The title complexes,
catena-poly[[[diaquadiethanolmanganese(II)]-
-1,4-bis(diphenylphosphinoyl)butane-
2O:
O'] dinitrate 1,4-bis(diphenylphosphinoyl)butane solvate], {[Mn(C
2H
6O)
2(C
28H
28O
2P
2)(H
2O)
2](NO
3)
2·C
28H
28O
2P
2}
n, (I), and
catena-poly[[[diaquadiethanolcobalt(II)]-
-1,4-bis(diphenylphosphinoyl)butane-
2O:
O'] dinitrate 1,4-bis(diphenylphosphinoyl)butane solvate], {[Co(C
2H
6O)
2(C
28H
28O
2P
2)(H
2O)
2](NO
3)
2·C
28H
28O
2P
2}
n, (II), are isostructural and centrosymmetric, with the
MII ions at centres of inversion. The coordination geometry is octahedral, with each metal ion coordinated by two
trans ethanol molecules, two
trans water molecules and two bridging 1,4-bis(diphenylphosphinoyl)butane ligands which link the coordination centres to form one-dimensional polymeric chains. Parallel chains are linked by hydrogen bonds to uncoordinated 1,4-bis(diphenylphosphinoyl)butane molecules, which are bisected by a centre of inversion. Further hydrogen bonds, weak C-H
O interactions to nitrate anions, and weak C-H
interactions serve to stabilize the structure. This study reports a development of the coordination chemistry of bis(diphenylphosphinoyl)alkanes, with the first reported structures of complexes of the first-row transition metals with 1,4-bis(diphenylphosphinoyl)butane.
Supporting information
CCDC references: 718102; 718103
Hot ethanol solutions of hydrated metal nitrates and the ligand [Please give
specific salts and details of molar quantities and liquid volumes]
were mixed. Slow evaporation of the resulting solutions led to the formation
of crystals suitable for X-ray diffraction studies.
All C-bound H atoms were refined isotropically in idealized positions, with
aromatic C—H = 0.95, methylene C—H = 0.99 and methyl C—H= 0.98 Å, and
were constrained to ride on their parent atoms. The H atoms of each functional
group were assigned a common refined isotropic displacement parameter. O-bound
H atoms were located in a difference map and refined isotropically with a
common isotropic displacement parameter.
For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and enCIFer (Allen et al., 2004).
(I)
catena-poly[[[diaquadiethanolmanganese(II)]-µ-1,4-
bis(diphenylphosphinoyl)butane-
κ2O:O'] dinitrate
1,4-bis(diphenylphosphinoyl)butane solvate]
top
Crystal data top
[Mn(C2H6O)2(C28H28O2P2)(H2O)2](NO3)2·C28H28O2P2 | F(000) = 1286 |
Mr = 1224.02 | Dx = 1.357 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7147 reflections |
a = 13.4134 (3) Å | θ = 1–27.5° |
b = 10.3270 (3) Å | µ = 0.39 mm−1 |
c = 22.1028 (6) Å | T = 120 K |
β = 101.900 (1)° | Cut plate, colourless |
V = 2995.88 (14) Å3 | 0.24 × 0.22 × 0.03 mm |
Z = 2 | |
Data collection top
Bruker Nonius 95mm CCD camera on κ-goniostat diffractometer | 6856 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 5673 reflections with I > 2σ(I) |
10cm confocal mirrors monochromator | Rint = 0.042 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 2.6° |
ϕ and ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.912, Tmax = 0.988 | l = −28→28 |
40734 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Only H-atom displacement parameters refined |
wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0438P)2 + 3.312P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
6856 reflections | Δρmax = 0.71 e Å−3 |
382 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | |
Crystal data top
[Mn(C2H6O)2(C28H28O2P2)(H2O)2](NO3)2·C28H28O2P2 | V = 2995.88 (14) Å3 |
Mr = 1224.02 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.4134 (3) Å | µ = 0.39 mm−1 |
b = 10.3270 (3) Å | T = 120 K |
c = 22.1028 (6) Å | 0.24 × 0.22 × 0.03 mm |
β = 101.900 (1)° | |
Data collection top
Bruker Nonius 95mm CCD camera on κ-goniostat diffractometer | 6856 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5673 reflections with I > 2σ(I) |
Tmin = 0.912, Tmax = 0.988 | Rint = 0.042 |
40734 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.111 | Only H-atom displacement parameters refined |
S = 1.05 | Δρmax = 0.71 e Å−3 |
6856 reflections | Δρmin = −0.43 e Å−3 |
382 parameters | |
Special details top
Experimental. SADABS was used to perform the Absorption correction parameter refinement
on 30561 reflections reduced R(int) from 0.0950 to 0.0356 Ratio of
minimum to maximum apparent transmission: 0.86259 The given Tmin and Tmax
were generated using the SHELX SIZE command |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.5000 | 0.5000 | 0.5000 | 0.01841 (11) | |
O1 | 0.54549 (11) | 0.63488 (14) | 0.43921 (7) | 0.0218 (3) | |
O2 | 0.42438 (14) | 0.38670 (19) | 0.41921 (8) | 0.0385 (4) | |
O3 | 0.34512 (13) | 0.58875 (17) | 0.49089 (8) | 0.0300 (4) | |
O4 | 0.32591 (14) | 0.8477 (2) | 0.59908 (11) | 0.0517 (5) | |
O5 | 0.17836 (16) | 0.84843 (19) | 0.62178 (10) | 0.0484 (5) | |
O6 | 0.22340 (16) | 0.68865 (18) | 0.57033 (9) | 0.0475 (5) | |
O7 | 0.24516 (11) | 0.35852 (16) | 0.45062 (7) | 0.0276 (4) | |
N1 | 0.24226 (15) | 0.79552 (19) | 0.59688 (9) | 0.0293 (4) | |
P1 | 0.57901 (4) | 0.75716 (5) | 0.41302 (2) | 0.01536 (12) | |
P2 | 0.14168 (4) | 0.30088 (5) | 0.42641 (2) | 0.01944 (13) | |
C1 | 0.48769 (15) | 0.8007 (2) | 0.34365 (9) | 0.0175 (4) | |
C2 | 0.48610 (17) | 0.9224 (2) | 0.31593 (10) | 0.0241 (5) | |
H2 | 0.5328 | 0.9875 | 0.3341 | 0.0403 (17)* | |
C3 | 0.41556 (19) | 0.9477 (2) | 0.26148 (10) | 0.0295 (5) | |
H3 | 0.4130 | 1.0311 | 0.2431 | 0.0403 (17)* | |
C4 | 0.34912 (18) | 0.8517 (2) | 0.23411 (10) | 0.0298 (5) | |
H4 | 0.3019 | 0.8692 | 0.1967 | 0.0403 (17)* | |
C5 | 0.35126 (18) | 0.7307 (2) | 0.26096 (11) | 0.0296 (5) | |
H5 | 0.3063 | 0.6648 | 0.2416 | 0.0403 (17)* | |
C6 | 0.41939 (16) | 0.7051 (2) | 0.31641 (10) | 0.0241 (5) | |
H6 | 0.4193 | 0.6228 | 0.3356 | 0.0403 (17)* | |
C7 | 0.69898 (15) | 0.7360 (2) | 0.38963 (9) | 0.0184 (4) | |
C8 | 0.75600 (18) | 0.8420 (2) | 0.37671 (11) | 0.0294 (5) | |
H8 | 0.7331 | 0.9277 | 0.3817 | 0.0403 (17)* | |
C9 | 0.84620 (19) | 0.8218 (3) | 0.35648 (13) | 0.0370 (6) | |
H9 | 0.8855 | 0.8937 | 0.3481 | 0.0403 (17)* | |
C10 | 0.87897 (18) | 0.6967 (3) | 0.34848 (12) | 0.0354 (6) | |
H10 | 0.9399 | 0.6833 | 0.3338 | 0.0403 (17)* | |
C11 | 0.82342 (17) | 0.5915 (2) | 0.36184 (11) | 0.0303 (5) | |
H11 | 0.8466 | 0.5061 | 0.3566 | 0.0403 (17)* | |
C12 | 0.73358 (16) | 0.6106 (2) | 0.38298 (10) | 0.0221 (4) | |
H12 | 0.6960 | 0.5384 | 0.3928 | 0.0403 (17)* | |
C13 | 0.59240 (15) | 0.8934 (2) | 0.46444 (9) | 0.0182 (4) | |
H13A | 0.6392 | 0.8696 | 0.5036 | 0.027 (2)* | |
H13B | 0.6241 | 0.9656 | 0.4457 | 0.027 (2)* | |
C14 | 0.49196 (15) | 0.9407 (2) | 0.47908 (9) | 0.0192 (4) | |
H14A | 0.4440 | 0.9626 | 0.4401 | 0.027 (2)* | |
H14B | 0.4612 | 0.8705 | 0.4996 | 0.027 (2)* | |
C15 | 0.4599 (2) | 0.3111 (3) | 0.37399 (14) | 0.0504 (8) | |
H15A | 0.4655 | 0.2197 | 0.3878 | 0.104 (11)* | |
H15B | 0.5291 | 0.3411 | 0.3715 | 0.104 (11)* | |
C16 | 0.3934 (2) | 0.3170 (3) | 0.31064 (13) | 0.0458 (7) | |
H16A | 0.3271 | 0.2780 | 0.3115 | 0.083 (7)* | |
H16B | 0.4258 | 0.2693 | 0.2816 | 0.083 (7)* | |
H16C | 0.3838 | 0.4075 | 0.2974 | 0.083 (7)* | |
C17 | 0.15004 (16) | 0.1269 (2) | 0.41961 (10) | 0.0218 (4) | |
C18 | 0.1118 (2) | 0.0418 (3) | 0.45708 (13) | 0.0391 (6) | |
H18 | 0.0718 | 0.0736 | 0.4847 | 0.0403 (17)* | |
C19 | 0.1310 (2) | −0.0898 (3) | 0.45488 (14) | 0.0493 (7) | |
H19 | 0.1037 | −0.1474 | 0.4808 | 0.0403 (17)* | |
C20 | 0.1893 (2) | −0.1376 (3) | 0.41554 (13) | 0.0421 (6) | |
H20 | 0.2015 | −0.2281 | 0.4139 | 0.0403 (17)* | |
C21 | 0.22986 (19) | −0.0542 (3) | 0.37873 (12) | 0.0360 (6) | |
H21 | 0.2713 | −0.0866 | 0.3521 | 0.0403 (17)* | |
C22 | 0.21033 (18) | 0.0779 (2) | 0.38039 (11) | 0.0319 (5) | |
H22 | 0.2382 | 0.1352 | 0.3546 | 0.0403 (17)* | |
C23 | 0.08777 (16) | 0.3656 (2) | 0.35085 (9) | 0.0209 (4) | |
C24 | −0.00681 (17) | 0.3234 (2) | 0.31805 (10) | 0.0259 (5) | |
H24 | −0.0421 | 0.2561 | 0.3342 | 0.0403 (17)* | |
C25 | −0.04910 (18) | 0.3801 (2) | 0.26170 (11) | 0.0311 (5) | |
H25 | −0.1135 | 0.3517 | 0.2392 | 0.0403 (17)* | |
C26 | 0.00246 (19) | 0.4782 (3) | 0.23824 (11) | 0.0334 (6) | |
H26 | −0.0267 | 0.5167 | 0.1996 | 0.0403 (17)* | |
C27 | 0.0961 (2) | 0.5204 (3) | 0.27071 (12) | 0.0358 (6) | |
H27 | 0.1311 | 0.5874 | 0.2543 | 0.0403 (17)* | |
C28 | 0.13894 (18) | 0.4649 (2) | 0.32719 (11) | 0.0292 (5) | |
H28 | 0.2030 | 0.4945 | 0.3497 | 0.0403 (17)* | |
C29 | 0.05135 (16) | 0.3373 (2) | 0.47382 (10) | 0.0218 (4) | |
H29A | −0.0160 | 0.3011 | 0.4544 | 0.027 (2)* | |
H29B | 0.0735 | 0.2961 | 0.5148 | 0.027 (2)* | |
C30 | 0.04168 (16) | 0.4840 (2) | 0.48209 (10) | 0.0233 (5) | |
H30A | 0.1076 | 0.5190 | 0.5047 | 0.027 (2)* | |
H30B | 0.0253 | 0.5260 | 0.4410 | 0.027 (2)* | |
H2E | 0.352 (3) | 0.351 (4) | 0.4229 (18) | 0.087 (8)* | |
H3A | 0.302 (3) | 0.526 (4) | 0.4765 (19) | 0.087 (8)* | |
H3B | 0.318 (3) | 0.637 (4) | 0.5163 (19) | 0.087 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0182 (2) | 0.0186 (2) | 0.0182 (2) | −0.00526 (17) | 0.00316 (16) | 0.00422 (17) |
O1 | 0.0231 (7) | 0.0199 (8) | 0.0235 (7) | −0.0022 (6) | 0.0074 (6) | 0.0070 (6) |
O2 | 0.0344 (10) | 0.0514 (12) | 0.0338 (9) | −0.0160 (9) | 0.0165 (8) | −0.0164 (8) |
O3 | 0.0275 (9) | 0.0253 (9) | 0.0386 (10) | 0.0044 (7) | 0.0099 (7) | 0.0037 (7) |
O4 | 0.0347 (11) | 0.0400 (11) | 0.0823 (15) | −0.0066 (9) | 0.0162 (10) | 0.0156 (11) |
O5 | 0.0543 (12) | 0.0357 (11) | 0.0647 (13) | 0.0007 (9) | 0.0339 (11) | −0.0041 (10) |
O6 | 0.0625 (13) | 0.0264 (10) | 0.0512 (12) | −0.0039 (9) | 0.0063 (10) | −0.0112 (9) |
O7 | 0.0195 (8) | 0.0324 (9) | 0.0306 (8) | −0.0031 (7) | 0.0046 (6) | −0.0051 (7) |
N1 | 0.0341 (11) | 0.0214 (10) | 0.0334 (10) | −0.0015 (8) | 0.0091 (9) | 0.0065 (8) |
P1 | 0.0171 (2) | 0.0139 (2) | 0.0166 (2) | 0.00039 (19) | 0.00702 (19) | 0.00100 (19) |
P2 | 0.0173 (3) | 0.0210 (3) | 0.0205 (3) | −0.0006 (2) | 0.0049 (2) | −0.0020 (2) |
C1 | 0.0198 (10) | 0.0179 (10) | 0.0163 (9) | 0.0022 (8) | 0.0073 (8) | −0.0007 (8) |
C2 | 0.0325 (12) | 0.0197 (11) | 0.0209 (10) | −0.0003 (9) | 0.0075 (9) | 0.0001 (8) |
C3 | 0.0413 (14) | 0.0244 (12) | 0.0234 (11) | 0.0074 (10) | 0.0077 (10) | 0.0055 (9) |
C4 | 0.0305 (12) | 0.0369 (13) | 0.0201 (10) | 0.0063 (10) | 0.0011 (9) | 0.0009 (10) |
C5 | 0.0268 (12) | 0.0318 (13) | 0.0285 (12) | −0.0031 (10) | 0.0016 (9) | −0.0039 (10) |
C6 | 0.0244 (11) | 0.0212 (11) | 0.0266 (11) | −0.0005 (9) | 0.0047 (9) | 0.0012 (9) |
C7 | 0.0194 (10) | 0.0190 (10) | 0.0183 (9) | 0.0032 (8) | 0.0076 (8) | 0.0002 (8) |
C8 | 0.0313 (12) | 0.0203 (11) | 0.0423 (13) | 0.0031 (9) | 0.0211 (10) | 0.0044 (10) |
C9 | 0.0336 (13) | 0.0345 (14) | 0.0506 (15) | 0.0000 (11) | 0.0261 (12) | 0.0066 (12) |
C10 | 0.0253 (12) | 0.0477 (16) | 0.0385 (13) | 0.0068 (11) | 0.0187 (10) | −0.0023 (12) |
C11 | 0.0271 (12) | 0.0320 (13) | 0.0320 (12) | 0.0093 (10) | 0.0066 (10) | −0.0099 (10) |
C12 | 0.0221 (10) | 0.0204 (11) | 0.0235 (10) | 0.0021 (8) | 0.0040 (8) | −0.0037 (8) |
C13 | 0.0176 (10) | 0.0192 (10) | 0.0186 (9) | 0.0012 (8) | 0.0053 (8) | −0.0031 (8) |
C14 | 0.0175 (10) | 0.0227 (11) | 0.0183 (9) | 0.0017 (8) | 0.0056 (8) | −0.0045 (8) |
C15 | 0.0479 (17) | 0.061 (2) | 0.0447 (16) | 0.0179 (15) | 0.0153 (13) | −0.0110 (15) |
C16 | 0.0568 (18) | 0.0478 (17) | 0.0373 (14) | −0.0146 (14) | 0.0205 (13) | −0.0114 (13) |
C17 | 0.0199 (10) | 0.0225 (11) | 0.0219 (10) | 0.0016 (8) | 0.0021 (8) | −0.0010 (8) |
C18 | 0.0510 (16) | 0.0298 (13) | 0.0438 (15) | 0.0037 (12) | 0.0263 (13) | 0.0023 (11) |
C19 | 0.069 (2) | 0.0299 (14) | 0.0548 (18) | 0.0033 (14) | 0.0254 (16) | 0.0127 (13) |
C20 | 0.0515 (17) | 0.0266 (13) | 0.0461 (15) | 0.0110 (12) | 0.0053 (13) | −0.0002 (12) |
C21 | 0.0300 (13) | 0.0372 (14) | 0.0394 (14) | 0.0067 (11) | 0.0042 (11) | −0.0117 (12) |
C22 | 0.0320 (13) | 0.0303 (13) | 0.0357 (13) | −0.0020 (10) | 0.0122 (10) | −0.0067 (10) |
C23 | 0.0222 (10) | 0.0213 (11) | 0.0207 (10) | 0.0028 (8) | 0.0079 (8) | −0.0024 (8) |
C24 | 0.0271 (11) | 0.0256 (12) | 0.0256 (11) | −0.0019 (9) | 0.0066 (9) | −0.0022 (9) |
C25 | 0.0293 (12) | 0.0366 (14) | 0.0258 (11) | 0.0008 (10) | 0.0015 (9) | −0.0013 (10) |
C26 | 0.0367 (13) | 0.0388 (15) | 0.0256 (12) | 0.0081 (11) | 0.0089 (10) | 0.0068 (10) |
C27 | 0.0366 (14) | 0.0353 (14) | 0.0383 (13) | 0.0004 (11) | 0.0145 (11) | 0.0119 (11) |
C28 | 0.0262 (12) | 0.0302 (12) | 0.0322 (12) | −0.0021 (10) | 0.0085 (9) | 0.0025 (10) |
C29 | 0.0217 (10) | 0.0236 (11) | 0.0212 (10) | 0.0006 (9) | 0.0072 (8) | −0.0017 (8) |
C30 | 0.0235 (11) | 0.0229 (11) | 0.0247 (11) | 0.0007 (9) | 0.0079 (9) | −0.0022 (9) |
Geometric parameters (Å, º) top
Mn1—O1i | 2.1109 (14) | C14—C14ii | 1.522 (4) |
Mn1—O1 | 2.1109 (14) | C14—H14A | 0.9900 |
Mn1—O2i | 2.1998 (17) | C14—H14B | 0.9900 |
Mn1—O2 | 2.1998 (17) | C15—O2 | 1.426 (3) |
Mn1—O3i | 2.2415 (16) | C15—C16 | 1.499 (4) |
Mn1—O3 | 2.2415 (16) | C15—H15A | 0.9900 |
P1—O1 | 1.4964 (15) | C15—H15B | 0.9900 |
P2—O7 | 1.5036 (16) | C16—H16A | 0.9800 |
O2—H2E | 1.06 (4) | C16—H16B | 0.9800 |
O3—H3A | 0.89 (4) | C16—H16C | 0.9800 |
O3—H3B | 0.88 (4) | C17—C18 | 1.377 (3) |
N1—O4 | 1.237 (3) | C17—C22 | 1.397 (3) |
N1—O5 | 1.237 (3) | C17—P2 | 1.809 (2) |
N1—O6 | 1.251 (3) | C18—C19 | 1.386 (4) |
C1—C2 | 1.396 (3) | C18—H18 | 0.9500 |
C1—C6 | 1.397 (3) | C19—C20 | 1.376 (4) |
C1—P1 | 1.811 (2) | C19—H19 | 0.9500 |
C2—C3 | 1.394 (3) | C20—C21 | 1.372 (4) |
C2—H2 | 0.9500 | C20—H20 | 0.9500 |
C3—C4 | 1.386 (3) | C21—C22 | 1.390 (4) |
C3—H3 | 0.9500 | C21—H21 | 0.9500 |
C4—C5 | 1.381 (3) | C22—H22 | 0.9500 |
C4—H4 | 0.9500 | C23—C28 | 1.395 (3) |
C5—C6 | 1.395 (3) | C23—C24 | 1.395 (3) |
C5—H5 | 0.9500 | C23—P2 | 1.806 (2) |
C6—H6 | 0.9500 | C24—C25 | 1.388 (3) |
C7—C12 | 1.394 (3) | C24—H24 | 0.9500 |
C7—C8 | 1.398 (3) | C25—C26 | 1.386 (3) |
C7—P1 | 1.802 (2) | C25—H25 | 0.9500 |
C8—C9 | 1.389 (3) | C26—C27 | 1.382 (4) |
C8—H8 | 0.9500 | C26—H26 | 0.9500 |
C9—C10 | 1.387 (4) | C27—C28 | 1.386 (3) |
C9—H9 | 0.9500 | C27—H27 | 0.9500 |
C10—C11 | 1.384 (4) | C28—H28 | 0.9500 |
C10—H10 | 0.9500 | C29—C30 | 1.534 (3) |
C11—C12 | 1.393 (3) | C29—P2 | 1.798 (2) |
C11—H11 | 0.9500 | C29—H29A | 0.9900 |
C12—H12 | 0.9500 | C29—H29B | 0.9900 |
C13—C14 | 1.529 (3) | C30—C30iii | 1.533 (4) |
C13—P1 | 1.795 (2) | C30—H30A | 0.9900 |
C13—H13A | 0.9900 | C30—H30B | 0.9900 |
C13—H13B | 0.9900 | | |
| | | |
O1—Mn1—O1i | 180.0 | H16A—C16—H16C | 109.5 |
O1—Mn1—O2 | 88.84 (6) | H16B—C16—H16C | 109.5 |
O1—Mn1—O2i | 91.16 (6) | C18—C17—C22 | 118.5 (2) |
O1i—Mn1—O2 | 91.16 (6) | C18—C17—P2 | 123.15 (18) |
O1i—Mn1—O2i | 88.84 (6) | C22—C17—P2 | 117.73 (17) |
O1—Mn1—O3 | 93.28 (6) | C17—C18—C19 | 120.6 (2) |
O1i—Mn1—O3 | 86.72 (6) | C17—C18—H18 | 119.7 |
O1i—Mn1—O3i | 93.28 (6) | C19—C18—H18 | 119.7 |
O1—Mn1—O3i | 86.72 (6) | C20—C19—C18 | 120.6 (3) |
O2—Mn1—O2i | 180.0 | C20—C19—H19 | 119.7 |
O2—Mn1—O3 | 83.16 (7) | C18—C19—H19 | 119.7 |
O2i—Mn1—O3i | 83.16 (7) | C21—C20—C19 | 119.7 (2) |
O2—Mn1—O3i | 96.84 (7) | C21—C20—H20 | 120.2 |
O2i—Mn1—O3 | 96.84 (7) | C19—C20—H20 | 120.2 |
O3i—Mn1—O3 | 180.00 (10) | C20—C21—C22 | 120.0 (2) |
C2—C1—C6 | 119.87 (19) | C20—C21—H21 | 120.0 |
C2—C1—P1 | 122.81 (16) | C22—C21—H21 | 120.0 |
C6—C1—P1 | 117.28 (16) | C21—C22—C17 | 120.5 (2) |
C3—C2—C1 | 119.6 (2) | C21—C22—H22 | 119.7 |
C3—C2—H2 | 120.2 | C17—C22—H22 | 119.7 |
C1—C2—H2 | 120.2 | C28—C23—C24 | 120.0 (2) |
C4—C3—C2 | 120.2 (2) | C28—C23—P2 | 119.01 (17) |
C4—C3—H3 | 119.9 | C24—C23—P2 | 120.85 (17) |
C2—C3—H3 | 119.9 | C25—C24—C23 | 119.6 (2) |
C5—C4—C3 | 120.3 (2) | C25—C24—H24 | 120.2 |
C5—C4—H4 | 119.8 | C23—C24—H24 | 120.2 |
C3—C4—H4 | 119.8 | C26—C25—C24 | 120.1 (2) |
C4—C5—C6 | 120.1 (2) | C26—C25—H25 | 120.0 |
C4—C5—H5 | 120.0 | C24—C25—H25 | 120.0 |
C6—C5—H5 | 120.0 | C27—C26—C25 | 120.4 (2) |
C5—C6—C1 | 119.8 (2) | C27—C26—H26 | 119.8 |
C5—C6—H6 | 120.1 | C25—C26—H26 | 119.8 |
C1—C6—H6 | 120.1 | C26—C27—C28 | 120.1 (2) |
C12—C7—C8 | 119.86 (19) | C26—C27—H27 | 119.9 |
C12—C7—P1 | 118.64 (16) | C28—C27—H27 | 119.9 |
C8—C7—P1 | 121.48 (16) | C27—C28—C23 | 119.8 (2) |
C9—C8—C7 | 119.8 (2) | C27—C28—H28 | 120.1 |
C9—C8—H8 | 120.1 | C23—C28—H28 | 120.1 |
C7—C8—H8 | 120.1 | C30—C29—P2 | 111.09 (15) |
C10—C9—C8 | 120.0 (2) | C30—C29—H29A | 109.4 |
C10—C9—H9 | 120.0 | P2—C29—H29A | 109.4 |
C8—C9—H9 | 120.0 | C30—C29—H29B | 109.4 |
C11—C10—C9 | 120.4 (2) | P2—C29—H29B | 109.4 |
C11—C10—H10 | 119.8 | H29A—C29—H29B | 108.0 |
C9—C10—H10 | 119.8 | C30iii—C30—C29 | 111.3 (2) |
C10—C11—C12 | 120.1 (2) | C30iii—C30—H30A | 109.4 |
C10—C11—H11 | 120.0 | C29—C30—H30A | 109.4 |
C12—C11—H11 | 120.0 | C30iii—C30—H30B | 109.4 |
C11—C12—C7 | 119.8 (2) | C29—C30—H30B | 109.4 |
C11—C12—H12 | 120.1 | H30A—C30—H30B | 108.0 |
C7—C12—H12 | 120.1 | O4—N1—O5 | 119.7 (2) |
C14—C13—P1 | 114.02 (14) | O4—N1—O6 | 119.8 (2) |
C14—C13—H13A | 108.7 | O5—N1—O6 | 120.4 (2) |
P1—C13—H13A | 108.7 | P1—O1—Mn1 | 162.25 (10) |
C14—C13—H13B | 108.7 | C15—O2—Mn1 | 134.06 (17) |
P1—C13—H13B | 108.7 | C15—O2—H2E | 108 (2) |
H13A—C13—H13B | 107.6 | Mn1—O2—H2E | 114 (2) |
C14ii—C14—C13 | 111.4 (2) | Mn1—O3—H3A | 105 (3) |
C14ii—C14—H14A | 109.3 | Mn1—O3—H3B | 132 (3) |
C13—C14—H14A | 109.3 | H3A—O3—H3B | 109 (4) |
C14ii—C14—H14B | 109.3 | O1—P1—C13 | 114.56 (9) |
C13—C14—H14B | 109.3 | O1—P1—C7 | 111.48 (9) |
H14A—C14—H14B | 108.0 | C13—P1—C7 | 107.34 (9) |
O2—C15—C16 | 114.3 (2) | O1—P1—C1 | 109.42 (9) |
O2—C15—H15A | 108.7 | C13—P1—C1 | 107.65 (9) |
C16—C15—H15A | 108.7 | C7—P1—C1 | 105.98 (9) |
O2—C15—H15B | 108.7 | O7—P2—C29 | 113.17 (10) |
C16—C15—H15B | 108.7 | O7—P2—C23 | 110.29 (10) |
H15A—C15—H15B | 107.6 | C29—P2—C23 | 105.79 (10) |
C15—C16—H16A | 109.5 | O7—P2—C17 | 110.75 (10) |
C15—C16—H16B | 109.5 | C29—P2—C17 | 108.50 (10) |
H16A—C16—H16B | 109.5 | C23—P2—C17 | 108.11 (10) |
C15—C16—H16C | 109.5 | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2E···O7 | 1.06 (4) | 1.67 (4) | 2.652 (2) | 152 (3) |
O3—H3A···O7 | 0.88 (4) | 1.93 (4) | 2.784 (2) | 163 (4) |
O3—H3B···O6 | 0.88 (4) | 1.99 (4) | 2.828 (3) | 159 (4) |
C8—H8···O4ii | 0.95 | 2.52 | 3.465 (3) | 177 |
C12—H12···O6i | 0.95 | 2.64 | 3.271 (3) | 124 |
C13—H13B···O4ii | 0.99 | 2.33 | 3.310 (3) | 171 |
C24—H24···O5iii | 0.95 | 2.49 | 3.387 (3) | 158 |
C30—H30A···O6 | 0.99 | 2.58 | 3.500 (3) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
(II)
catena-poly[[[diaquadiethanolcobalt(II)]-µ-1,4-
bis(diphenylphosphinoyl)butane-
κ2O:O'] dinitrate
1,4-bis(diphenylphosphinoyl)butane solvate]
top
Crystal data top
[Co(C2H6O)2(C28H28O2P2)(H2O)2](NO3)2·C28H28O2P2 | F(000) = 1290 |
Mr = 1228.01 | Dx = 1.378 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6761 reflections |
a = 13.3646 (5) Å | θ = 2.9–27.5° |
b = 10.2517 (5) Å | µ = 0.47 mm−1 |
c = 22.0744 (11) Å | T = 120 K |
β = 101.920 (3)° | Plate, light pink |
V = 2959.2 (2) Å3 | 0.16 × 0.14 × 0.03 mm |
Z = 2 | |
Data collection top
Bruker Nonius 95mm CCD camera on κ-goniostat diffractometer | 6806 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 4594 reflections with I > 2σ(I) |
10cm confocal mirrors monochromator | Rint = 0.093 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 3.0° |
ϕ and ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→12 |
Tmin = 0.929, Tmax = 0.986 | l = −28→28 |
36332 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.062 | Only H-atom displacement parameters refined |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0347P)2 + 4.4666P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.002 |
6806 reflections | Δρmax = 0.53 e Å−3 |
382 parameters | Δρmin = −0.38 e Å−3 |
0 restraints | |
Crystal data top
[Co(C2H6O)2(C28H28O2P2)(H2O)2](NO3)2·C28H28O2P2 | V = 2959.2 (2) Å3 |
Mr = 1228.01 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.3646 (5) Å | µ = 0.47 mm−1 |
b = 10.2517 (5) Å | T = 120 K |
c = 22.0744 (11) Å | 0.16 × 0.14 × 0.03 mm |
β = 101.920 (3)° | |
Data collection top
Bruker Nonius 95mm CCD camera on κ-goniostat diffractometer | 6806 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4594 reflections with I > 2σ(I) |
Tmin = 0.929, Tmax = 0.986 | Rint = 0.093 |
36332 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.135 | Only H-atom displacement parameters refined |
S = 1.03 | Δρmax = 0.53 e Å−3 |
6806 reflections | Δρmin = −0.38 e Å−3 |
382 parameters | |
Special details top
Experimental. SADABS was used to perform the Absorption correction Parameter refinement
on 21506 reflections reduced R(int) from 0.1322 to 0.0683 Ratio of
minimum to maximum apparent transmission: 0.730864 The given Tmin and Tmax
were generated using the SHELX SIZE command |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Co1 | 0.5000 | 0.5000 | 0.5000 | 0.02356 (16) | |
O1 | 0.54485 (16) | 0.6287 (2) | 0.44000 (10) | 0.0281 (5) | |
O2 | 0.4306 (2) | 0.3875 (3) | 0.42348 (14) | 0.0459 (8) | |
O3 | 0.35165 (19) | 0.5880 (2) | 0.48968 (13) | 0.0311 (6) | |
O4 | 0.3272 (2) | 0.8543 (3) | 0.60046 (15) | 0.0598 (9) | |
O5 | 0.1757 (2) | 0.8484 (3) | 0.61870 (14) | 0.0508 (7) | |
O6 | 0.2302 (2) | 0.6910 (3) | 0.56933 (13) | 0.0496 (7) | |
O7 | 0.24660 (16) | 0.3599 (2) | 0.45024 (10) | 0.0305 (5) | |
N1 | 0.2435 (2) | 0.7981 (3) | 0.59612 (14) | 0.0341 (7) | |
P1 | 0.57808 (6) | 0.75211 (8) | 0.41424 (4) | 0.02229 (19) | |
P2 | 0.14325 (6) | 0.30089 (8) | 0.42649 (4) | 0.0234 (2) | |
C1 | 0.4865 (2) | 0.7956 (3) | 0.34467 (14) | 0.0240 (7) | |
C2 | 0.4853 (3) | 0.9172 (3) | 0.31660 (15) | 0.0299 (8) | |
H2 | 0.5322 | 0.9829 | 0.3347 | 0.036 (2)* | |
C3 | 0.4150 (3) | 0.9421 (4) | 0.26199 (16) | 0.0339 (8) | |
H3 | 0.4132 | 1.0258 | 0.2433 | 0.036 (2)* | |
C4 | 0.3482 (3) | 0.8470 (4) | 0.23466 (16) | 0.0355 (8) | |
H4 | 0.3011 | 0.8650 | 0.1971 | 0.036 (2)* | |
C5 | 0.3494 (3) | 0.7253 (4) | 0.26164 (17) | 0.0359 (9) | |
H5 | 0.3040 | 0.6592 | 0.2423 | 0.036 (2)* | |
C6 | 0.4174 (2) | 0.7000 (3) | 0.31727 (16) | 0.0317 (8) | |
H6 | 0.4168 | 0.6173 | 0.3366 | 0.036 (2)* | |
C7 | 0.6986 (2) | 0.7318 (3) | 0.39050 (14) | 0.0245 (7) | |
C8 | 0.7564 (3) | 0.8375 (3) | 0.37793 (16) | 0.0329 (8) | |
H8 | 0.7341 | 0.9238 | 0.3835 | 0.036 (2)* | |
C9 | 0.8462 (3) | 0.8176 (4) | 0.35742 (18) | 0.0385 (9) | |
H9 | 0.8856 | 0.8901 | 0.3492 | 0.036 (2)* | |
C10 | 0.8787 (3) | 0.6921 (4) | 0.34885 (17) | 0.0368 (9) | |
H10 | 0.9394 | 0.6786 | 0.3337 | 0.036 (2)* | |
C11 | 0.8234 (3) | 0.5869 (4) | 0.36224 (16) | 0.0335 (8) | |
H11 | 0.8468 | 0.5009 | 0.3571 | 0.036 (2)* | |
C12 | 0.7328 (2) | 0.6060 (3) | 0.38335 (15) | 0.0262 (7) | |
H12 | 0.6948 | 0.5331 | 0.3928 | 0.036 (2)* | |
C13 | 0.5917 (2) | 0.8894 (3) | 0.46526 (15) | 0.0239 (7) | |
H13A | 0.6374 | 0.8647 | 0.5048 | 0.032 (3)* | |
H13B | 0.6253 | 0.9608 | 0.4468 | 0.032 (3)* | |
C14 | 0.4915 (2) | 0.9404 (3) | 0.47897 (15) | 0.0252 (7) | |
H14A | 0.4446 | 0.9635 | 0.4396 | 0.032 (3)* | |
H14B | 0.4587 | 0.8707 | 0.4991 | 0.032 (3)* | |
C15 | 0.4691 (4) | 0.3186 (5) | 0.3773 (2) | 0.0651 (14) | |
H15A | 0.4865 | 0.2290 | 0.3926 | 0.109 (15)* | |
H15B | 0.5336 | 0.3611 | 0.3724 | 0.109 (15)* | |
C16 | 0.4003 (4) | 0.3090 (5) | 0.3144 (2) | 0.0666 (14) | |
H16A | 0.3351 | 0.2694 | 0.3182 | 0.111 (12)* | |
H16B | 0.4330 | 0.2549 | 0.2874 | 0.111 (12)* | |
H16C | 0.3878 | 0.3964 | 0.2965 | 0.111 (12)* | |
C17 | 0.1521 (2) | 0.1263 (3) | 0.42010 (15) | 0.0249 (7) | |
C18 | 0.1122 (3) | 0.0406 (3) | 0.45741 (18) | 0.0385 (9) | |
H18 | 0.0718 | 0.0727 | 0.4849 | 0.036 (2)* | |
C19 | 0.1310 (3) | −0.0914 (4) | 0.4548 (2) | 0.0495 (11) | |
H19 | 0.1028 | −0.1496 | 0.4803 | 0.036 (2)* | |
C20 | 0.1899 (3) | −0.1399 (4) | 0.41594 (18) | 0.0405 (9) | |
H20 | 0.2028 | −0.2309 | 0.4148 | 0.036 (2)* | |
C21 | 0.2303 (3) | −0.0557 (4) | 0.37860 (18) | 0.0379 (9) | |
H21 | 0.2711 | −0.0886 | 0.3516 | 0.036 (2)* | |
C22 | 0.2112 (3) | 0.0762 (3) | 0.38053 (16) | 0.0338 (8) | |
H22 | 0.2388 | 0.1337 | 0.3545 | 0.036 (2)* | |
C23 | 0.0881 (2) | 0.3648 (3) | 0.35034 (15) | 0.0244 (7) | |
C24 | −0.0060 (2) | 0.3220 (3) | 0.31819 (16) | 0.0292 (8) | |
H24 | −0.0412 | 0.2547 | 0.3348 | 0.036 (2)* | |
C25 | −0.0487 (3) | 0.3779 (3) | 0.26152 (16) | 0.0313 (8) | |
H25 | −0.1134 | 0.3489 | 0.2392 | 0.036 (2)* | |
C26 | 0.0026 (3) | 0.4757 (3) | 0.23738 (17) | 0.0339 (8) | |
H26 | −0.0269 | 0.5138 | 0.1986 | 0.036 (2)* | |
C27 | 0.0963 (3) | 0.5177 (4) | 0.26960 (17) | 0.0375 (9) | |
H27 | 0.1315 | 0.5846 | 0.2527 | 0.036 (2)* | |
C28 | 0.1399 (3) | 0.4638 (3) | 0.32624 (16) | 0.0322 (8) | |
H28 | 0.2044 | 0.4937 | 0.3485 | 0.036 (2)* | |
C29 | 0.0525 (2) | 0.3377 (3) | 0.47389 (15) | 0.0245 (7) | |
H29A | −0.0149 | 0.3005 | 0.4546 | 0.032 (3)* | |
H29B | 0.0750 | 0.2966 | 0.5150 | 0.032 (3)* | |
C30 | 0.0416 (2) | 0.4846 (3) | 0.48197 (15) | 0.0262 (7) | |
H30B | 0.0244 | 0.5267 | 0.4408 | 0.032 (3)* | |
H30A | 0.1076 | 0.5209 | 0.5043 | 0.032 (3)* | |
H2E | 0.387 (4) | 0.366 (5) | 0.431 (2) | 0.072 (10)* | |
H3A | 0.312 (4) | 0.527 (5) | 0.480 (2) | 0.072 (10)* | |
H3B | 0.332 (4) | 0.630 (5) | 0.512 (2) | 0.072 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0200 (3) | 0.0194 (3) | 0.0316 (4) | −0.0026 (3) | 0.0060 (3) | 0.0045 (3) |
O1 | 0.0255 (12) | 0.0240 (12) | 0.0363 (14) | −0.0031 (10) | 0.0097 (10) | 0.0083 (10) |
O2 | 0.0402 (17) | 0.0519 (18) | 0.0514 (18) | −0.0198 (14) | 0.0231 (14) | −0.0185 (14) |
O3 | 0.0259 (13) | 0.0246 (14) | 0.0431 (16) | 0.0032 (10) | 0.0080 (11) | 0.0055 (12) |
O4 | 0.0401 (16) | 0.0519 (19) | 0.089 (2) | −0.0072 (14) | 0.0178 (16) | 0.0161 (17) |
O5 | 0.0550 (17) | 0.0392 (16) | 0.068 (2) | 0.0027 (14) | 0.0346 (15) | 0.0002 (14) |
O6 | 0.0661 (19) | 0.0282 (15) | 0.0511 (18) | 0.0012 (13) | 0.0040 (14) | −0.0053 (13) |
O7 | 0.0220 (11) | 0.0349 (14) | 0.0336 (14) | −0.0045 (10) | 0.0038 (10) | −0.0011 (11) |
N1 | 0.0350 (17) | 0.0295 (17) | 0.0381 (18) | −0.0024 (14) | 0.0083 (14) | 0.0103 (14) |
P1 | 0.0214 (4) | 0.0204 (4) | 0.0261 (4) | 0.0008 (3) | 0.0073 (3) | 0.0025 (4) |
P2 | 0.0209 (4) | 0.0238 (5) | 0.0252 (4) | −0.0007 (3) | 0.0045 (3) | 0.0004 (4) |
C1 | 0.0240 (16) | 0.0251 (17) | 0.0245 (17) | 0.0033 (14) | 0.0089 (13) | −0.0015 (14) |
C2 | 0.0330 (19) | 0.0300 (19) | 0.0272 (19) | −0.0001 (15) | 0.0073 (15) | 0.0003 (15) |
C3 | 0.041 (2) | 0.031 (2) | 0.030 (2) | 0.0057 (17) | 0.0077 (16) | 0.0040 (16) |
C4 | 0.035 (2) | 0.042 (2) | 0.0275 (19) | 0.0054 (17) | 0.0011 (15) | −0.0007 (16) |
C5 | 0.0278 (19) | 0.038 (2) | 0.040 (2) | −0.0030 (16) | 0.0017 (16) | −0.0053 (17) |
C6 | 0.0280 (18) | 0.0250 (19) | 0.042 (2) | −0.0036 (15) | 0.0058 (16) | −0.0006 (16) |
C7 | 0.0266 (17) | 0.0239 (18) | 0.0239 (17) | 0.0032 (14) | 0.0073 (13) | 0.0015 (13) |
C8 | 0.0339 (19) | 0.0264 (19) | 0.043 (2) | 0.0039 (15) | 0.0197 (16) | 0.0058 (16) |
C9 | 0.034 (2) | 0.036 (2) | 0.051 (2) | −0.0018 (17) | 0.0213 (18) | 0.0047 (18) |
C10 | 0.0295 (19) | 0.045 (2) | 0.040 (2) | 0.0062 (17) | 0.0174 (16) | −0.0017 (18) |
C11 | 0.0308 (19) | 0.031 (2) | 0.038 (2) | 0.0097 (16) | 0.0064 (16) | −0.0047 (16) |
C12 | 0.0268 (17) | 0.0236 (18) | 0.0274 (18) | 0.0006 (14) | 0.0040 (14) | −0.0019 (14) |
C13 | 0.0221 (16) | 0.0241 (17) | 0.0258 (18) | 0.0019 (13) | 0.0056 (13) | −0.0007 (14) |
C14 | 0.0266 (17) | 0.0252 (18) | 0.0243 (17) | 0.0005 (14) | 0.0066 (14) | −0.0015 (14) |
C15 | 0.060 (3) | 0.075 (4) | 0.058 (3) | 0.023 (3) | 0.007 (2) | −0.004 (3) |
C16 | 0.073 (3) | 0.074 (4) | 0.060 (3) | −0.025 (3) | 0.033 (3) | −0.017 (3) |
C17 | 0.0192 (15) | 0.0296 (18) | 0.0243 (17) | 0.0021 (14) | 0.0010 (13) | −0.0008 (14) |
C18 | 0.047 (2) | 0.029 (2) | 0.046 (2) | 0.0029 (17) | 0.0238 (19) | 0.0008 (17) |
C19 | 0.061 (3) | 0.036 (2) | 0.056 (3) | 0.004 (2) | 0.025 (2) | 0.013 (2) |
C20 | 0.047 (2) | 0.027 (2) | 0.043 (2) | 0.0110 (18) | −0.0018 (18) | 0.0017 (17) |
C21 | 0.0309 (19) | 0.040 (2) | 0.041 (2) | 0.0099 (17) | 0.0054 (16) | −0.0082 (18) |
C22 | 0.0337 (19) | 0.034 (2) | 0.035 (2) | −0.0019 (16) | 0.0102 (16) | −0.0017 (16) |
C23 | 0.0268 (17) | 0.0233 (17) | 0.0239 (17) | 0.0032 (14) | 0.0074 (13) | −0.0019 (13) |
C24 | 0.0281 (18) | 0.0267 (18) | 0.0334 (19) | −0.0020 (15) | 0.0077 (15) | 0.0006 (15) |
C25 | 0.0272 (18) | 0.033 (2) | 0.031 (2) | 0.0016 (15) | 0.0009 (15) | −0.0029 (16) |
C26 | 0.036 (2) | 0.036 (2) | 0.031 (2) | 0.0062 (16) | 0.0089 (16) | 0.0063 (16) |
C27 | 0.039 (2) | 0.037 (2) | 0.040 (2) | 0.0014 (17) | 0.0155 (17) | 0.0130 (17) |
C28 | 0.0269 (18) | 0.033 (2) | 0.039 (2) | −0.0042 (15) | 0.0101 (15) | 0.0021 (16) |
C29 | 0.0250 (17) | 0.0251 (18) | 0.0238 (17) | −0.0005 (14) | 0.0059 (13) | −0.0002 (13) |
C30 | 0.0223 (16) | 0.0270 (19) | 0.0296 (18) | 0.0014 (14) | 0.0061 (14) | 0.0005 (14) |
Geometric parameters (Å, º) top
Co1—O1i | 2.045 (2) | C14—C14ii | 1.524 (6) |
Co1—O1 | 2.045 (2) | C14—H14A | 0.9900 |
Co1—O2i | 2.097 (3) | C14—H14B | 0.9900 |
Co1—O2 | 2.097 (3) | C15—O2 | 1.422 (5) |
Co1—O3 | 2.147 (2) | C15—C16 | 1.502 (6) |
Co1—O3i | 2.147 (2) | C15—H15A | 0.9900 |
P1—O1 | 1.492 (2) | C15—H15B | 0.9900 |
P2—O7 | 1.500 (2) | C16—H16A | 0.9800 |
O2—H2E | 0.68 (5) | C16—H16B | 0.9800 |
O3—H3A | 0.82 (5) | C16—H16C | 0.9800 |
O3—H3B | 0.75 (5) | C17—C18 | 1.384 (5) |
N1—O5 | 1.233 (4) | C17—C22 | 1.392 (4) |
N1—O6 | 1.243 (4) | C17—P2 | 1.801 (3) |
N1—O4 | 1.244 (4) | C18—C19 | 1.380 (5) |
C1—C2 | 1.391 (5) | C18—H18 | 0.9500 |
C1—C6 | 1.396 (4) | C19—C20 | 1.371 (5) |
C1—P1 | 1.811 (3) | C19—H19 | 0.9500 |
C2—C3 | 1.390 (5) | C20—C21 | 1.378 (5) |
C2—H2 | 0.9500 | C20—H20 | 0.9500 |
C3—C4 | 1.375 (5) | C21—C22 | 1.378 (5) |
C3—H3 | 0.9500 | C21—H21 | 0.9500 |
C4—C5 | 1.381 (5) | C22—H22 | 0.9500 |
C4—H4 | 0.9500 | C23—C24 | 1.381 (4) |
C5—C6 | 1.393 (5) | C23—C28 | 1.395 (4) |
C5—H5 | 0.9500 | C23—P2 | 1.813 (3) |
C6—H6 | 0.9500 | C24—C25 | 1.387 (5) |
C7—C12 | 1.388 (4) | C24—H24 | 0.9500 |
C7—C8 | 1.392 (4) | C25—C26 | 1.382 (5) |
C7—P1 | 1.806 (3) | C25—H25 | 0.9500 |
C8—C9 | 1.382 (5) | C26—C27 | 1.376 (5) |
C8—H8 | 0.9500 | C26—H26 | 0.9500 |
C9—C10 | 1.383 (5) | C27—C28 | 1.381 (5) |
C9—H9 | 0.9500 | C27—H27 | 0.9500 |
C10—C11 | 1.374 (5) | C28—H28 | 0.9500 |
C10—H10 | 0.9500 | C29—C30 | 1.527 (4) |
C11—C12 | 1.398 (4) | C29—P2 | 1.798 (3) |
C11—H11 | 0.9500 | C29—H29A | 0.9900 |
C12—H12 | 0.9500 | C29—H29B | 0.9900 |
C13—C14 | 1.525 (4) | C30—C30iii | 1.529 (6) |
C13—P1 | 1.788 (3) | C30—H30B | 0.9900 |
C13—H13A | 0.9900 | C30—H30A | 0.9900 |
C13—H13B | 0.9900 | | |
| | | |
O1—Co1—O1i | 180.0 | H16A—C16—H16C | 109.5 |
O1—Co1—O2 | 88.46 (10) | H16B—C16—H16C | 109.5 |
O1i—Co1—O2i | 88.46 (10) | C18—C17—C22 | 118.5 (3) |
O1—Co1—O2i | 91.54 (10) | C18—C17—P2 | 123.0 (3) |
O1i—Co1—O2 | 91.54 (10) | C22—C17—P2 | 118.1 (3) |
O1—Co1—O3 | 92.75 (9) | C19—C18—C17 | 120.1 (3) |
O1i—Co1—O3 | 87.25 (9) | C19—C18—H18 | 119.9 |
O2—Co1—O2i | 180.0 | C17—C18—H18 | 119.9 |
O2—Co1—O3 | 84.30 (11) | C20—C19—C18 | 120.9 (4) |
O2—Co1—O3i | 95.70 (11) | C20—C19—H19 | 119.5 |
O3—Co1—O3i | 180.00 (15) | C18—C19—H19 | 119.5 |
O2i—Co1—O3 | 95.70 (11) | C19—C20—C21 | 119.6 (4) |
O1i—Co1—O3i | 92.75 (9) | C19—C20—H20 | 120.2 |
O1—Co1—O3i | 87.25 (9) | C21—C20—H20 | 120.2 |
O2i—Co1—O3i | 84.30 (11) | C20—C21—C22 | 119.9 (3) |
C2—C1—C6 | 119.4 (3) | C20—C21—H21 | 120.1 |
C2—C1—P1 | 122.8 (3) | C22—C21—H21 | 120.1 |
C6—C1—P1 | 117.7 (3) | C21—C22—C17 | 120.9 (3) |
C3—C2—C1 | 119.6 (3) | C21—C22—H22 | 119.5 |
C3—C2—H2 | 120.2 | C17—C22—H22 | 119.5 |
C1—C2—H2 | 120.2 | C24—C23—C28 | 120.4 (3) |
C4—C3—C2 | 120.8 (3) | C24—C23—P2 | 121.0 (2) |
C4—C3—H3 | 119.6 | C28—C23—P2 | 118.5 (2) |
C2—C3—H3 | 119.6 | C23—C24—C25 | 119.5 (3) |
C3—C4—C5 | 120.2 (3) | C23—C24—H24 | 120.2 |
C3—C4—H4 | 119.9 | C25—C24—H24 | 120.2 |
C5—C4—H4 | 119.9 | C26—C25—C24 | 120.2 (3) |
C4—C5—C6 | 119.7 (3) | C26—C25—H25 | 119.9 |
C4—C5—H5 | 120.1 | C24—C25—H25 | 119.9 |
C6—C5—H5 | 120.1 | C27—C26—C25 | 119.9 (3) |
C5—C6—C1 | 120.3 (3) | C27—C26—H26 | 120.0 |
C5—C6—H6 | 119.9 | C25—C26—H26 | 120.0 |
C1—C6—H6 | 119.9 | C26—C27—C28 | 120.8 (3) |
C12—C7—C8 | 119.4 (3) | C26—C27—H27 | 119.6 |
C12—C7—P1 | 118.3 (2) | C28—C27—H27 | 119.6 |
C8—C7—P1 | 122.2 (2) | C27—C28—C23 | 119.1 (3) |
C9—C8—C7 | 120.4 (3) | C27—C28—H28 | 120.4 |
C9—C8—H8 | 119.8 | C23—C28—H28 | 120.4 |
C7—C8—H8 | 119.8 | C30—C29—P2 | 111.5 (2) |
C8—C9—C10 | 120.0 (3) | C30—C29—H29A | 109.3 |
C8—C9—H9 | 120.0 | P2—C29—H29A | 109.3 |
C10—C9—H9 | 120.0 | C30—C29—H29B | 109.3 |
C11—C10—C9 | 120.2 (3) | P2—C29—H29B | 109.3 |
C11—C10—H10 | 119.9 | H29A—C29—H29B | 108.0 |
C9—C10—H10 | 119.9 | C29—C30—C30iii | 111.2 (3) |
C10—C11—C12 | 120.2 (3) | C29—C30—H30B | 109.4 |
C10—C11—H11 | 119.9 | C30iii—C30—H30B | 109.4 |
C12—C11—H11 | 119.9 | C29—C30—H30A | 109.4 |
C7—C12—C11 | 119.8 (3) | C30iii—C30—H30A | 109.4 |
C7—C12—H12 | 120.1 | H30B—C30—H30A | 108.0 |
C11—C12—H12 | 120.1 | O5—N1—O6 | 121.1 (3) |
C14—C13—P1 | 114.6 (2) | O5—N1—O4 | 120.0 (3) |
C14—C13—H13A | 108.6 | O6—N1—O4 | 118.9 (3) |
P1—C13—H13A | 108.6 | P1—O1—Co1 | 160.74 (15) |
C14—C13—H13B | 108.6 | C15—O2—Co1 | 133.3 (3) |
P1—C13—H13B | 108.6 | C15—O2—H2E | 119 (5) |
H13A—C13—H13B | 107.6 | Co1—O2—H2E | 103 (5) |
C14ii—C14—C13 | 111.7 (3) | Co1—O3—H3A | 104 (3) |
C14ii—C14—H14A | 109.3 | Co1—O3—H3B | 128 (4) |
C13—C14—H14A | 109.3 | H3A—O3—H3B | 108 (5) |
C14ii—C14—H14B | 109.3 | O1—P1—C13 | 115.27 (14) |
C13—C14—H14B | 109.3 | O1—P1—C7 | 111.48 (14) |
H14A—C14—H14B | 107.9 | C13—P1—C7 | 107.04 (15) |
O2—C15—C16 | 116.9 (4) | O1—P1—C1 | 109.25 (14) |
O2—C15—H15A | 108.1 | C13—P1—C1 | 107.66 (15) |
C16—C15—H15A | 108.1 | C7—P1—C1 | 105.64 (14) |
O2—C15—H15B | 108.1 | O7—P2—C29 | 113.27 (14) |
C16—C15—H15B | 108.1 | O7—P2—C17 | 110.96 (14) |
H15A—C15—H15B | 107.3 | C29—P2—C17 | 108.50 (15) |
C15—C16—H16A | 109.5 | O7—P2—C23 | 110.31 (14) |
C15—C16—H16B | 109.5 | C29—P2—C23 | 105.64 (15) |
H16A—C16—H16B | 109.5 | C17—P2—C23 | 107.88 (15) |
C15—C16—H16C | 109.5 | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2E···O7 | 0.68 (5) | 2.01 (5) | 2.660 (4) | 163 (6) |
O3—H3A···O7 | 0.82 (5) | 1.97 (5) | 2.774 (3) | 166 (5) |
O3—H3B···O6 | 0.74 (5) | 2.13 (5) | 2.832 (4) | 157 (5) |
C8—H8···O4ii | 0.95 | 2.47 | 3.418 (4) | 178 |
C12—H12···O6i | 0.95 | 2.58 | 3.224 (4) | 126 |
C13—H13B···O4ii | 0.99 | 2.32 | 3.292 (4) | 169 |
C24—H24···O5iii | 0.95 | 2.48 | 3.383 (4) | 158 |
C30—H30A···O6 | 0.99 | 2.61 | 3.541 (4) | 157 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Mn(C2H6O)2(C28H28O2P2)(H2O)2](NO3)2·C28H28O2P2 | [Co(C2H6O)2(C28H28O2P2)(H2O)2](NO3)2·C28H28O2P2 |
Mr | 1224.02 | 1228.01 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 13.4134 (3), 10.3270 (3), 22.1028 (6) | 13.3646 (5), 10.2517 (5), 22.0744 (11) |
β (°) | 101.900 (1) | 101.920 (3) |
V (Å3) | 2995.88 (14) | 2959.2 (2) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.39 | 0.47 |
Crystal size (mm) | 0.24 × 0.22 × 0.03 | 0.16 × 0.14 × 0.03 |
|
Data collection |
Diffractometer | Bruker Nonius 95mm CCD camera on κ-goniostat diffractometer | Bruker Nonius 95mm CCD camera on κ-goniostat diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.912, 0.988 | 0.929, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 40734, 6856, 5673 | 36332, 6806, 4594 |
Rint | 0.042 | 0.093 |
(sin θ/λ)max (Å−1) | 0.652 | 0.652 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.111, 1.05 | 0.062, 0.135, 1.03 |
No. of reflections | 6856 | 6806 |
No. of parameters | 382 | 382 |
H-atom treatment | Only H-atom displacement parameters refined | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.71, −0.43 | 0.53, −0.38 |
Selected geometric parameters (Å, º) for (I) topMn1—O1 | 2.1109 (14) | P1—O1 | 1.4964 (15) |
Mn1—O2 | 2.1998 (17) | P2—O7 | 1.5036 (16) |
Mn1—O3 | 2.2415 (16) | | |
| | | |
O1—Mn1—O1i | 180.0 | O2—Mn1—O2i | 180.0 |
O1—Mn1—O2 | 88.84 (6) | O2—Mn1—O3 | 83.16 (7) |
O1—Mn1—O2i | 91.16 (6) | O2—Mn1—O3i | 96.84 (7) |
O1—Mn1—O3 | 93.28 (6) | O3i—Mn1—O3 | 180.00 (10) |
O1i—Mn1—O3 | 86.72 (6) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2E···O7 | 1.06 (4) | 1.67 (4) | 2.652 (2) | 152 (3) |
O3—H3A···O7 | 0.88 (4) | 1.93 (4) | 2.784 (2) | 163 (4) |
O3—H3B···O6 | 0.88 (4) | 1.99 (4) | 2.828 (3) | 159 (4) |
C8—H8···O4ii | 0.95 | 2.52 | 3.465 (3) | 177 |
C12—H12···O6i | 0.95 | 2.64 | 3.271 (3) | 124 |
C13—H13B···O4ii | 0.99 | 2.33 | 3.310 (3) | 171 |
C24—H24···O5iii | 0.95 | 2.49 | 3.387 (3) | 158 |
C30—H30A···O6 | 0.99 | 2.58 | 3.500 (3) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (II) topCo1—O1 | 2.045 (2) | P1—O1 | 1.492 (2) |
Co1—O2 | 2.097 (3) | P2—O7 | 1.500 (2) |
Co1—O3 | 2.147 (2) | | |
| | | |
O1—Co1—O1i | 180.0 | O2—Co1—O2i | 180.0 |
O1—Co1—O2 | 88.46 (10) | O2—Co1—O3 | 84.30 (11) |
O1—Co1—O2i | 91.54 (10) | O2—Co1—O3i | 95.70 (11) |
O1—Co1—O3 | 92.75 (9) | O3—Co1—O3i | 180.00 (15) |
O1i—Co1—O3 | 87.25 (9) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2E···O7 | 0.68 (5) | 2.01 (5) | 2.660 (4) | 163 (6) |
O3—H3A···O7 | 0.82 (5) | 1.97 (5) | 2.774 (3) | 166 (5) |
O3—H3B···O6 | 0.74 (5) | 2.13 (5) | 2.832 (4) | 157 (5) |
C8—H8···O4ii | 0.95 | 2.47 | 3.418 (4) | 178 |
C12—H12···O6i | 0.95 | 2.58 | 3.224 (4) | 126 |
C13—H13B···O4ii | 0.99 | 2.32 | 3.292 (4) | 169 |
C24—H24···O5iii | 0.95 | 2.48 | 3.383 (4) | 158 |
C30—H30A···O6 | 0.99 | 2.61 | 3.541 (4) | 157 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
In combination with various transition metals, 1,4-bis(diphenylphosphino)butane (dppb) has proved to be an effective catalyst for many organic reactions (see, for example, Bogado et al., 2003; Farnetti & Marsich, 2004; Sundermeier et al., 2003). Because of these catalytic effects, the coordination chemistry of dppb has received much attention. Although there are many structurally characterized examples of dppb complexes of the transition metals [for example: NiII (Câmpian et al., 2007), AgI (Aslanidis et al., 2004) and RuII (Brito et al., 2007)], the oxidized form of the ligand, 1,4-bis(diphenylphosphinoyl)butane (dppbO2) has received little attention. There are examples of dppbO2 coordination to the lanthanides (Spichal et al., 2006) and to tin (Teo et al., 2008), and there are examples of 1,3-bis(diphenylphosphinoyl)propane (dpppO2) coordination to CoII (Harding et al., 2007) and CuII (Platt & Lees, 2007), but to date there are no characterized examples of dppbO2 coordination to the d-block elements. We report here the first examples of the coordination of dppbO2 to the first-row transition metals.
The structures of (I) and (II), {trans-[M(EtOH)2(H2O)2(µ-dppbO2)](NO3)2.dppbO2}n, are essentially isomorphous. The structures are centrosymmetric and the coordination geometry is octahedral, MO6, with the MII ions sitting at centres of inversion. Each metal ion is coordinated by two ethanol molecules, two water molecules and two bridging 1,4-bis(diphenylphosphinoyl)butane (dppbO2) ligands in an all-trans configuration to form one-dimensional polymeric chains. Parallel chains are linked by hydrogen bonds to uncoordinated dppbO2 molecules. M—O bond lengths [2.111 (1)–2.242 (2) Å for Mn and 2.045 (2)–2.147 (2) Å for Co] are typical of those of other octahedrally coordinated O-donor MnII and CoII complexes, for example [Mn(C14H8N2O6)(H2O)4]n [2.141 (2)-2.226 (2) Å; Tang et al.,2007], [Mn(C10H8O5S)(H2O)4]n [2.153 (2)–2.244 (2) Å; Su et al., 2006], {[Co(C8H7NO2)2(H2O)2](NO3)2}n [2.063 (1)–2.108 (1) Å; Domasevitch, 2008] and [Co(dbm)2(µ-dppeO2)]n [2.153 (2)-2.244 (2) Å; Harding et al., 2007].
The coordination geometries of the MII ions each show elongation along one axis. Both complexes show similar elongation along the axis of the trans-coordinated water molecules, O3—Co—O3(1 - x, 1 - y, 1 - z). Lengthening of these bonds is consistent with the water molecules being hydrogen-bonded to adjacent phosphine oxide groups (O3—H3A···O7) and nitrate anions (O3—H3A···O6). Such elongation is also consistent with Jahn–Teller distortion, and this may be expected to be observed in complexes of the CoII d7 ion. For the MnII d5 ion however, Jahn–Teller effects are not expected to be significant. The greater distortion observed in the MnII complex is attributed to the role of hydrogen bonding having a greater influence over the generally weaker M—O bonds in the Mn complex. All M—O bonds are longer in the Mn complex than the Co complex, in keeping with the Irving–Williams series, which indicates stability in the order Mn < Fe < Co.
The metal centres are linked by bridging dppbO2 ligands, which are bisected by an inversion centre. The aliphatic chains of the dppbO2 ligands adopt an all-anti conformation, aligning the P═O groups in a strict antiparallel arrangement which affords the linear propagation of the coordination polymer along the crystallographic b axis. Adjacent chains are linked via hydrogen bonds to form a two-dimensional network running parallel to the (001) plane.
The hydrogen-bonding network consists of classical O—H···O hydrogen bonds and C—H···O interactions. One hydrogen bond, O3—H3B···O6, binds the nitrate ion to a coordinated water molecule. Two other hydrogen bonds, O3—H3A···O7 and O2—H2E···O7, are the primary means of attachment of the uncoordinated dppbO2 molecules which form the link between the parallel polymeric chains. Weaker C—H···O interactions serve to stabilize further both the position of the nitrate ion within the structure and the orientation of the dppbO2 molecules. The hydrogen-bonding parameters for (I) are given in Table 2, and those for (II) in Table 4.
Weak methylene–phenyl and phenyl–phenyl (edge to face) C—H···π interactions, with H···π (centroid) distances of 2.83 and 2.79 Å, respectively, in (I), and 2.80 and 2.76 Å, respectively, in (II), stabilize the arrangements between polymer chains and dppbO2 molecules within the (001) sheets. In the first of these interactions, methylene atom C29 acts as donor, via atom H29B, to the C7–C12 ring at (1 - x, 1 - y, 1 - z). In the second interaction, phenyl atom C21 acts as donor, via atom H21, to the C1–C6 ring at (x, -1 + y, z). The stacking of the (001) sheets is stabilized by two further C—H···π interactions: a phenyl–phenyl (edge to face) interaction between neighbouring dppbO2 molecules, with H···π (centroid) distances of 2.90 [(I)] and 2.89 Å [(II)], and a methyl–phenyl interaction between adjacent polymeric chains, with H···π (centroid) distances of 2.91 Å [(I)] and 2.96 Å [(II)]. In the phenyl–phenyl interaction, atom C26 acts as donor, via atom H26, to the C17–C22 ring at (-x, 1/2 + y, 1/2 - z), and in the methyl–phenyl interaction, atom C16 acts as donor, via atom H16B, to the C1–C6 ring at (1 - x, -1/2 + y, 1/2 - z). The observed H···π (centroid) distances for the four interactions in both structures (2.76–2.96 Å) are markedly shorter than those reported for similar interactions in the solid-state alkyl bisdiphenylphosphine oxides (3.00–3.65 Å; Calcagno et al., 2000). We attribute this to the effects of both coordinate bonding to the metal atoms and intramolecular hydrogen bonding stabilizing the dppbO2 molecules in closer proximity.