique cations in the asymmetric unit of (I) form two sets of hydrogen-bonded dimers (Fig. 2). Cations A and C form a hydrogen-bonded dimer via atoms N6 and N7 to give a ten-membered ring with two donors and two acceptors (N6A···N7C and N6C···N7A) [graph set R22(10); Bernstein et al., 1995]. Cation B similarly dimerizes with a neighbouring cation Bi at (-x, -y + 1, -z + 1) [N7B···N6Bi and N6Bi···N7B]. This pair lies on a crystallographic centre of symmetry, with the two hydrogen bonds having the same length. The angle between the planes of the two hydrogen-bonded dimers is 53.53 (6)°. There is additional hydrogen bonding to I- anions via the other N6 H atom (N6A···I47, N6B···I47 and N6C···I46). The triiodide anion is not involved in hydrogen bonding. Details of the hydrogen bonds are given in Table 2. A packing diagram is presented in Fig. 3 and illustrates the presence of alternating layers of B dimers and A···C dimers, as viewed down the b axis. Additionally, the hydrogen bonds to the anions are shown.
The triiodide anion is proposed to be a result of air oxidation of the I- anions present in the reaction mixture. This is a well documented reaction known to occur in acidic environments. According to a review by Svensson & Kloo (2003), the triiodide parameters of (I) are well within the expected range. Using these published parameters, the triiodide ion in (I) is defined as essentially linear, with I44—I43—I45 = 178.980 (11)°, and symmetric [I44—I43 = 2.9079 (4) Å and I43—I45 = 2.9186 (4) Å]. The triiodide anions in (I) do not have close contacts with any components of the unit cell.