Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113000814/fa3292sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113000814/fa3292Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270113000814/fa3292sup3.pdf |
CCDC reference: 905960
[(CH3)3CNH]2P(O)OP(O)[NHC(CH3)3]2 (L) was prepared according to the literature method of Pourayoubi et al. (2012). To a solution of MnCl2.4H2O (2 mmol) in CH3OH (5 ml), a solution of L (2 mmol) in CH3OH–DMF (5 ml; Solvent ratio?) was added and the mixture was refluxed for 48 h. Crystals of (I) were obtained from the reaction solution by slow evaporation at room temperature.
H atoms attached to C atoms were placed at calculated positions (C—H = 0.96 Å) and refined as riding. N-bound and water H atoms were found in difference Fourier maps and their coordinates were refined with distance restraints of 0.87 (1) and 0.84 (1) Å for N—H and O—H bonds, respectively. H atoms were refined with Uiso(H) = 1.5Ueq(C,O) for the methyl groups and water molecules, or 1.2Ueq(N,C) for the NH and CH2 groups.
Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006), enCIFer (Allen, et al., 2004) and PLATON (Spek, 2009).
[Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O | Z = 1 |
Mr = 1105 | F(000) = 595 |
Triclinic, P1 | Dx = 1.241 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.5418 Å |
a = 10.9780 (3) Å | Cell parameters from 22455 reflections |
b = 12.7452 (3) Å | θ = 3.9–67.0° |
c = 12.7755 (3) Å | µ = 4.12 mm−1 |
α = 63.131 (2)° | T = 120 K |
β = 68.173 (2)° | Prism, colourless |
γ = 83.141 (2)° | 0.31 × 0.21 × 0.14 mm |
V = 1477.67 (7) Å3 |
Agilent Xcalibur Gemini diffractometer with Atlas CCD area detector | 5236 independent reflections |
Radiation source: Enhance Ultra (Cu) X-ray Source | 5047 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.025 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 67.2°, θmin = 3.9° |
Rotation method data acquisition using ω scans | h = −13→13 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −15→15 |
Tmin = 0.4, Tmax = 1 | l = −15→15 |
34111 measured reflections |
Refinement on F2 | 178 constraints |
R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.086 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2) |
S = 1.71 | (Δ/σ)max = 0.001 |
5236 reflections | Δρmax = 0.29 e Å−3 |
313 parameters | Δρmin = −0.19 e Å−3 |
6 restraints |
[Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O | γ = 83.141 (2)° |
Mr = 1105 | V = 1477.67 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.9780 (3) Å | Cu Kα radiation |
b = 12.7452 (3) Å | µ = 4.12 mm−1 |
c = 12.7755 (3) Å | T = 120 K |
α = 63.131 (2)° | 0.31 × 0.21 × 0.14 mm |
β = 68.173 (2)° |
Agilent Xcalibur Gemini diffractometer with Atlas CCD area detector | 5236 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | 5047 reflections with I > 2σ(I) |
Tmin = 0.4, Tmax = 1 | Rint = 0.025 |
34111 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 6 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.71 | Δρmax = 0.29 e Å−3 |
5236 reflections | Δρmin = −0.19 e Å−3 |
313 parameters |
Experimental. IR (KBr, ν, cm-1): 3385, 3228, 2959, 1665, 1417, 1220, 1062, 940. Diffractometer: Agilent Xcalibur diffractometer Gemini: CCD detector Atlas, collimator Ultra Cu with mirrors. |
Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement. The program used for refinement, JANA2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0 | 0 | 0.5 | 0.01406 (14) | |
Cl3 | −0.05750 (4) | 0.60632 (3) | 0.12953 (3) | 0.02734 (17) | |
P1 | 0.15121 (3) | 0.22242 (3) | 0.21148 (3) | 0.01501 (16) | |
P2 | −0.13996 (3) | 0.22446 (3) | 0.32386 (3) | 0.01521 (16) | |
O1 | 0.14859 (9) | 0.11383 (8) | 0.32508 (9) | 0.0179 (4) | |
O2 | 0.00683 (9) | 0.27075 (8) | 0.22353 (9) | 0.0184 (4) | |
O3 | −0.14244 (9) | 0.10609 (8) | 0.42604 (9) | 0.0189 (4) | |
O4 | 0.01874 (10) | 0.11446 (9) | 0.58018 (10) | 0.0232 (5) | |
O5 | 0.19480 (11) | 0.52830 (10) | −0.03968 (11) | 0.0281 (5) | |
N1 | 0.18812 (11) | 0.20774 (10) | 0.08315 (11) | 0.0175 (5) | |
N2 | 0.24943 (12) | 0.32713 (11) | 0.18038 (11) | 0.0192 (5) | |
N3 | −0.23336 (11) | 0.22640 (11) | 0.24976 (11) | 0.0191 (5) | |
N4 | −0.17621 (11) | 0.33175 (10) | 0.36368 (11) | 0.0193 (5) | |
N5 | −0.04955 (14) | 0.19954 (12) | 0.71258 (12) | 0.0284 (6) | |
C1 | 0.31684 (14) | 0.17805 (13) | 0.01130 (13) | 0.0213 (6) | |
C2 | 0.40984 (17) | 0.28773 (16) | −0.07706 (17) | 0.0379 (8) | |
C3 | 0.28792 (18) | 0.12668 (18) | −0.06488 (18) | 0.0395 (9) | |
C4 | 0.38036 (15) | 0.08784 (14) | 0.09991 (15) | 0.0277 (7) | |
C5 | 0.26973 (14) | 0.36444 (13) | 0.26833 (13) | 0.0211 (6) | |
C6 | 0.37160 (17) | 0.46815 (15) | 0.18549 (16) | 0.0321 (8) | |
C7 | 0.14121 (15) | 0.40380 (14) | 0.33907 (15) | 0.0261 (7) | |
C8 | 0.32208 (15) | 0.26422 (14) | 0.36036 (14) | 0.0253 (7) | |
C9 | −0.25505 (14) | 0.13216 (13) | 0.21864 (14) | 0.0219 (6) | |
C10 | −0.32477 (15) | 0.18935 (15) | 0.12432 (15) | 0.0286 (7) | |
C11 | −0.34230 (18) | 0.03219 (15) | 0.33743 (16) | 0.0352 (8) | |
C12 | −0.12470 (15) | 0.08829 (15) | 0.15808 (16) | 0.0274 (7) | |
C13 | −0.30457 (14) | 0.34725 (14) | 0.44969 (14) | 0.0248 (7) | |
C14 | −0.38653 (17) | 0.42674 (17) | 0.37363 (18) | 0.0363 (8) | |
C15 | −0.27235 (18) | 0.40683 (17) | 0.51746 (17) | 0.0364 (9) | |
C16 | −0.37995 (16) | 0.22940 (16) | 0.54432 (16) | 0.0355 (8) | |
C17 | −0.06868 (15) | 0.13880 (13) | 0.65793 (14) | 0.0238 (7) | |
C18 | 0.0814 (2) | 0.24002 (19) | 0.6854 (2) | 0.0473 (10) | |
C19 | −0.1570 (2) | 0.22430 (18) | 0.80495 (19) | 0.0484 (10) | |
H2A | 0.488311 | 0.26815 | −0.129321 | 0.0569* | |
H2B | 0.36752 | 0.347366 | −0.128895 | 0.0569* | |
H2C | 0.432214 | 0.316671 | −0.028567 | 0.0569* | |
H3A | 0.368463 | 0.105416 | −0.112937 | 0.0592* | |
H3B | 0.22902 | 0.057981 | −0.008867 | 0.0592* | |
H3C | 0.2481 | 0.184341 | −0.120738 | 0.0592* | |
H4A | 0.461604 | 0.067333 | 0.05198 | 0.0416* | |
H4B | 0.397316 | 0.120597 | 0.14798 | 0.0416* | |
H4C | 0.322276 | 0.01858 | 0.155743 | 0.0416* | |
H6A | 0.385766 | 0.498688 | 0.236591 | 0.0482* | |
H6B | 0.452763 | 0.442253 | 0.143864 | 0.0482* | |
H6C | 0.340398 | 0.528771 | 0.123867 | 0.0482* | |
H7A | 0.157275 | 0.432039 | 0.391122 | 0.0392* | |
H7B | 0.108467 | 0.465751 | 0.279691 | 0.0392* | |
H7C | 0.077417 | 0.338249 | 0.390679 | 0.0392* | |
H8A | 0.339889 | 0.290589 | 0.413016 | 0.038* | |
H8B | 0.257756 | 0.199071 | 0.411538 | 0.038* | |
H8C | 0.401619 | 0.239759 | 0.314599 | 0.038* | |
H10A | −0.343278 | 0.131914 | 0.102227 | 0.0428* | |
H10B | −0.405588 | 0.218992 | 0.161165 | 0.0428* | |
H10C | −0.269325 | 0.253122 | 0.050206 | 0.0428* | |
H11A | −0.359428 | −0.027348 | 0.317421 | 0.0528* | |
H11B | −0.298809 | −0.001227 | 0.397231 | 0.0528* | |
H11C | −0.423827 | 0.061947 | 0.372731 | 0.0528* | |
H12A | −0.141555 | 0.027264 | 0.139975 | 0.041* | |
H12B | −0.073216 | 0.152435 | 0.081462 | 0.041* | |
H12C | −0.077442 | 0.057613 | 0.214778 | 0.041* | |
H14A | −0.468652 | 0.437609 | 0.429426 | 0.0544* | |
H14B | −0.339671 | 0.501777 | 0.315691 | 0.0544* | |
H14C | −0.402889 | 0.390913 | 0.327869 | 0.0544* | |
H15A | −0.352318 | 0.417646 | 0.57571 | 0.0546* | |
H15B | −0.217399 | 0.358205 | 0.562199 | 0.0546* | |
H15C | −0.227087 | 0.482052 | 0.457009 | 0.0546* | |
H16A | −0.458962 | 0.241474 | 0.602587 | 0.0533* | |
H16B | −0.402141 | 0.194102 | 0.500904 | 0.0533* | |
H16C | −0.326334 | 0.178253 | 0.589195 | 0.0533* | |
H17 | −0.157169 | 0.112136 | 0.68098 | 0.0285* | |
H18A | 0.089579 | 0.229913 | 0.761625 | 0.071* | |
H18B | 0.145029 | 0.195103 | 0.650148 | 0.071* | |
H18C | 0.096524 | 0.321874 | 0.626386 | 0.071* | |
H19A | −0.158804 | 0.307853 | 0.778015 | 0.0727* | |
H19B | −0.238565 | 0.19491 | 0.813704 | 0.0727* | |
H19C | −0.145012 | 0.18655 | 0.884372 | 0.0727* | |
H1N | 0.1430 (15) | 0.2450 (13) | 0.0368 (14) | 0.021* | |
H2N | 0.2521 (17) | 0.3861 (11) | 0.1105 (11) | 0.0231* | |
H3N | −0.2348 (17) | 0.2942 (10) | 0.1913 (13) | 0.023* | |
H4N | −0.1290 (15) | 0.3968 (10) | 0.3108 (13) | 0.0232* | |
H5O | 0.1610 (19) | 0.4923 (16) | −0.0632 (19) | 0.0421* | |
H5P | 0.1242 (14) | 0.5424 (19) | 0.0081 (17) | 0.0421* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01810 (16) | 0.01246 (16) | 0.01237 (16) | 0.00084 (11) | −0.00539 (12) | −0.00615 (13) |
Cl3 | 0.0359 (2) | 0.0236 (2) | 0.0267 (2) | 0.00375 (15) | −0.01539 (16) | −0.01184 (16) |
P1 | 0.01486 (17) | 0.01498 (19) | 0.01430 (19) | 0.00015 (13) | −0.00446 (13) | −0.00618 (15) |
P2 | 0.01485 (17) | 0.01630 (19) | 0.01460 (18) | 0.00184 (13) | −0.00496 (14) | −0.00741 (15) |
O1 | 0.0177 (4) | 0.0171 (5) | 0.0155 (5) | 0.0009 (4) | −0.0055 (4) | −0.0048 (4) |
O2 | 0.0164 (5) | 0.0173 (5) | 0.0164 (5) | 0.0024 (4) | −0.0039 (4) | −0.0051 (4) |
O3 | 0.0179 (4) | 0.0184 (5) | 0.0177 (5) | 0.0015 (4) | −0.0060 (4) | −0.0062 (4) |
O4 | 0.0292 (5) | 0.0231 (5) | 0.0214 (5) | −0.0012 (4) | −0.0065 (4) | −0.0145 (5) |
O5 | 0.0351 (6) | 0.0247 (6) | 0.0268 (6) | 0.0018 (5) | −0.0133 (5) | −0.0116 (5) |
N1 | 0.0167 (5) | 0.0198 (6) | 0.0165 (6) | 0.0032 (4) | −0.0068 (5) | −0.0082 (5) |
N2 | 0.0231 (6) | 0.0177 (6) | 0.0160 (6) | −0.0026 (5) | −0.0068 (5) | −0.0061 (5) |
N3 | 0.0216 (6) | 0.0195 (6) | 0.0183 (6) | 0.0024 (5) | −0.0093 (5) | −0.0086 (5) |
N4 | 0.0175 (6) | 0.0198 (6) | 0.0207 (6) | 0.0020 (5) | −0.0045 (5) | −0.0110 (5) |
N5 | 0.0412 (8) | 0.0237 (7) | 0.0226 (7) | 0.0012 (6) | −0.0082 (6) | −0.0146 (6) |
C1 | 0.0206 (7) | 0.0244 (8) | 0.0206 (7) | 0.0043 (6) | −0.0051 (6) | −0.0140 (6) |
C2 | 0.0268 (8) | 0.0334 (9) | 0.0324 (9) | −0.0010 (7) | 0.0056 (7) | −0.0094 (8) |
C3 | 0.0393 (9) | 0.0586 (12) | 0.0449 (11) | 0.0178 (8) | −0.0211 (8) | −0.0417 (10) |
C4 | 0.0232 (7) | 0.0307 (8) | 0.0309 (8) | 0.0089 (6) | −0.0104 (7) | −0.0162 (7) |
C5 | 0.0229 (7) | 0.0226 (7) | 0.0216 (7) | −0.0018 (6) | −0.0091 (6) | −0.0113 (6) |
C6 | 0.0364 (9) | 0.0309 (9) | 0.0292 (9) | −0.0122 (7) | −0.0121 (7) | −0.0098 (7) |
C7 | 0.0288 (8) | 0.0272 (8) | 0.0307 (8) | 0.0053 (6) | −0.0129 (7) | −0.0188 (7) |
C8 | 0.0246 (7) | 0.0308 (8) | 0.0236 (8) | 0.0023 (6) | −0.0115 (6) | −0.0124 (7) |
C9 | 0.0211 (7) | 0.0253 (8) | 0.0236 (8) | −0.0008 (6) | −0.0076 (6) | −0.0140 (7) |
C10 | 0.0246 (7) | 0.0409 (9) | 0.0296 (8) | 0.0043 (7) | −0.0126 (7) | −0.0216 (8) |
C11 | 0.0421 (9) | 0.0315 (9) | 0.0296 (9) | −0.0128 (7) | −0.0076 (8) | −0.0121 (8) |
C12 | 0.0269 (8) | 0.0310 (8) | 0.0349 (9) | 0.0068 (6) | −0.0137 (7) | −0.0225 (7) |
C13 | 0.0227 (7) | 0.0303 (8) | 0.0248 (8) | 0.0086 (6) | −0.0061 (6) | −0.0184 (7) |
C14 | 0.0283 (8) | 0.0473 (11) | 0.0403 (10) | 0.0178 (8) | −0.0159 (7) | −0.0260 (9) |
C15 | 0.0407 (9) | 0.0435 (10) | 0.0380 (10) | 0.0108 (8) | −0.0146 (8) | −0.0301 (9) |
C16 | 0.0287 (8) | 0.0400 (10) | 0.0286 (9) | 0.0007 (7) | 0.0025 (7) | −0.0174 (8) |
C17 | 0.0276 (8) | 0.0197 (7) | 0.0233 (8) | 0.0010 (6) | −0.0082 (6) | −0.0095 (6) |
C18 | 0.0541 (12) | 0.0545 (13) | 0.0495 (12) | −0.0099 (9) | −0.0152 (10) | −0.0359 (11) |
C19 | 0.0592 (12) | 0.0476 (12) | 0.0403 (11) | 0.0046 (9) | −0.0033 (9) | −0.0327 (10) |
Mn1—O1 | 2.1642 (8) | C5—C8 | 1.521 (2) |
Mn1—O1i | 2.1642 (8) | C6—H6A | 0.96 |
Mn1—O3 | 2.1459 (10) | C6—H6B | 0.96 |
Mn1—O3i | 2.1459 (10) | C6—H6C | 0.96 |
Mn1—O4 | 2.1906 (15) | C7—H7A | 0.96 |
Mn1—O4i | 2.1906 (15) | C7—H7B | 0.96 |
P1—O1 | 1.4783 (9) | C7—H7C | 0.96 |
P1—O2 | 1.6082 (10) | C8—H8A | 0.96 |
P1—N1 | 1.6287 (16) | C8—H8B | 0.96 |
P1—N2 | 1.6271 (15) | C8—H8C | 0.96 |
P2—O2 | 1.6110 (8) | C9—C10 | 1.526 (3) |
P2—O3 | 1.4779 (9) | C9—C11 | 1.5189 (18) |
P2—N3 | 1.6256 (17) | C9—C12 | 1.528 (2) |
P2—N4 | 1.6235 (16) | C10—H10A | 0.96 |
O4—C17 | 1.2258 (19) | C10—H10B | 0.96 |
O5—H5O | 0.83 (3) | C10—H10C | 0.96 |
O5—H5P | 0.848 (17) | C11—H11A | 0.96 |
N1—C1 | 1.4847 (18) | C11—H11B | 0.96 |
N1—H1N | 0.854 (17) | C11—H11C | 0.96 |
N2—C5 | 1.494 (3) | C12—H12A | 0.96 |
N2—H2N | 0.862 (12) | C12—H12B | 0.96 |
N3—C9 | 1.493 (3) | C12—H12C | 0.96 |
N3—H3N | 0.853 (11) | C13—C14 | 1.524 (3) |
N4—C13 | 1.4867 (18) | C13—C15 | 1.529 (4) |
N4—H4N | 0.865 (12) | C13—C16 | 1.521 (2) |
N5—C17 | 1.329 (3) | C14—H14A | 0.96 |
N5—C18 | 1.449 (3) | C14—H14B | 0.96 |
N5—C19 | 1.448 (3) | C14—H14C | 0.96 |
C1—C2 | 1.526 (2) | C15—H15A | 0.96 |
C1—C3 | 1.527 (4) | C15—H15B | 0.96 |
C1—C4 | 1.519 (2) | C15—H15C | 0.96 |
C2—H2A | 0.96 | C16—H16A | 0.96 |
C2—H2B | 0.96 | C16—H16B | 0.96 |
C2—H2C | 0.96 | C16—H16C | 0.96 |
C3—H3A | 0.96 | C17—H17 | 0.96 |
C3—H3B | 0.96 | C18—H18A | 0.96 |
C3—H3C | 0.96 | C18—H18B | 0.96 |
C4—H4A | 0.96 | C18—H18C | 0.96 |
C4—H4B | 0.96 | C19—H19A | 0.96 |
C4—H4C | 0.96 | C19—H19B | 0.96 |
C5—C6 | 1.525 (2) | C19—H19C | 0.96 |
C5—C7 | 1.534 (2) | ||
O1—Mn1—O1i | 180 | C5—C7—H7B | 109.4711 |
O1—Mn1—O3 | 86.84 (3) | C5—C7—H7C | 109.4718 |
O1—Mn1—O3i | 93.16 (3) | H7A—C7—H7B | 109.471 |
O1—Mn1—O4 | 88.41 (4) | H7A—C7—H7C | 109.4714 |
O1—Mn1—O4i | 91.59 (4) | H7B—C7—H7C | 109.4708 |
O1i—Mn1—O3 | 93.16 (3) | C5—C8—H8A | 109.4716 |
O1i—Mn1—O3i | 86.84 (3) | C5—C8—H8B | 109.4711 |
O1i—Mn1—O4 | 91.59 (4) | C5—C8—H8C | 109.471 |
O1i—Mn1—O4i | 88.41 (4) | H8A—C8—H8B | 109.472 |
O3—Mn1—O3i | 180 | H8A—C8—H8C | 109.471 |
O3—Mn1—O4 | 92.70 (5) | H8B—C8—H8C | 109.4706 |
O3—Mn1—O4i | 87.30 (5) | N3—C9—C10 | 105.74 (13) |
O3i—Mn1—O4 | 87.30 (5) | N3—C9—C11 | 109.08 (15) |
O3i—Mn1—O4i | 92.70 (5) | N3—C9—C12 | 111.24 (14) |
O4—Mn1—O4i | 180 | C10—C9—C11 | 110.20 (14) |
O1—P1—N1 | 116.10 (7) | C10—C9—C12 | 109.19 (15) |
O1—P1—N2 | 112.68 (7) | C11—C9—C12 | 111.25 (13) |
N1—P1—N2 | 107.42 (7) | C9—C10—H10A | 109.4713 |
O3—P2—N3 | 111.71 (7) | C9—C10—H10B | 109.4715 |
O3—P2—N4 | 116.20 (7) | C9—C10—H10C | 109.4714 |
N3—P2—N4 | 108.59 (7) | H10A—C10—H10B | 109.4707 |
Mn1—O1—P1 | 136.46 (6) | H10A—C10—H10C | 109.4707 |
Mn1—O3—P2 | 135.47 (6) | H10B—C10—H10C | 109.4717 |
Mn1—O4—C17 | 127.17 (12) | C9—C11—H11A | 109.4709 |
P1—O2—P2 | 135.55 (6) | C9—C11—H11B | 109.4717 |
H5O—O5—H5P | 98 (2) | C9—C11—H11C | 109.4716 |
P1—N1—C1 | 127.04 (12) | H11A—C11—H11B | 109.4714 |
P1—N1—H1N | 116.8 (12) | H11A—C11—H11C | 109.4704 |
C1—N1—H1N | 111.8 (10) | H11B—C11—H11C | 109.4712 |
P1—N2—C5 | 129.16 (8) | C9—C12—H12A | 109.4717 |
P1—N2—H2N | 109.0 (13) | C9—C12—H12B | 109.4718 |
C5—N2—H2N | 112.3 (12) | C9—C12—H12C | 109.4713 |
P2—N3—C9 | 127.64 (10) | H12A—C12—H12B | 109.4712 |
P2—N3—H3N | 113.5 (14) | H12A—C12—H12C | 109.4699 |
C9—N3—H3N | 110.2 (13) | H12B—C12—H12C | 109.4713 |
P2—N4—C13 | 126.80 (11) | N4—C13—C14 | 109.77 (13) |
P2—N4—H4N | 115.3 (11) | N4—C13—C15 | 106.05 (14) |
N1—C1—C2 | 110.99 (13) | N4—C13—C16 | 111.30 (14) |
N1—C1—C3 | 106.17 (14) | C14—C13—C15 | 109.65 (16) |
N1—C1—C4 | 110.66 (12) | C14—C13—C16 | 109.74 (15) |
C2—C1—C3 | 109.83 (14) | C15—C13—C16 | 110.26 (15) |
C2—C1—C4 | 109.09 (14) | C13—C14—H14A | 109.4716 |
C3—C1—C4 | 110.07 (15) | C13—C14—H14B | 109.4709 |
C1—C2—H2A | 109.4712 | C13—C14—H14C | 109.471 |
C1—C2—H2B | 109.4712 | H14A—C14—H14B | 109.4709 |
C1—C2—H2C | 109.4707 | H14A—C14—H14C | 109.4711 |
H2A—C2—H2B | 109.4709 | H14B—C14—H14C | 109.4718 |
H2A—C2—H2C | 109.4716 | C13—C15—H15A | 109.4711 |
H2B—C2—H2C | 109.4717 | C13—C15—H15B | 109.4712 |
C1—C3—H3A | 109.4714 | C13—C15—H15C | 109.4708 |
C1—C3—H3B | 109.4713 | H15A—C15—H15B | 109.4715 |
C1—C3—H3C | 109.4707 | H15A—C15—H15C | 109.4718 |
H3A—C3—H3B | 109.4718 | H15B—C15—H15C | 109.471 |
H3A—C3—H3C | 109.4707 | C13—C16—H16A | 109.4715 |
H3B—C3—H3C | 109.4715 | C13—C16—H16B | 109.4708 |
C1—C4—H4A | 109.471 | C13—C16—H16C | 109.4718 |
C1—C4—H4B | 109.471 | H16A—C16—H16B | 109.4711 |
C1—C4—H4C | 109.4714 | H16A—C16—H16C | 109.4711 |
H4A—C4—H4B | 109.472 | H16B—C16—H16C | 109.4711 |
H4A—C4—H4C | 109.4713 | O4—C17—N5 | 124.59 (16) |
H4B—C4—H4C | 109.4706 | O4—C17—H17 | 117.7053 |
N2—C5—C6 | 105.54 (13) | N5—C17—H17 | 117.7035 |
N2—C5—C7 | 110.63 (14) | N5—C18—H18A | 109.4716 |
N2—C5—C8 | 110.12 (14) | N5—C18—H18B | 109.4705 |
C6—C5—C7 | 109.90 (14) | N5—C18—H18C | 109.4715 |
C6—C5—C8 | 110.01 (14) | H18A—C18—H18B | 109.471 |
C7—C5—C8 | 110.53 (12) | H18A—C18—H18C | 109.472 |
C5—C6—H6A | 109.4715 | H18B—C18—H18C | 109.4707 |
C5—C6—H6B | 109.4711 | N5—C19—H19A | 109.4713 |
C5—C6—H6C | 109.4714 | N5—C19—H19B | 109.4701 |
H6A—C6—H6B | 109.4707 | N5—C19—H19C | 109.4716 |
H6A—C6—H6C | 109.4712 | H19A—C19—H19B | 109.4714 |
H6B—C6—H6C | 109.4714 | H19A—C19—H19C | 109.4721 |
C5—C7—H7A | 109.4712 | H19B—C19—H19C | 109.4709 |
O3—Mn1—O1—P1 | 5.26 (10) | N4—P2—O2—P1 | 119.27 (10) |
O4—Mn1—O1—P1 | −87.53 (10) | O2—P2—O3—Mn1 | 18.90 (11) |
O3i—Mn1—O1—P1 | −174.74 (10) | N3—P2—O3—Mn1 | 140.86 (9) |
O4i—Mn1—O1—P1 | 92.47 (10) | N4—P2—O3—Mn1 | −93.81 (10) |
O1—Mn1—O3—P2 | −18.05 (9) | O2—P2—N3—C9 | 86.70 (13) |
O4—Mn1—O3—P2 | 70.21 (9) | O3—P2—N3—C9 | −37.02 (14) |
O1i—Mn1—O3—P2 | 161.95 (9) | N4—P2—N3—C9 | −166.47 (12) |
O4i—Mn1—O3—P2 | −109.79 (9) | O2—P2—N4—C13 | 175.77 (12) |
O1—Mn1—O4—C17 | 145.79 (13) | O3—P2—N4—C13 | −64.43 (14) |
O3—Mn1—O4—C17 | 59.03 (13) | N3—P2—N4—C13 | 62.47 (13) |
O1i—Mn1—O4—C17 | −34.21 (13) | Mn1—O4—C17—N5 | 173.10 (12) |
O3i—Mn1—O4—C17 | −120.97 (13) | P1—N1—C1—C2 | −83.14 (16) |
O2—P1—O1—Mn1 | 2.80 (12) | P1—N1—C1—C3 | 157.55 (13) |
N1—P1—O1—Mn1 | −110.00 (10) | P1—N1—C1—C4 | 38.1 (2) |
N2—P1—O1—Mn1 | 125.52 (10) | P1—N2—C5—C6 | −179.01 (13) |
O1—P1—O2—P2 | −5.78 (12) | P1—N2—C5—C7 | −60.18 (19) |
N1—P1—O2—P2 | 117.20 (10) | P1—N2—C5—C8 | 62.30 (19) |
N2—P1—O2—P2 | −130.69 (10) | P2—N3—C9—C10 | −167.37 (11) |
O1—P1—N1—C1 | −67.63 (15) | P2—N3—C9—C11 | 74.13 (17) |
O2—P1—N1—C1 | 172.72 (13) | P2—N3—C9—C12 | −48.96 (17) |
N2—P1—N1—C1 | 59.52 (15) | P2—N4—C13—C14 | −94.88 (17) |
O1—P1—N2—C5 | −41.55 (17) | P2—N4—C13—C15 | 146.74 (13) |
O2—P1—N2—C5 | 82.69 (15) | P2—N4—C13—C16 | 26.81 (19) |
N1—P1—N2—C5 | −170.67 (14) | C18—N5—C17—O4 | −1.7 (3) |
O3—P2—O2—P1 | −3.77 (12) | C19—N5—C17—O4 | −179.29 (17) |
N3—P2—O2—P1 | −127.47 (10) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl3ii | 0.85 (2) | 2.53 (2) | 3.3644 (13) | 166 (1) |
N2—H2N···O5 | 0.86 (1) | 2.20 (1) | 3.0346 (16) | 163 (2) |
N3—H3N···O5ii | 0.85 (1) | 2.17 (1) | 3.0072 (14) | 167 (2) |
N4—H4N···Cl3 | 0.87 (1) | 2.58 (1) | 3.4090 (11) | 160 (2) |
O5—H5O···Cl3ii | 0.83 (3) | 2.37 (3) | 3.1965 (17) | 178 (2) |
O5—H5P···Cl3 | 0.85 (2) | 2.35 (2) | 3.1885 (12) | 172 (2) |
Symmetry code: (ii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O |
Mr | 1105 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 10.9780 (3), 12.7452 (3), 12.7755 (3) |
α, β, γ (°) | 63.131 (2), 68.173 (2), 83.141 (2) |
V (Å3) | 1477.67 (7) |
Z | 1 |
Radiation type | Cu Kα |
µ (mm−1) | 4.12 |
Crystal size (mm) | 0.31 × 0.21 × 0.14 |
Data collection | |
Diffractometer | Agilent Xcalibur Gemini diffractometer with Atlas CCD area detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2010) |
Tmin, Tmax | 0.4, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34111, 5236, 5047 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.086, 1.71 |
No. of reflections | 5236 |
No. of parameters | 313 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.19 |
Computer programs: CrysAlis PRO (Agilent, 2010), SIR2002 (Burla et al., 2003), DIAMOND (Brandenburg & Putz, 2005), JANA2006 (Petříček et al., 2006), enCIFer (Allen, et al., 2004) and PLATON (Spek, 2009).
Mn1—O1 | 2.1642 (8) | P1—N2 | 1.6271 (15) |
Mn1—O3 | 2.1459 (10) | P2—O2 | 1.6110 (8) |
Mn1—O4 | 2.1906 (15) | P2—O3 | 1.4779 (9) |
P1—O1 | 1.4783 (9) | P2—N3 | 1.6256 (17) |
P1—O2 | 1.6082 (10) | P2—N4 | 1.6235 (16) |
P1—N1 | 1.6287 (16) | ||
O1—Mn1—O3 | 86.84 (3) | N1—P1—N2 | 107.42 (7) |
O1—Mn1—O3i | 93.16 (3) | O3—P2—N3 | 111.71 (7) |
O1—Mn1—O4 | 88.41 (4) | O3—P2—N4 | 116.20 (7) |
O1—Mn1—O4i | 91.59 (4) | N3—P2—N4 | 108.59 (7) |
O3—Mn1—O4 | 92.70 (5) | Mn1—O1—P1 | 136.46 (6) |
O3—Mn1—O4i | 87.30 (5) | Mn1—O3—P2 | 135.47 (6) |
O1—P1—N1 | 116.10 (7) | Mn1—O4—C17 | 127.17 (12) |
O1—P1—N2 | 112.68 (7) | P1—O2—P2 | 135.55 (6) |
N1—P1—O1—Mn1 | −110.00 (10) | N3—P2—O3—Mn1 | 140.86 (9) |
N2—P1—O1—Mn1 | 125.52 (10) | N4—P2—O3—Mn1 | −93.81 (10) |
O1—P1—O2—P2 | −5.78 (12) | Mn1—O4—C17—N5 | 173.10 (12) |
O3—P2—O2—P1 | −3.77 (12) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl3ii | 0.854 (17) | 2.531 (16) | 3.3644 (13) | 165.5 (14) |
N2—H2N···O5 | 0.862 (12) | 2.200 (14) | 3.0346 (16) | 162.9 (16) |
N3—H3N···O5ii | 0.853 (11) | 2.170 (10) | 3.0072 (14) | 167.3 (18) |
N4—H4N···Cl3 | 0.865 (12) | 2.583 (10) | 3.4090 (11) | 160.2 (16) |
O5—H5O···Cl3ii | 0.83 (3) | 2.37 (3) | 3.1965 (17) | 177.9 (18) |
O5—H5P···Cl3 | 0.848 (17) | 2.346 (19) | 3.1885 (12) | 172 (2) |
Symmetry code: (ii) −x, −y+1, −z. |
Phosphoramidate complexes are characterized by phosphoryl (PO) donor ligands containing the N—P═O group. A scarcely studied class of these compounds, the pyrophosphoramide complexes, of which only four chelate complexes of octamethylpyrophosphoramide (OMPA) are known, have an (N)2P(O)OP(O)(N)2 skeleton, where (N)2 denotes two tertiary N atoms belonging to an amide group (Joesten et al., 1970; Hussain et al., 1970). The geometries of the six-membered pyrophosphate–metal chelate rings in the OMPA complexes are comparable with those observed for complexes of β-ketoenolates having the (O)C—C—C(O) skeleton (Hussain et al., 1970).
In the present study, a novel pyrophosphoramide ligand with the fragment (NH)2P(O)OP(O)(NH)2 was used for the first time to synthesize the title chelate complex, denoted [Mn(L)2{OC(H)N(CH3)2}2]Cl2.2H2O, (I). Its structural features are compared in what follows with those of phosphoramidate complexes with chelating ligands having the C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2 fragments, in which six-membered chelate rings are found. The structures of 36 such phosphoramidate complexes, found in the Cambridge Structural Database (CSD, Version 5.32, May 2011 update; Allen, 2002), as well as four structures published recently in IUCr journals (Trush et al., 2011; Amirkhanov et al., 2010; Shatrava et al., 2010; Litsis et al., 2010), were used in the comparison.
The asymmetric unit of (I) (Fig. 1) contains half of the [Mn(L)2{OC(H)N(CH3)2}2]2+ dication, which sits on an inversion centre, one chloride anion and one water molecule. The coordination geometry at the MnII centre is octahedral, with a slight elongation towards the dimethylformamide ligand (Table 1). The carbonyl group of dimethylformamide is tilted some 53° from the Mn—O axis [Mn1—O4—C17 = 127.2 (1)°].
The P═O, P—O and P—N bond lengths (Table 1) are within the expected ranges for bis- and tris-OMPA complexes (Joesten et al., 1970; Hussain et al., 1970). Fig. 2 shows a histogram of the P═O bond lengths for previously reported complexes with phosphoramide ligands having C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2 skeletons. Disordered P═O groups were excluded, as were complexes with an (OR)2P(O)N-P(O)(OR)2 skeleton and Cs+ and K+ metal ions. Moreover, the P═O groups of one complicated complex were excluded. The data show that the maximum population of the distribution is found in the range 1.46–1.50 Å and, as expected, the P═O bonds in complexes tend to be longer than the unligated P═O double bond (1.45 Å; Corbridge, 1995).
The shortest P═O bonds are found in a complex of lanthanum with a P(O)NP(O) skeleton, viz. [La2{(C2H5O)2P(O)NP(O)(OC2H5)2}6] [P═ O = 1.43 (1) Å; CSD refcode KOKKEA; Dvorkin et al., 1990], and in a complex of zinc with a C(S)NP(O) skeleton, [Zn{C10H15NHC(S)NP(O)(OC3H7)2}2] [P═O = 1.426 (3) °; AAQEBEE; Safin et al., 2010]. The longest P═O bond [1.5203 (4) Å] occurs in [Co{O4C10H20NC(S)NP(O)(OC3H7)2}2] (UKOXIC; Babashkina et al., 2010), where C(S)NP(O) is the chelating fragment.
The Mn—O(P) bonds in (I) (Table 1) are, as expected, somewhat longer than the M—O(P) bonds in OMPA complexes of Cu, Co and Mg. For example, in [Cu{[(CH3)2N]2P(O)OP(O)[N(CH3)2]2}2](ClO4)2 (OMPOCU), the Cu—O(P) bond lengths are 1.936 (2) and 1.946 (1) Å.
Both the P═O [1.4783 (9) and 1.4779 (9) Å] and P—O [1.6082 (10) and 1.6110 (8) Å] bond lengths are nearly identical in (I) and in the free ligand [P═O = 1.4791 (12) and 1.4806 (12) Å; P—O = 1.6191 (17) and 1.6194 (16) Å; Pourayoubi et al., 2012]. In the free ligand, the two phosphoryl groups have a relative gauche disposition [O—P—O—P torsion angles = 57.79 (11) and 59.76 (11)°]; when coordinated to MnII, they adopt a syn disposition [O1—P1—O2—P2 = -5.78 (12)° and O3—P2—O2—P1 = -3.77 (12)°]. The P—O—P bond angle of (I) [135.55 (6)°] is more open than that in the free ligand [126.85 (8)°].
For comparative purposes, we note that only one complex of MnII containing a monodentate phosphoric triamide ligand has been reported to date, namely [MnCl2{P(O)[N(CH3)2]3}2] (VAYWEY; Jin et al., 2005). In that complex, the MnII atom is bonded to two O atoms from two hexamethylphosphoramide (HMPA) ligands and two Cl atoms, with a distorted tetrahedral coordination. In VAYWEY, the P═O bond [1.489 (1) Å] is slightly longer and Mn—O(P) [2.047 (1) Å] is shorter than those of (I).
Similar to what was found for other pyrophosphate chelate complexes, in (I) the pyrophosphate chelate ring, including its O═P—O—P═O fragment, is almost planar (see Table S1 in the Supplementary materials). The notable difference between the P═O bond lengths [1.4783 (9) and 1.4779 (9) Å] and the P—O bond lengths [1.608 (1) and 1.6110 (9) Å] reflects the absence of appreciable electron delocalization in the ring. Thus, the planarity cannot be attributed to dπ-pπ delocalization.
The degree of planarity of the chelate ring in previously reported phosphoramidate complexes with ligands containing the C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2 fragments was surveyed by calculating the least-squares plane containing the metal atom, the two atoms coordinated to the metal atom and the N atom {for the C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2, P(O)] skeleton} or O atom [in the (N)2P(O)OP(O)(N)2 skeleton] (see Table S1 in the Supplementary materials). The minimum deviation from planarity occurs in complexes with a P(O)OP(O) skeleton, i.e. containing O, P and M atoms. The maximum deviation is found in complexes with a C(S)NP(O) skeleton, having six different O, P, N, C, S and M atoms. For example, in the cobalt complex with a C(S)NP(O) skeleton, [Co{C6H5C(S)NP(O)(OC3H7)2}2{C6H5C(S)NHP(O)(OC3H7)2}2] (BERNIW; Sokolov et al., 2004), the distances from the plane through the chelate are 0.012 (2) for P, 0.091 (8) for C and 0.356 Å for Co, while for the Mg complex of Mg with a P(O)OP(O) skeleton, [Mg{[(CH3)2N]2P(O)OP(O)[N(CH3)2]2}3](ClO4)2 (MEPOMG; Joesten et al., 1970), the distances from the plane through the chelate are 0.047 Å for two P atoms and 0.00 Å for Mg.
Crystals of the free ligand, [(CH3)3CNH]2P(O)OP(O)[NHC(CH3)3]2 (Pourayoubi et al., 2012), possess [N—H][N—H]···O(P) hydrogen bonds. These are replaced, after coordination of the ligand to the MnII centre, by Mn—O═P bonds. In (I), since the O atoms of two phosphoryl groups are involved in the Mn—O═P bonds, the two N—H units in each [(CH3)3CNH]2P(O) fragment take part separately in hydrogen bonding with the chloride anion and with the water O atom, forming two N—H···Cl and two N—H···O hydrogen bonds for each ligand (Table 2). The water O atom interacts with two N—H units. These hydrogen bonds lead to a linear aggregate along [011] (Fig. 3). The chloride anion also receives two weak O—H···Cl hydrogen bonds.
In summary, the structure of the first pyrophosphoramide complex containing an (NH)2P(O)OP(O)(NH)2 skeleton has been analysed and compared with four analogous bis- and tris-OMPA complexes. Characteristic features of analogous phosphoramidate complexes with C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2 skeletons, including the P═O bond lengths and the planarity of the chelate rings, have also been examined.