Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103024892/fa1036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103024892/fa1036Isup2.hkl |
CCDC reference: 220534
The complex was prepared according to the procedure reported by Das et al. (2001).
H atoms attached to N atoms of (I) were found in a difference map but were placed in idealized positions (N—H = 0.88 Å) and constrained to ride on their parent atoms [Uiso(H) = 1.2Ueq(N)].
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.
(C2H9N5)[Mn(C2H7N5)3](NO3)6 | Z = 2 |
Mr = 833.52 | F(000) = 858 |
Triclinic, P1 | Dx = 1.811 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4222 (19) Å | Cell parameters from 2688 reflections |
b = 12.803 (3) Å | θ = 2.4–26.5° |
c = 14.452 (3) Å | µ = 0.55 mm−1 |
α = 105.673 (2)° | T = 184 K |
β = 104.037 (2)° | Block, red |
γ = 104.891 (2)° | 0.25 × 0.20 × 0.20 mm |
V = 1528.3 (5) Å3 |
SMART 1K CCD area-detector diffractometer | 5274 independent reflections |
Radiation source: fine-focus sealed tube | 4160 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −11→11 |
Tmin = 0.874, Tmax = 0.898 | k = −15→15 |
6316 measured reflections | l = −15→17 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.058P)2] where P = (Fo2 + 2Fc2)/3 |
5274 reflections | (Δ/σ)max < 0.001 |
479 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
(C2H9N5)[Mn(C2H7N5)3](NO3)6 | γ = 104.891 (2)° |
Mr = 833.52 | V = 1528.3 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.4222 (19) Å | Mo Kα radiation |
b = 12.803 (3) Å | µ = 0.55 mm−1 |
c = 14.452 (3) Å | T = 184 K |
α = 105.673 (2)° | 0.25 × 0.20 × 0.20 mm |
β = 104.037 (2)° |
SMART 1K CCD area-detector diffractometer | 5274 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 4160 reflections with I > 2σ(I) |
Tmin = 0.874, Tmax = 0.898 | Rint = 0.022 |
6316 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.41 e Å−3 |
5274 reflections | Δρmin = −0.55 e Å−3 |
479 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 | ||
Mn1 | 0.26973 (5) | 0.33181 (4) | 0.13314 (3) | 0.01802 (14) | |
N1 | 0.1220 (3) | 0.3343 (2) | 0.20574 (18) | 0.0203 (6) | |
H1 | 0.0276 | 0.2842 | 0.1700 | 0.024* | |
N2 | 0.0191 (3) | 0.3822 (2) | 0.3351 (2) | 0.0286 (6) | |
H2A | −0.0725 | 0.3292 | 0.2972 | 0.034* | |
H2B | 0.0335 | 0.4258 | 0.3975 | 0.034* | |
N3 | 0.2738 (3) | 0.4796 (2) | 0.36239 (19) | 0.0262 (6) | |
H3 | 0.2743 | 0.5212 | 0.4220 | 0.031* | |
N4 | 0.4211 (3) | 0.4511 (2) | 0.25510 (18) | 0.0209 (6) | |
H4 | 0.5150 | 0.4744 | 0.2510 | 0.025* | |
N5 | 0.5320 (3) | 0.5868 (2) | 0.41870 (19) | 0.0306 (7) | |
H5A | 0.6236 | 0.6077 | 0.4109 | 0.037* | |
H5B | 0.5205 | 0.6205 | 0.4767 | 0.037* | |
C1 | 0.1359 (3) | 0.3964 (3) | 0.2980 (2) | 0.0220 (7) | |
C2 | 0.4118 (3) | 0.5047 (2) | 0.3433 (2) | 0.0224 (7) | |
N6 | 0.2130 (3) | 0.4427 (2) | 0.07551 (18) | 0.0207 (6) | |
H6 | 0.1875 | 0.4958 | 0.1141 | 0.025* | |
N7 | 0.1430 (3) | 0.5095 (2) | −0.0566 (2) | 0.0289 (6) | |
H7A | 0.0984 | 0.5522 | −0.0238 | 0.035* | |
H7B | 0.1437 | 0.5086 | −0.1176 | 0.035* | |
N8 | 0.2746 (3) | 0.3816 (2) | −0.07158 (19) | 0.0227 (6) | |
H8 | 0.2386 | 0.3624 | −0.1383 | 0.027* | |
N9 | 0.4186 (3) | 0.3410 (2) | 0.06021 (18) | 0.0200 (6) | |
H9 | 0.5118 | 0.3421 | 0.0916 | 0.024* | |
N10 | 0.4771 (3) | 0.3199 (2) | −0.0892 (2) | 0.0293 (6) | |
H10A | 0.5560 | 0.2984 | −0.0661 | 0.035* | |
H10B | 0.4547 | 0.3243 | −0.1505 | 0.035* | |
C3 | 0.2091 (3) | 0.4462 (2) | −0.0140 (2) | 0.0211 (7) | |
C4 | 0.3917 (3) | 0.3457 (2) | −0.0315 (2) | 0.0217 (7) | |
N11 | 0.3346 (3) | 0.2140 (2) | 0.17085 (19) | 0.0199 (5) | |
H11 | 0.3701 | 0.2268 | 0.2366 | 0.024* | |
N12 | 0.4179 (3) | 0.0574 (2) | 0.1385 (2) | 0.0266 (6) | |
H12A | 0.4814 | 0.0825 | 0.2018 | 0.032* | |
H12B | 0.4118 | −0.0076 | 0.0943 | 0.032* | |
N13 | 0.2369 (3) | 0.0721 (2) | 0.00952 (18) | 0.0199 (6) | |
H13 | 0.2555 | 0.0174 | −0.0325 | 0.024* | |
N14 | 0.1098 (3) | 0.2058 (2) | 0.01792 (18) | 0.0193 (5) | |
H14 | 0.0219 | 0.2172 | −0.0054 | 0.023* | |
N15 | 0.0056 (3) | 0.0296 (2) | −0.11539 (19) | 0.0237 (6) | |
H15A | −0.0762 | 0.0463 | −0.1422 | 0.028* | |
H15B | 0.0140 | −0.0371 | −0.1453 | 0.028* | |
C5 | 0.1165 (3) | 0.1053 (2) | −0.0297 (2) | 0.0186 (6) | |
C6 | 0.3314 (3) | 0.1175 (2) | 0.1098 (2) | 0.0194 (7) | |
N16 | 0.0987 (3) | 0.8390 (2) | 0.5659 (2) | 0.0270 (6) | |
H16A | 0.0249 | 0.8384 | 0.5934 | 0.032* | |
H16B | 0.1877 | 0.8358 | 0.5998 | 0.032* | |
N17 | −0.0553 (3) | 0.8495 (2) | 0.4233 (2) | 0.0298 (6) | |
H17A | −0.1299 | 0.8490 | 0.4500 | 0.036* | |
H17B | −0.0692 | 0.8533 | 0.3620 | 0.036* | |
N18 | 0.1872 (3) | 0.8458 (2) | 0.42912 (19) | 0.0246 (6) | |
H18 | 0.1574 | 0.8363 | 0.3639 | 0.030* | |
N19 | 0.4153 (3) | 0.9236 (2) | 0.57026 (19) | 0.0261 (6) | |
H19A | 0.5143 | 0.9335 | 0.5976 | 0.031* | |
H19B | 0.3667 | 0.9563 | 0.6077 | 0.031* | |
N20 | 0.4079 (3) | 0.8099 (2) | 0.4155 (2) | 0.0263 (6) | |
H20A | 0.5068 | 0.8183 | 0.4407 | 0.032* | |
H20B | 0.3547 | 0.7677 | 0.3509 | 0.032* | |
C7 | 0.0760 (3) | 0.8447 (3) | 0.4745 (2) | 0.0225 (7) | |
C8 | 0.3404 (3) | 0.8600 (3) | 0.4737 (2) | 0.0222 (7) | |
N21 | 0.7110 (3) | 0.2101 (2) | 0.0802 (2) | 0.0244 (6) | |
O1 | 0.7321 (3) | 0.30816 (18) | 0.13895 (16) | 0.0307 (5) | |
O2 | 0.5951 (2) | 0.16052 (19) | 0.00081 (17) | 0.0327 (6) | |
O3 | 0.8082 (2) | 0.16062 (18) | 0.10169 (18) | 0.0318 (6) | |
N22 | 0.6568 (3) | 0.3131 (2) | 0.3958 (2) | 0.0245 (6) | |
O4 | 0.6754 (2) | 0.25013 (19) | 0.32034 (16) | 0.0310 (5) | |
O5 | 0.7708 (2) | 0.3715 (2) | 0.47552 (17) | 0.0349 (6) | |
O6 | 0.5238 (2) | 0.31558 (19) | 0.39233 (17) | 0.0301 (5) | |
N23 | 0.8362 (3) | 0.5831 (2) | 0.3120 (2) | 0.0309 (7) | |
O7 | 0.7125 (3) | 0.5779 (2) | 0.24814 (18) | 0.0402 (6) | |
O8 | 0.9560 (3) | 0.5959 (2) | 0.28914 (19) | 0.0427 (6) | |
O9 | 0.8314 (3) | 0.5750 (2) | 0.39474 (18) | 0.0437 (6) | |
N24 | 0.7762 (3) | 0.8825 (2) | 0.6299 (2) | 0.0265 (6) | |
O10 | 0.7169 (2) | 0.9387 (2) | 0.68310 (17) | 0.0340 (6) | |
O11 | 0.8824 (3) | 0.8512 (2) | 0.66983 (18) | 0.0371 (6) | |
O12 | 0.7287 (3) | 0.8562 (2) | 0.53412 (17) | 0.0416 (6) | |
N25 | 0.1679 (3) | 0.7363 (2) | 0.1652 (2) | 0.0252 (6) | |
O13 | 0.2391 (3) | 0.67981 (19) | 0.20335 (17) | 0.0341 (6) | |
O14 | 0.1249 (3) | 0.8077 (2) | 0.21814 (17) | 0.0352 (6) | |
O15 | 0.1383 (3) | 0.7204 (2) | 0.07225 (17) | 0.0339 (6) | |
N26 | 0.2725 (3) | 0.0783 (2) | 0.7437 (2) | 0.0306 (7) | |
O16 | 0.1725 (3) | 0.1214 (2) | 0.76133 (18) | 0.0399 (6) | |
O17 | 0.3379 (3) | 0.1043 (2) | 0.68261 (18) | 0.0380 (6) | |
O18 | 0.3074 (3) | 0.0120 (2) | 0.78622 (19) | 0.0491 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0186 (2) | 0.0161 (2) | 0.0171 (3) | 0.00619 (19) | 0.0036 (2) | 0.00460 (19) |
N1 | 0.0160 (12) | 0.0194 (13) | 0.0203 (14) | 0.0044 (11) | 0.0029 (11) | 0.0039 (11) |
N2 | 0.0258 (14) | 0.0309 (16) | 0.0235 (15) | 0.0063 (12) | 0.0106 (13) | 0.0022 (12) |
N3 | 0.0233 (14) | 0.0270 (15) | 0.0186 (14) | 0.0052 (12) | 0.0060 (12) | −0.0023 (12) |
N4 | 0.0169 (13) | 0.0203 (14) | 0.0227 (14) | 0.0053 (11) | 0.0054 (12) | 0.0055 (11) |
N5 | 0.0240 (14) | 0.0298 (16) | 0.0224 (15) | 0.0025 (13) | 0.0029 (13) | −0.0037 (13) |
C1 | 0.0238 (16) | 0.0211 (17) | 0.0224 (17) | 0.0122 (14) | 0.0053 (15) | 0.0075 (14) |
C2 | 0.0241 (16) | 0.0160 (16) | 0.0229 (17) | 0.0064 (14) | 0.0042 (15) | 0.0040 (14) |
N6 | 0.0230 (13) | 0.0181 (13) | 0.0217 (14) | 0.0101 (11) | 0.0066 (12) | 0.0059 (11) |
N7 | 0.0365 (16) | 0.0333 (16) | 0.0256 (15) | 0.0219 (14) | 0.0104 (14) | 0.0147 (13) |
N8 | 0.0260 (14) | 0.0255 (14) | 0.0155 (13) | 0.0114 (12) | 0.0029 (12) | 0.0069 (11) |
N9 | 0.0170 (13) | 0.0232 (14) | 0.0191 (14) | 0.0076 (11) | 0.0037 (11) | 0.0078 (11) |
N10 | 0.0299 (15) | 0.0377 (17) | 0.0260 (15) | 0.0169 (13) | 0.0108 (13) | 0.0139 (13) |
C3 | 0.0203 (16) | 0.0176 (16) | 0.0225 (17) | 0.0046 (13) | 0.0036 (14) | 0.0076 (13) |
C4 | 0.0211 (16) | 0.0139 (15) | 0.0244 (18) | 0.0015 (13) | 0.0057 (14) | 0.0042 (13) |
N11 | 0.0245 (13) | 0.0197 (13) | 0.0166 (13) | 0.0097 (11) | 0.0055 (12) | 0.0072 (11) |
N12 | 0.0333 (15) | 0.0262 (15) | 0.0198 (14) | 0.0176 (13) | 0.0024 (13) | 0.0062 (12) |
N13 | 0.0224 (13) | 0.0192 (13) | 0.0177 (13) | 0.0112 (11) | 0.0051 (12) | 0.0034 (11) |
N14 | 0.0168 (12) | 0.0193 (14) | 0.0205 (14) | 0.0070 (11) | 0.0041 (11) | 0.0062 (11) |
N15 | 0.0222 (13) | 0.0202 (14) | 0.0219 (14) | 0.0060 (12) | 0.0018 (12) | 0.0037 (12) |
C5 | 0.0213 (16) | 0.0195 (16) | 0.0152 (16) | 0.0047 (13) | 0.0074 (14) | 0.0079 (13) |
C6 | 0.0167 (15) | 0.0199 (16) | 0.0217 (17) | 0.0048 (13) | 0.0066 (14) | 0.0088 (14) |
N16 | 0.0190 (13) | 0.0386 (16) | 0.0272 (16) | 0.0123 (12) | 0.0083 (12) | 0.0147 (13) |
N17 | 0.0256 (15) | 0.0407 (17) | 0.0282 (16) | 0.0175 (13) | 0.0086 (13) | 0.0146 (14) |
N18 | 0.0237 (14) | 0.0325 (15) | 0.0189 (14) | 0.0120 (12) | 0.0055 (12) | 0.0103 (12) |
N19 | 0.0180 (13) | 0.0325 (16) | 0.0249 (15) | 0.0087 (12) | 0.0070 (12) | 0.0061 (13) |
N20 | 0.0209 (13) | 0.0307 (15) | 0.0246 (15) | 0.0118 (12) | 0.0050 (12) | 0.0053 (12) |
C7 | 0.0232 (17) | 0.0214 (17) | 0.0219 (17) | 0.0093 (14) | 0.0056 (15) | 0.0062 (14) |
C8 | 0.0182 (16) | 0.0227 (17) | 0.0266 (18) | 0.0060 (14) | 0.0061 (15) | 0.0124 (15) |
N21 | 0.0239 (14) | 0.0228 (15) | 0.0276 (15) | 0.0078 (12) | 0.0096 (13) | 0.0099 (13) |
O1 | 0.0390 (13) | 0.0193 (12) | 0.0302 (13) | 0.0113 (11) | 0.0102 (12) | 0.0034 (10) |
O2 | 0.0235 (12) | 0.0309 (13) | 0.0328 (14) | 0.0099 (11) | −0.0004 (11) | 0.0028 (11) |
O3 | 0.0241 (12) | 0.0226 (12) | 0.0428 (15) | 0.0114 (10) | 0.0008 (11) | 0.0087 (11) |
N22 | 0.0288 (15) | 0.0236 (15) | 0.0213 (15) | 0.0107 (13) | 0.0056 (13) | 0.0091 (12) |
O4 | 0.0332 (13) | 0.0362 (14) | 0.0209 (12) | 0.0140 (11) | 0.0094 (11) | 0.0039 (10) |
O5 | 0.0274 (12) | 0.0375 (14) | 0.0236 (13) | 0.0102 (11) | −0.0024 (11) | −0.0033 (11) |
O6 | 0.0237 (12) | 0.0394 (14) | 0.0276 (13) | 0.0154 (11) | 0.0070 (11) | 0.0096 (11) |
N23 | 0.0317 (16) | 0.0269 (16) | 0.0299 (17) | 0.0045 (13) | 0.0093 (15) | 0.0100 (13) |
O7 | 0.0270 (13) | 0.0558 (17) | 0.0344 (15) | 0.0043 (12) | 0.0036 (12) | 0.0262 (13) |
O8 | 0.0346 (14) | 0.0497 (16) | 0.0471 (16) | 0.0138 (12) | 0.0207 (13) | 0.0169 (13) |
O9 | 0.0399 (14) | 0.0645 (18) | 0.0314 (15) | 0.0164 (13) | 0.0108 (13) | 0.0268 (13) |
N24 | 0.0201 (14) | 0.0284 (15) | 0.0254 (16) | 0.0038 (12) | 0.0045 (13) | 0.0080 (13) |
O10 | 0.0301 (13) | 0.0402 (14) | 0.0285 (13) | 0.0184 (11) | 0.0086 (11) | 0.0025 (11) |
O11 | 0.0356 (13) | 0.0530 (16) | 0.0350 (14) | 0.0277 (13) | 0.0152 (12) | 0.0195 (12) |
O12 | 0.0264 (13) | 0.0694 (18) | 0.0230 (14) | 0.0162 (13) | 0.0061 (11) | 0.0094 (13) |
N25 | 0.0241 (14) | 0.0248 (15) | 0.0235 (15) | 0.0080 (12) | 0.0040 (13) | 0.0075 (12) |
O13 | 0.0410 (14) | 0.0353 (14) | 0.0264 (13) | 0.0246 (12) | 0.0015 (12) | 0.0090 (11) |
O14 | 0.0507 (15) | 0.0371 (14) | 0.0282 (13) | 0.0299 (12) | 0.0157 (12) | 0.0112 (11) |
O15 | 0.0425 (14) | 0.0390 (14) | 0.0221 (13) | 0.0208 (12) | 0.0073 (12) | 0.0105 (11) |
N26 | 0.0306 (15) | 0.0314 (16) | 0.0209 (15) | 0.0103 (14) | 0.0003 (13) | 0.0035 (13) |
O16 | 0.0446 (14) | 0.0576 (17) | 0.0417 (15) | 0.0359 (14) | 0.0257 (13) | 0.0270 (13) |
O17 | 0.0395 (14) | 0.0442 (15) | 0.0424 (15) | 0.0189 (12) | 0.0263 (13) | 0.0182 (12) |
O18 | 0.0686 (18) | 0.0501 (17) | 0.0371 (15) | 0.0358 (15) | 0.0074 (15) | 0.0230 (14) |
Mn1—N4 | 1.918 (2) | N13—H13 | 0.8800 |
Mn1—N11 | 1.924 (2) | N14—C5 | 1.311 (4) |
Mn1—N14 | 1.931 (2) | N14—H14 | 0.8800 |
Mn1—N1 | 1.937 (2) | N15—C5 | 1.330 (4) |
Mn1—N9 | 1.947 (2) | N15—H15A | 0.8800 |
Mn1—N6 | 1.952 (2) | N15—H15B | 0.8800 |
N1—C1 | 1.309 (4) | N16—C7 | 1.311 (4) |
N1—H1 | 0.8800 | N16—H16A | 0.8800 |
N2—C1 | 1.330 (4) | N16—H16B | 0.8800 |
N2—H2A | 0.8800 | N17—C7 | 1.304 (4) |
N2—H2B | 0.8800 | N17—H17A | 0.8800 |
N3—C1 | 1.362 (4) | N17—H17B | 0.8800 |
N3—C2 | 1.371 (4) | N18—C7 | 1.364 (4) |
N3—H3 | 0.8800 | N18—C8 | 1.372 (4) |
N4—C2 | 1.310 (4) | N18—H18 | 0.8800 |
N4—H4 | 0.8800 | N19—C8 | 1.312 (4) |
N5—C2 | 1.321 (4) | N19—H19A | 0.8800 |
N5—H5A | 0.8800 | N19—H19B | 0.8800 |
N5—H5B | 0.8800 | N20—C8 | 1.305 (4) |
N6—C3 | 1.299 (4) | N20—H20A | 0.8800 |
N6—H6 | 0.8800 | N20—H20B | 0.8800 |
N7—C3 | 1.329 (3) | N21—O1 | 1.245 (3) |
N7—H7A | 0.8800 | N21—O2 | 1.247 (3) |
N7—H7B | 0.8800 | N21—O3 | 1.266 (3) |
N8—C4 | 1.364 (4) | N22—O4 | 1.249 (3) |
N8—C3 | 1.376 (4) | N22—O5 | 1.250 (3) |
N8—H8 | 0.8800 | N22—O6 | 1.252 (3) |
N9—C4 | 1.309 (4) | N23—O8 | 1.235 (3) |
N9—H9 | 0.8800 | N23—O9 | 1.239 (3) |
N10—C4 | 1.328 (4) | N23—O7 | 1.272 (3) |
N10—H10A | 0.8800 | N24—O10 | 1.240 (3) |
N10—H10B | 0.8800 | N24—O11 | 1.243 (3) |
N11—C6 | 1.298 (4) | N24—O12 | 1.265 (3) |
N11—H11 | 0.8800 | N25—O14 | 1.243 (3) |
N12—C6 | 1.327 (3) | N25—O13 | 1.250 (3) |
N12—H12A | 0.8800 | N25—O15 | 1.252 (3) |
N12—H12B | 0.8800 | N26—O18 | 1.239 (3) |
N13—C5 | 1.362 (3) | N26—O16 | 1.250 (3) |
N13—C6 | 1.372 (4) | N26—O17 | 1.259 (3) |
N4—Mn1—N11 | 91.80 (10) | Mn1—N11—H11 | 116.5 |
N4—Mn1—N14 | 175.03 (10) | C6—N12—H12A | 120.0 |
N11—Mn1—N14 | 85.68 (10) | C6—N12—H12B | 120.0 |
N4—Mn1—N1 | 86.43 (10) | H12A—N12—H12B | 120.0 |
N11—Mn1—N1 | 96.47 (10) | C5—N13—C6 | 124.8 (2) |
N14—Mn1—N1 | 89.59 (10) | C5—N13—H13 | 117.6 |
N4—Mn1—N9 | 91.95 (10) | C6—N13—H13 | 117.6 |
N11—Mn1—N9 | 87.65 (10) | C5—N14—Mn1 | 127.7 (2) |
N14—Mn1—N9 | 92.22 (10) | C5—N14—H14 | 116.1 |
N1—Mn1—N9 | 175.62 (10) | Mn1—N14—H14 | 116.1 |
N4—Mn1—N6 | 92.87 (10) | C5—N15—H15A | 120.0 |
N11—Mn1—N6 | 170.82 (10) | C5—N15—H15B | 120.0 |
N14—Mn1—N6 | 90.22 (10) | H15A—N15—H15B | 120.0 |
N1—Mn1—N6 | 91.70 (10) | N14—C5—N15 | 122.5 (3) |
N9—Mn1—N6 | 84.30 (10) | N14—C5—N13 | 120.6 (3) |
C1—N1—Mn1 | 132.2 (2) | N15—C5—N13 | 116.8 (3) |
C1—N1—H1 | 113.9 | N11—C6—N12 | 123.3 (3) |
Mn1—N1—H1 | 113.9 | N11—C6—N13 | 120.9 (3) |
C1—N2—H2A | 120.0 | N12—C6—N13 | 115.8 (3) |
C1—N2—H2B | 120.0 | C7—N16—H16A | 120.0 |
H2A—N2—H2B | 120.0 | C7—N16—H16B | 120.0 |
C1—N3—C2 | 126.2 (3) | H16A—N16—H16B | 120.0 |
C1—N3—H3 | 116.9 | C7—N17—H17A | 120.0 |
C2—N3—H3 | 116.9 | C7—N17—H17B | 120.0 |
C2—N4—Mn1 | 132.4 (2) | H17A—N17—H17B | 120.0 |
C2—N4—H4 | 113.8 | C7—N18—C8 | 127.3 (3) |
Mn1—N4—H4 | 113.8 | C7—N18—H18 | 116.3 |
C2—N5—H5A | 120.0 | C8—N18—H18 | 116.3 |
C2—N5—H5B | 120.0 | C8—N19—H19A | 120.0 |
H5A—N5—H5B | 120.0 | C8—N19—H19B | 120.0 |
N1—C1—N2 | 122.9 (3) | H19A—N19—H19B | 120.0 |
N1—C1—N3 | 121.2 (3) | C8—N20—H20A | 120.0 |
N2—C1—N3 | 115.9 (3) | C8—N20—H20B | 120.0 |
N4—C2—N5 | 123.0 (3) | H20A—N20—H20B | 120.0 |
N4—C2—N3 | 121.4 (3) | N17—C7—N16 | 120.8 (3) |
N5—C2—N3 | 115.5 (3) | N17—C7—N18 | 117.3 (3) |
C3—N6—Mn1 | 126.6 (2) | N16—C7—N18 | 121.9 (3) |
C3—N6—H6 | 116.7 | N20—C8—N19 | 122.0 (3) |
Mn1—N6—H6 | 116.7 | N20—C8—N18 | 117.1 (3) |
C3—N7—H7A | 120.0 | N19—C8—N18 | 120.8 (3) |
C3—N7—H7B | 120.0 | O1—N21—O2 | 120.5 (2) |
H7A—N7—H7B | 120.0 | O1—N21—O3 | 119.5 (3) |
C4—N8—C3 | 124.0 (3) | O2—N21—O3 | 119.9 (2) |
C4—N8—H8 | 118.0 | O4—N22—O5 | 119.8 (2) |
C3—N8—H8 | 118.0 | O4—N22—O6 | 120.1 (3) |
C4—N9—Mn1 | 125.5 (2) | O5—N22—O6 | 120.1 (3) |
C4—N9—H9 | 117.2 | O8—N23—O9 | 122.6 (3) |
Mn1—N9—H9 | 117.2 | O8—N23—O7 | 118.9 (3) |
C4—N10—H10A | 120.0 | O9—N23—O7 | 118.5 (3) |
C4—N10—H10B | 120.0 | O10—N24—O11 | 120.6 (3) |
H10A—N10—H10B | 120.0 | O10—N24—O12 | 120.1 (3) |
N6—C3—N7 | 123.7 (3) | O11—N24—O12 | 119.3 (3) |
N6—C3—N8 | 120.6 (3) | O14—N25—O13 | 121.0 (3) |
N7—C3—N8 | 115.7 (3) | O14—N25—O15 | 119.3 (2) |
N9—C4—N10 | 123.2 (3) | O13—N25—O15 | 119.6 (3) |
N9—C4—N8 | 120.5 (3) | O18—N26—O16 | 120.5 (3) |
N10—C4—N8 | 116.3 (3) | O18—N26—O17 | 120.7 (3) |
C6—N11—Mn1 | 127.0 (2) | O16—N26—O17 | 118.9 (3) |
C6—N11—H11 | 116.5 | ||
N4—Mn1—N1—C1 | 0.6 (3) | C4—N8—C3—N6 | −25.0 (4) |
N11—Mn1—N1—C1 | 92.0 (3) | C4—N8—C3—N7 | 155.5 (3) |
N14—Mn1—N1—C1 | 177.6 (3) | Mn1—N9—C4—N10 | −160.6 (2) |
N6—Mn1—N1—C1 | −92.2 (3) | Mn1—N9—C4—N8 | 21.4 (4) |
N11—Mn1—N4—C2 | −97.4 (3) | C3—N8—C4—N9 | 20.2 (4) |
N1—Mn1—N4—C2 | −1.1 (3) | C3—N8—C4—N10 | −157.9 (3) |
N9—Mn1—N4—C2 | 174.9 (3) | N4—Mn1—N11—C6 | −148.9 (2) |
N6—Mn1—N4—C2 | 90.5 (3) | N14—Mn1—N11—C6 | 35.4 (2) |
Mn1—N1—C1—N2 | −177.9 (2) | N1—Mn1—N11—C6 | 124.5 (2) |
Mn1—N1—C1—N3 | 1.3 (4) | N9—Mn1—N11—C6 | −57.0 (2) |
C2—N3—C1—N1 | −3.5 (5) | N11—Mn1—N14—C5 | −30.2 (2) |
C2—N3—C1—N2 | 175.8 (3) | N1—Mn1—N14—C5 | −126.7 (2) |
Mn1—N4—C2—N5 | −179.4 (2) | N9—Mn1—N14—C5 | 57.2 (2) |
Mn1—N4—C2—N3 | −0.5 (4) | N6—Mn1—N14—C5 | 141.6 (2) |
C1—N3—C2—N4 | 3.1 (5) | Mn1—N14—C5—N15 | −172.3 (2) |
C1—N3—C2—N5 | −177.9 (3) | Mn1—N14—C5—N13 | 10.1 (4) |
N4—Mn1—N6—C3 | 127.5 (3) | C6—N13—C5—N14 | 20.5 (4) |
N14—Mn1—N6—C3 | −56.4 (3) | C6—N13—C5—N15 | −157.2 (3) |
N1—Mn1—N6—C3 | −146.0 (2) | Mn1—N11—C6—N12 | 159.1 (2) |
N9—Mn1—N6—C3 | 35.8 (2) | Mn1—N11—C6—N13 | −20.4 (4) |
N4—Mn1—N9—C4 | −133.0 (2) | C5—N13—C6—N11 | −15.4 (4) |
N11—Mn1—N9—C4 | 135.3 (2) | C5—N13—C6—N12 | 165.1 (3) |
N14—Mn1—N9—C4 | 49.7 (2) | C8—N18—C7—N17 | 168.7 (3) |
N6—Mn1—N9—C4 | −40.3 (2) | C8—N18—C7—N16 | −11.3 (5) |
Mn1—N6—C3—N7 | 167.2 (2) | C7—N18—C8—N20 | 150.3 (3) |
Mn1—N6—C3—N8 | −12.3 (4) | C7—N18—C8—N19 | −31.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N20—H20B···O13 | 0.88 | 1.99 | 2.866 (3) | 177 |
N20—H20A···O12 | 0.88 | 2.05 | 2.906 (3) | 165 |
N19—H19B···O17i | 0.88 | 2.03 | 2.818 (3) | 148 |
N19—H19A···O10 | 0.88 | 1.98 | 2.841 (3) | 165 |
N18—H18···O14 | 0.88 | 1.97 | 2.839 (3) | 170 |
N17—H17B···O16ii | 0.88 | 1.97 | 2.792 (3) | 156 |
N17—H17A···O12iii | 0.88 | 2.01 | 2.883 (3) | 170 |
N16—H16A···O11iii | 0.88 | 1.94 | 2.820 (3) | 173 |
N16—H16B···O4iv | 0.88 | 2.21 | 3.017 (3) | 152 |
N14—H14···O15v | 0.88 | 2.04 | 2.894 (3) | 162 |
N13—H13···O3vi | 0.88 | 2.08 | 2.841 (3) | 144 |
N12—H12B···O2vi | 0.88 | 2.04 | 2.919 (3) | 177 |
N11—H11···O6 | 0.88 | 2.16 | 2.984 (3) | 157 |
N9—H9···O1 | 0.88 | 2.21 | 3.077 (3) | 167 |
N7—H7B···O8vii | 0.88 | 2.29 | 3.060 (4) | 146 |
N7—H7A···O15 | 0.88 | 2.10 | 2.854 (3) | 143 |
N6—H6···O13 | 0.88 | 2.22 | 3.009 (3) | 150 |
N5—H5B···O6iv | 0.88 | 2.04 | 2.913 (3) | 175 |
N5—H5A···O9 | 0.88 | 2.16 | 2.961 (4) | 152 |
N4—H4···O7 | 0.88 | 2.00 | 2.848 (3) | 160 |
N3—H3···O5iv | 0.88 | 1.94 | 2.788 (3) | 161 |
N1—H1···O3iii | 0.88 | 2.06 | 2.934 (3) | 173 |
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z; (vi) −x+1, −y, −z; (vii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | (C2H9N5)[Mn(C2H7N5)3](NO3)6 |
Mr | 833.52 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 184 |
a, b, c (Å) | 9.4222 (19), 12.803 (3), 14.452 (3) |
α, β, γ (°) | 105.673 (2), 104.037 (2), 104.891 (2) |
V (Å3) | 1528.3 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.55 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
Data collection | |
Diffractometer | SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.874, 0.898 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6316, 5274, 4160 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.110, 0.98 |
No. of reflections | 5274 |
No. of parameters | 479 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.55 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1999), SHELXTL/PC.
Mn1—N4 | 1.918 (2) | Mn1—N1 | 1.937 (2) |
Mn1—N11 | 1.924 (2) | Mn1—N9 | 1.947 (2) |
Mn1—N14 | 1.931 (2) | Mn1—N6 | 1.952 (2) |
N4—Mn1—N11 | 91.80 (10) | N14—Mn1—N9 | 92.22 (10) |
N4—Mn1—N14 | 175.03 (10) | N1—Mn1—N9 | 175.62 (10) |
N11—Mn1—N14 | 85.68 (10) | N4—Mn1—N6 | 92.87 (10) |
N4—Mn1—N1 | 86.43 (10) | N11—Mn1—N6 | 170.82 (10) |
N11—Mn1—N1 | 96.47 (10) | N14—Mn1—N6 | 90.22 (10) |
N14—Mn1—N1 | 89.59 (10) | N1—Mn1—N6 | 91.70 (10) |
N4—Mn1—N9 | 91.95 (10) | N9—Mn1—N6 | 84.30 (10) |
N11—Mn1—N9 | 87.65 (10) | ||
N4—Mn1—N1—C1 | 0.6 (3) | N14—Mn1—N11—C6 | 35.4 (2) |
N9—Mn1—N6—C3 | 35.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N20—H20B···O13 | 0.88 | 1.99 | 2.866 (3) | 177 |
N20—H20A···O12 | 0.88 | 2.05 | 2.906 (3) | 165 |
N19—H19B···O17i | 0.88 | 2.03 | 2.818 (3) | 148 |
N19—H19A···O10 | 0.88 | 1.98 | 2.841 (3) | 165 |
N18—H18···O14 | 0.88 | 1.97 | 2.839 (3) | 170 |
N17—H17B···O16ii | 0.88 | 1.97 | 2.792 (3) | 156 |
N17—H17A···O12iii | 0.88 | 2.01 | 2.883 (3) | 170 |
N16—H16A···O11iii | 0.88 | 1.94 | 2.820 (3) | 173 |
N16—H16B···O4iv | 0.88 | 2.21 | 3.017 (3) | 152 |
N14—H14···O15v | 0.88 | 2.04 | 2.894 (3) | 162 |
N13—H13···O3vi | 0.88 | 2.08 | 2.841 (3) | 144 |
N12—H12B···O2vi | 0.88 | 2.04 | 2.919 (3) | 177 |
N11—H11···O6 | 0.88 | 2.16 | 2.984 (3) | 157 |
N9—H9···O1 | 0.88 | 2.21 | 3.077 (3) | 167 |
N7—H7B···O8vii | 0.88 | 2.29 | 3.060 (4) | 146 |
N7—H7A···O15 | 0.88 | 2.10 | 2.854 (3) | 143 |
N6—H6···O13 | 0.88 | 2.22 | 3.009 (3) | 150 |
N5—H5B···O6iv | 0.88 | 2.04 | 2.913 (3) | 175 |
N5—H5A···O9 | 0.88 | 2.16 | 2.961 (4) | 152 |
N4—H4···O7 | 0.88 | 2.00 | 2.848 (3) | 160 |
N3—H3···O5iv | 0.88 | 1.94 | 2.788 (3) | 161 |
N1—H1···O3iii | 0.88 | 2.06 | 2.934 (3) | 173 |
Symmetry codes: (i) x, y+1, z; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z; (vi) −x+1, −y, −z; (vii) −x+1, −y+1, −z. |
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Das et al.(2001) reported the synthesis and crystal structure of [MnIV(C2H7N5)3]4+, a rare stable mononuclear complex of manganese(IV) in aqueous solution. We have also encountered this cation, but in crystals in which it coexists with biguanide, forming a complex structure of overall formula [Mn(C2H7N5)3][C2H9N5](NO3)6, which can be viewed as a mixture of [Mn(C2H7N5)3](NO3)4 and [C2H9N5]·(NO3)2. In this complex, (I), we find a double hydrogen-bonding interaction between the biguanide and nitrate groups, which has rarely been observed in crystal structures but which is proposed as a molecular recognition mode for guanidinium group-recognizing anionic entities, such as carboxylates, phosphates, sulfates and nitrates, in biological systems (Baggio et al., 1997; Liu et al., 2001; Lu et al., 2001; Best et al., 2003). We report here the structural characterization of (I).
A single-crystal of the complex was prepared according to the procedure described by Das et al. (2001). However, not only is the stoichiometry of our crystal different from that of Das et al., but the quality of the crystal is also much improved. The R value [0.0455] for the present structure, with the triclinic space group P1, is better than that (0.0943) of the previously reported monoclinic crystal, with space group I2/a (Das et al., 2001).
The geometric parameters of (I) are listed in Table 1 and the molecular conformation is illustrated in Fig.1. The crystal structure of [Mn(C2H7N5)3][C2H9N5](NO3)6 consists of three different chemical moieties, namely the [MnIV(C2H7N5)3]4+ cation, the [C2H9N5]2+ cation and six nitrate anions (Fig. 1). The [MnIV(C2H7N5)3]4+ cation is similar to that reported by Das et al. In the complex tetracation, six N atoms from three neutral biguanide moieties coordinate to MnIV, forming an octahedron. The Mn—N bonds range from 1.918 (2)–1.952 (2) Å. The bite angles of the biguanide ligands at MnIV are 86.43 (10)° for N4—Mn1—N1, 85.68 (10)° for N11—Mn1—N14 and 84.30 (10)° for N9—Mn1—N6. The free biguanide moieties exist in the form of divalent cations, with charge balance achieved by six nitrate anions. Thus two forms of biguanide moieties, viz. divalent cations and neutral molecules (as ligands), are present in the crystal. There are hydrogen bonds between all biguanide and nitrate groups (Table 2). The biguanides, whether coordinated to Mn4+ (neutral) or free (divalent cations), interact with nitrates through strong double hydrogen bonds. In the double hydrogen bonds (Fig.2), the D···A distances are between 2.820 (3) and 2.906 (3) Å, forming an elongated hexagon that was suggested for guanidinium group-recognizing anions such as amino acids (Galán, 1992; Kanyo et al., 1996; Metzger et al., 1996) and nucleotides (Andreu et al., 1994; Kato et al., 1994; Lu et al., 2001; Schliessl & Schmidtchen, 1994). In previous reports, the guanidinium group, present in the side chain of the amino acid arginine, being a vital component of enzymatic catalytic domains that participate in the binding of anionic substrates (Christianson & Lipscomb, 1989; Cotton et al., 1979), attracted great attention. An array of receptors containing guanidinium groups for the purpose of binding anions has been designed and synthesized (Best et al., 2003). It has been proven that a strong interaction between the guanidinium groups and anions through charge pairing and hydrogen bonding facilitates the recognition of small target anions by receptors containing guanidinium groups in competitive solvent systems (Best et al., 2003), but few crystal structure studies have been reported to date. Our result provides direct crystallographic evidence for this interaction.