The title copper complex, [Cu(H
2P
2O
7)(C
15H
11N
3)]
2·4.5H
2O, consists of two very similar independent Cu(Tpy)H
2P
2O
7 monomeric units (Tpy is 2,2':6',2''-terpyridine) plus four and a half water molecules of hydration, some of which are disordered. Tpy units bind through the usual triple bite
via their N atoms, and the H
2P
2O
72- anions coordinate through two O atoms from two different phosphate units. Each independent CuN
3O
2 chromophore can be described as a slightly deformed square pyramid, with one of them having a sixth, semicoordinated, O atom from a centrosymmetrically related CuN
3O
2 unit in a weakly bound second apical position suggesting an octahedral environment for the cation and weak dimerization of the molecule. The two independent complex molecules are connected
via two strong O-H
O interactions between the phosphate groups to form hydrogen-bonded dinuclear units, further linked into [111] columns, resulting in a very complex three-dimensional supramolecular structure through a variety of classical and nonclassical hydrogen bonds, as well as
-
interactions.
Supporting information
CCDC reference: 829690
Cu2P2O7 (0.26 g, 1 mmol) was added to 50 ml of an alcohol–water
(v:v, 1:1) solution containing dissolved 2,2':6',2''-terpyridine
(0.26 g, 1 mmol) and stirred for 4 h at room temperature. A few drops of
concentrated phosphoric acid (85%) was added to clear the solution which was
then filtered. After 2 weeks green crystals were separated and dried in air.
Analysis calculated for C30H26Cu2N6O14P4.4.5(H2O): C, 35.06; H,
3.44; N, 8.18. Found: C, 35.15; H, 3.45; N, 8.22. Yield based on Cu2P2O7
55%.
Two hydration water molecules (O4W and O5W) present positional
disorder of different kinds, leading to some apparently odd short contacts,
but easily accountable when disorder is taken into account. O5W is only
partially occupied, with an occupancy factor which refined to a value slightly
larger than 0.5. In its final position the oxygen atom `bumps' its
O5Wxi [symmetry code: (xi) 2 - x, 2 - y, 1 - z]
centrosymmetric image 1.830 (1) Å away, so they cannot be but mutually
exclusive and the corresponding occupancy factor was accordingly fixed at
0.50. There is, in addition, a short O5W···O7Bviii [symmetry
code: (viii) x, 1 + y, z] distance of 2.870 (4) Å, which
can in principle be explained by a hydrogen bond donated by the depleted water
molecule O5W and accepted by the pyrophosphate. On the other hand,
O4W is fully occupied, but rather near [2.839 (4) Å] the
inversion-related O4Wxii [symmetry code: (xii) 1 - x, 1 -
y, 1 - z], a fact only accountable through hydrogen bonding but
inconsistent with an inversion centre between the two identical moieties. In
addition, no clear H images could be found in the difference map, for
what rotational disorder is to be assumed. This disordered model would
allow for the possibility of hydrogen-bonding interaction between the two
neighbours, while permitting an `average' inversion operation which would
apply `truly' only for the oxygen atoms but not to the H2O groups as a
whole. This is not unusual in water solvates built up around a symmetry
centre. All the H atoms in the structure (except those corresponding to the
disordered water molecules O4W and O5W) could be located in a
difference Fourier; those attached to O were further refined with restraints
[for water molecules: O—H: 0.85 (1), H···H: 1.35 (2) Å; for phosphate
groups: O—H: 0.85 (1), P···H: 2.05 (2) Å]. H atoms attached to C were placed
at calculated positions (C—H: 0.93 Å) and allowed to ride. In all cases
displacement factors were taken as U(H)iso = 1.2Uhost.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation,
1988); cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation,
1988); data reduction: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation,
1988); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Bis[(dihydrogen pyrophosphato-
κ2O,
O')(2,2':6',2''-
terpyridine-
κ2N,
N')copper(II)] 4.5-hydrate
top
Crystal data top
[Cu(H2P2O7)(C15H11N3)]2·4.5H2O | Z = 2 |
Mr = 1026.60 | F(000) = 1046 |
Triclinic, P1 | Dx = 1.788 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.2894 (17) Å | Cell parameters from 25 reflections |
b = 13.539 (2) Å | θ = 7.5–12.5° |
c = 13.606 (2) Å | µ = 1.37 mm−1 |
α = 73.915 (13)° | T = 295 K |
β = 78.438 (14)° | Block, blue |
γ = 74.410 (12)° | 0.32 × 0.30 × 0.26 mm |
V = 1906.8 (5) Å3 | |
Data collection top
Rigaku AFC6 diffractometer | 5449 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 26.0°, θmin = 1.6° |
ω/2θ scans | h = −13→13 |
Absorption correction: ψ scan North et al., 1968. | k = −16→1 |
Tmin = 0.61, Tmax = 0.70 | l = −16→16 |
8505 measured reflections | 3 standard reflections every 150 reflections |
7493 independent reflections | intensity decay: 1% |
Refinement top
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0533P)2 + 0.7109P] where P = (Fo2 + 2Fc2)/3 |
7493 reflections | (Δ/σ)max = 0.001 |
581 parameters | Δρmax = 0.52 e Å−3 |
18 restraints | Δρmin = −0.58 e Å−3 |
Crystal data top
[Cu(H2P2O7)(C15H11N3)]2·4.5H2O | γ = 74.410 (12)° |
Mr = 1026.60 | V = 1906.8 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.2894 (17) Å | Mo Kα radiation |
b = 13.539 (2) Å | µ = 1.37 mm−1 |
c = 13.606 (2) Å | T = 295 K |
α = 73.915 (13)° | 0.32 × 0.30 × 0.26 mm |
β = 78.438 (14)° | |
Data collection top
Rigaku AFC6 diffractometer | 5449 reflections with I > 2σ(I) |
Absorption correction: ψ scan North et al., 1968. | Rint = 0.024 |
Tmin = 0.61, Tmax = 0.70 | 3 standard reflections every 150 reflections |
8505 measured reflections | intensity decay: 1% |
7493 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 18 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.52 e Å−3 |
7493 reflections | Δρmin = −0.58 e Å−3 |
581 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | 0.91119 (4) | 0.48453 (3) | 0.90371 (3) | 0.02615 (11) | |
Cu2 | 0.64597 (3) | −0.03332 (3) | 0.55620 (3) | 0.02569 (10) | |
P1A | 0.97504 (7) | 0.24110 (6) | 0.92865 (6) | 0.02497 (18) | |
P2A | 0.78864 (8) | 0.35606 (6) | 0.79143 (6) | 0.02576 (18) | |
O1A | 0.9914 (2) | 0.33932 (17) | 0.95128 (18) | 0.0321 (5) | |
O2A | 0.8714 (2) | 0.20098 (19) | 1.01331 (17) | 0.0349 (5) | |
H2A | 0.856 (3) | 0.1455 (18) | 1.008 (2) | 0.042* | |
O3A | 1.0885 (2) | 0.15682 (19) | 0.91752 (19) | 0.0383 (6) | |
O4A | 0.9188 (2) | 0.27478 (17) | 0.82086 (16) | 0.0275 (5) | |
O5A | 0.6869 (2) | 0.29362 (19) | 0.85088 (19) | 0.0346 (5) | |
H5A | 0.693 (3) | 0.2394 (18) | 0.829 (2) | 0.042* | |
O6A | 0.7964 (2) | 0.37223 (18) | 0.67704 (18) | 0.0363 (6) | |
O7A | 0.7716 (2) | 0.45047 (17) | 0.83289 (18) | 0.0329 (5) | |
P1B | 0.50394 (8) | 0.20339 (7) | 0.55952 (7) | 0.02971 (19) | |
P2B | 0.72701 (7) | 0.13331 (6) | 0.66680 (6) | 0.02347 (17) | |
O1B | 0.5178 (2) | 0.09465 (17) | 0.54477 (18) | 0.0319 (5) | |
O2B | 0.5474 (3) | 0.2762 (2) | 0.4602 (2) | 0.0452 (6) | |
H2B | 0.510 (3) | 0.3412 (9) | 0.4501 (19) | 0.054* | |
O3B | 0.3737 (2) | 0.25169 (19) | 0.60538 (19) | 0.0378 (6) | |
O4B | 0.5877 (2) | 0.19400 (19) | 0.64573 (19) | 0.0378 (6) | |
O5B | 0.8100 (2) | 0.21130 (19) | 0.60294 (18) | 0.0363 (6) | |
H5B | 0.803 (3) | 0.2625 (17) | 0.630 (2) | 0.044* | |
O6B | 0.7233 (2) | 0.12023 (17) | 0.78110 (17) | 0.0303 (5) | |
O7B | 0.7645 (2) | 0.03633 (17) | 0.62635 (18) | 0.0308 (5) | |
N1A | 0.7869 (3) | 0.5036 (2) | 1.0320 (2) | 0.0304 (6) | |
N2A | 0.8690 (2) | 0.6367 (2) | 0.8781 (2) | 0.0259 (6) | |
N3A | 1.0366 (2) | 0.5209 (2) | 0.7759 (2) | 0.0289 (6) | |
C1A | 0.7477 (3) | 0.4275 (3) | 1.1067 (3) | 0.0381 (8) | |
H1A | 0.7856 | 0.3575 | 1.1061 | 0.046* | |
C2A | 0.6531 (4) | 0.4484 (3) | 1.1849 (3) | 0.0438 (9) | |
H2C | 0.6290 | 0.3936 | 1.2369 | 0.053* | |
C3A | 0.5944 (4) | 0.5525 (3) | 1.1846 (3) | 0.0478 (10) | |
H3C | 0.5304 | 0.5688 | 1.2364 | 0.057* | |
C4A | 0.6329 (3) | 0.6319 (3) | 1.1058 (3) | 0.0423 (9) | |
H4A | 0.5936 | 0.7022 | 1.1030 | 0.051* | |
C5A | 0.7304 (3) | 0.6053 (3) | 1.0314 (3) | 0.0297 (7) | |
C6A | 0.7802 (3) | 0.6825 (3) | 0.9438 (3) | 0.0279 (7) | |
C7A | 0.7441 (3) | 0.7921 (3) | 0.9257 (3) | 0.0337 (8) | |
H7A | 0.6840 | 0.8244 | 0.9716 | 0.040* | |
C8A | 0.7997 (3) | 0.8514 (3) | 0.8381 (3) | 0.0369 (8) | |
H8A | 0.7753 | 0.9247 | 0.8237 | 0.044* | |
C9A | 0.8927 (3) | 0.8025 (3) | 0.7704 (3) | 0.0342 (8) | |
H9A | 0.9304 | 0.8423 | 0.7113 | 0.041* | |
C10A | 0.9269 (3) | 0.6930 (2) | 0.7941 (2) | 0.0273 (7) | |
C11A | 1.0257 (3) | 0.6265 (2) | 0.7354 (2) | 0.0272 (7) | |
C12A | 1.1024 (3) | 0.6649 (3) | 0.6477 (3) | 0.0351 (8) | |
H12A | 1.0926 | 0.7373 | 0.6205 | 0.042* | |
C13A | 1.1933 (4) | 0.5947 (3) | 0.6011 (3) | 0.0406 (8) | |
H13A | 1.2468 | 0.6192 | 0.5434 | 0.049* | |
C14A | 1.2039 (3) | 0.4867 (3) | 0.6418 (3) | 0.0392 (8) | |
H14A | 1.2632 | 0.4380 | 0.6108 | 0.047* | |
C15A | 1.1246 (3) | 0.4535 (3) | 0.7288 (3) | 0.0354 (8) | |
H15A | 1.1322 | 0.3814 | 0.7561 | 0.042* | |
N1B | 0.7522 (2) | −0.0023 (2) | 0.4168 (2) | 0.0278 (6) | |
N2B | 0.7415 (2) | −0.1747 (2) | 0.5514 (2) | 0.0259 (6) | |
N3B | 0.5681 (2) | −0.1181 (2) | 0.6908 (2) | 0.0276 (6) | |
C1B | 0.7506 (3) | 0.0917 (3) | 0.3517 (3) | 0.0357 (8) | |
H1B | 0.6945 | 0.1508 | 0.3686 | 0.043* | |
C2B | 0.8303 (4) | 0.1040 (3) | 0.2594 (3) | 0.0414 (9) | |
H2D | 0.8283 | 0.1707 | 0.2157 | 0.050* | |
C3B | 0.9114 (4) | 0.0179 (3) | 0.2335 (3) | 0.0446 (9) | |
H3B | 0.9640 | 0.0251 | 0.1712 | 0.053* | |
C4B | 0.9154 (3) | −0.0811 (3) | 0.3004 (3) | 0.0369 (8) | |
H4B | 0.9711 | −0.1408 | 0.2844 | 0.044* | |
C5B | 0.8342 (3) | −0.0880 (3) | 0.3914 (2) | 0.0266 (7) | |
C6B | 0.8266 (3) | −0.1879 (3) | 0.4692 (2) | 0.0267 (7) | |
C7B | 0.8941 (3) | −0.2893 (3) | 0.4624 (3) | 0.0368 (8) | |
H7B | 0.9554 | −0.2995 | 0.4069 | 0.044* | |
C8B | 0.8676 (3) | −0.3739 (3) | 0.5397 (3) | 0.0394 (8) | |
H8B | 0.9116 | −0.4418 | 0.5363 | 0.047* | |
C9B | 0.7762 (3) | −0.3592 (3) | 0.6226 (3) | 0.0354 (8) | |
H9B | 0.7571 | −0.4164 | 0.6741 | 0.042* | |
C10B | 0.7145 (3) | −0.2572 (3) | 0.6263 (3) | 0.0279 (7) | |
C11B | 0.6142 (3) | −0.2237 (3) | 0.7081 (3) | 0.0290 (7) | |
C12B | 0.5713 (3) | −0.2934 (3) | 0.7953 (3) | 0.0364 (8) | |
H12B | 0.6027 | −0.3658 | 0.8050 | 0.044* | |
C13B | 0.4800 (3) | −0.2521 (3) | 0.8679 (3) | 0.0422 (9) | |
H13B | 0.4495 | −0.2966 | 0.9272 | 0.051* | |
C14B | 0.4357 (3) | −0.1447 (3) | 0.8510 (3) | 0.0429 (9) | |
H14B | 0.3760 | −0.1157 | 0.8993 | 0.051* | |
C15B | 0.4807 (3) | −0.0804 (3) | 0.7615 (3) | 0.0368 (8) | |
H15B | 0.4489 | −0.0079 | 0.7500 | 0.044* | |
O1W | 0.3134 (3) | 0.1603 (4) | 0.8022 (3) | 0.0823 (12) | |
H1WA | 0.2394 (19) | 0.160 (4) | 0.829 (3) | 0.099* | |
H1WB | 0.313 (4) | 0.202 (4) | 0.744 (2) | 0.099* | |
O2W | 0.8150 (3) | 0.0419 (2) | 0.9779 (2) | 0.0463 (7) | |
H2WA | 0.840 (4) | −0.0221 (12) | 1.008 (3) | 0.056* | |
H2WB | 0.796 (4) | 0.043 (3) | 0.9202 (17) | 0.056* | |
O3W | 0.4998 (3) | 0.0852 (3) | 0.9177 (2) | 0.0630 (9) | |
H3WB | 0.566 (2) | 0.093 (4) | 0.877 (3) | 0.076* | |
H3WA | 0.453 (3) | 0.073 (2) | 0.883 (3) | 0.076* | |
O4W | 0.4414 (3) | 0.4860 (2) | 0.4234 (3) | 0.0647 (9) | |
O5W | 1.0048 (5) | 0.9335 (5) | 0.5415 (4) | 0.0515 (14) | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0312 (2) | 0.01854 (19) | 0.0286 (2) | −0.00577 (15) | −0.00429 (16) | −0.00523 (15) |
Cu2 | 0.0273 (2) | 0.02001 (19) | 0.0263 (2) | −0.00198 (15) | −0.00021 (15) | −0.00557 (15) |
P1A | 0.0272 (4) | 0.0178 (4) | 0.0271 (4) | −0.0026 (3) | −0.0046 (3) | −0.0026 (3) |
P2A | 0.0308 (4) | 0.0183 (4) | 0.0290 (4) | −0.0047 (3) | −0.0082 (3) | −0.0048 (3) |
O1A | 0.0385 (13) | 0.0209 (11) | 0.0390 (13) | −0.0061 (10) | −0.0157 (11) | −0.0036 (10) |
O2A | 0.0442 (14) | 0.0324 (13) | 0.0283 (12) | −0.0157 (11) | 0.0019 (10) | −0.0055 (10) |
O3A | 0.0347 (13) | 0.0263 (12) | 0.0462 (15) | 0.0040 (10) | −0.0073 (11) | −0.0056 (11) |
O4A | 0.0287 (11) | 0.0240 (11) | 0.0271 (11) | −0.0014 (9) | −0.0018 (9) | −0.0074 (9) |
O5A | 0.0317 (12) | 0.0281 (13) | 0.0456 (14) | −0.0076 (10) | −0.0031 (11) | −0.0118 (11) |
O6A | 0.0547 (15) | 0.0266 (12) | 0.0320 (13) | −0.0133 (11) | −0.0147 (11) | −0.0038 (10) |
O7A | 0.0394 (13) | 0.0197 (11) | 0.0431 (14) | −0.0015 (10) | −0.0157 (11) | −0.0109 (10) |
P1B | 0.0305 (4) | 0.0224 (4) | 0.0359 (5) | 0.0019 (3) | −0.0128 (4) | −0.0082 (4) |
P2B | 0.0247 (4) | 0.0201 (4) | 0.0261 (4) | −0.0040 (3) | −0.0054 (3) | −0.0057 (3) |
O1B | 0.0274 (12) | 0.0254 (12) | 0.0428 (13) | −0.0002 (9) | −0.0090 (10) | −0.0104 (10) |
O2B | 0.0522 (16) | 0.0300 (13) | 0.0427 (15) | −0.0032 (12) | 0.0011 (12) | −0.0026 (12) |
O3B | 0.0266 (12) | 0.0351 (13) | 0.0475 (15) | 0.0085 (10) | −0.0095 (11) | −0.0147 (12) |
O4B | 0.0310 (12) | 0.0379 (14) | 0.0483 (15) | 0.0069 (11) | −0.0179 (11) | −0.0218 (12) |
O5B | 0.0466 (14) | 0.0309 (13) | 0.0343 (13) | −0.0180 (11) | 0.0012 (11) | −0.0081 (10) |
O6B | 0.0395 (13) | 0.0265 (12) | 0.0267 (11) | −0.0097 (10) | −0.0073 (10) | −0.0053 (9) |
O7B | 0.0318 (12) | 0.0234 (11) | 0.0386 (13) | −0.0001 (9) | −0.0110 (10) | −0.0111 (10) |
N1A | 0.0339 (15) | 0.0259 (14) | 0.0314 (15) | −0.0073 (12) | −0.0039 (12) | −0.0066 (12) |
N2A | 0.0295 (14) | 0.0215 (13) | 0.0291 (14) | −0.0064 (11) | −0.0066 (11) | −0.0073 (11) |
N3A | 0.0293 (14) | 0.0248 (14) | 0.0316 (14) | −0.0067 (11) | −0.0034 (11) | −0.0051 (12) |
C1A | 0.044 (2) | 0.0315 (19) | 0.039 (2) | −0.0129 (16) | −0.0048 (16) | −0.0057 (16) |
C2A | 0.045 (2) | 0.047 (2) | 0.040 (2) | −0.0203 (19) | −0.0038 (17) | −0.0033 (18) |
C3A | 0.040 (2) | 0.058 (3) | 0.040 (2) | −0.0104 (19) | 0.0047 (17) | −0.0102 (19) |
C4A | 0.040 (2) | 0.041 (2) | 0.041 (2) | −0.0039 (17) | −0.0026 (16) | −0.0097 (17) |
C5A | 0.0299 (17) | 0.0311 (17) | 0.0298 (17) | −0.0070 (14) | −0.0046 (13) | −0.0094 (14) |
C6A | 0.0296 (16) | 0.0258 (16) | 0.0310 (17) | −0.0048 (13) | −0.0095 (13) | −0.0089 (14) |
C7A | 0.0378 (18) | 0.0262 (17) | 0.0370 (19) | 0.0013 (14) | −0.0089 (15) | −0.0126 (15) |
C8A | 0.047 (2) | 0.0205 (16) | 0.043 (2) | −0.0049 (15) | −0.0135 (17) | −0.0058 (15) |
C9A | 0.0424 (19) | 0.0246 (17) | 0.0362 (18) | −0.0097 (15) | −0.0106 (15) | −0.0026 (14) |
C10A | 0.0292 (16) | 0.0238 (16) | 0.0305 (17) | −0.0096 (13) | −0.0081 (13) | −0.0023 (13) |
C11A | 0.0294 (16) | 0.0238 (16) | 0.0274 (16) | −0.0065 (13) | −0.0074 (13) | −0.0015 (13) |
C12A | 0.0368 (19) | 0.0296 (18) | 0.0342 (18) | −0.0086 (15) | −0.0062 (15) | 0.0018 (15) |
C13A | 0.041 (2) | 0.040 (2) | 0.0346 (19) | −0.0084 (17) | −0.0011 (16) | −0.0013 (16) |
C14A | 0.041 (2) | 0.036 (2) | 0.037 (2) | −0.0030 (16) | −0.0009 (16) | −0.0116 (16) |
C15A | 0.0360 (18) | 0.0283 (18) | 0.0393 (19) | −0.0058 (15) | −0.0025 (15) | −0.0074 (15) |
N1B | 0.0274 (14) | 0.0281 (14) | 0.0274 (14) | −0.0053 (11) | −0.0019 (11) | −0.0083 (11) |
N2B | 0.0260 (13) | 0.0256 (14) | 0.0284 (14) | −0.0051 (11) | −0.0065 (11) | −0.0089 (11) |
N3B | 0.0269 (14) | 0.0257 (14) | 0.0296 (14) | −0.0054 (11) | −0.0036 (11) | −0.0065 (11) |
C1B | 0.0383 (19) | 0.0315 (19) | 0.0344 (19) | −0.0056 (15) | −0.0035 (15) | −0.0062 (15) |
C2B | 0.046 (2) | 0.043 (2) | 0.0319 (19) | −0.0178 (18) | −0.0004 (16) | 0.0008 (16) |
C3B | 0.039 (2) | 0.060 (3) | 0.0320 (19) | −0.0133 (19) | 0.0041 (16) | −0.0109 (18) |
C4B | 0.0336 (18) | 0.043 (2) | 0.0334 (18) | −0.0035 (16) | −0.0007 (15) | −0.0152 (16) |
C5B | 0.0240 (15) | 0.0303 (17) | 0.0279 (16) | −0.0068 (13) | −0.0031 (12) | −0.0105 (14) |
C6B | 0.0223 (15) | 0.0296 (17) | 0.0304 (16) | −0.0024 (13) | −0.0061 (13) | −0.0126 (14) |
C7B | 0.0308 (18) | 0.0354 (19) | 0.044 (2) | 0.0007 (15) | −0.0046 (15) | −0.0171 (17) |
C8B | 0.0376 (19) | 0.0256 (18) | 0.055 (2) | 0.0058 (15) | −0.0146 (17) | −0.0164 (17) |
C9B | 0.044 (2) | 0.0202 (16) | 0.043 (2) | −0.0037 (14) | −0.0164 (16) | −0.0053 (15) |
C10B | 0.0283 (16) | 0.0241 (16) | 0.0326 (17) | −0.0065 (13) | −0.0082 (13) | −0.0055 (13) |
C11B | 0.0315 (17) | 0.0286 (17) | 0.0286 (16) | −0.0089 (14) | −0.0075 (13) | −0.0052 (14) |
C12B | 0.041 (2) | 0.0339 (19) | 0.0351 (19) | −0.0165 (16) | −0.0093 (15) | 0.0005 (15) |
C13B | 0.041 (2) | 0.053 (2) | 0.0320 (19) | −0.0230 (19) | 0.0001 (16) | −0.0013 (17) |
C14B | 0.0338 (19) | 0.062 (3) | 0.0339 (19) | −0.0161 (18) | 0.0051 (15) | −0.0141 (18) |
C15B | 0.0340 (19) | 0.039 (2) | 0.0371 (19) | −0.0066 (16) | −0.0007 (15) | −0.0130 (16) |
O1W | 0.0416 (18) | 0.110 (3) | 0.072 (2) | −0.011 (2) | 0.0136 (16) | −0.005 (2) |
O2W | 0.0667 (19) | 0.0253 (13) | 0.0474 (16) | −0.0100 (13) | −0.0191 (14) | −0.0020 (12) |
O3W | 0.0450 (17) | 0.087 (2) | 0.0565 (19) | −0.0233 (17) | 0.0070 (14) | −0.0188 (18) |
O4W | 0.083 (2) | 0.0391 (17) | 0.064 (2) | −0.0132 (16) | 0.0002 (17) | −0.0066 (14) |
O5W | 0.043 (3) | 0.060 (4) | 0.045 (3) | −0.006 (3) | −0.005 (2) | −0.009 (3) |
Geometric parameters (Å, º) top
Cu1—O1A | 1.918 (2) | C8A—H8A | 0.9300 |
Cu1—N2A | 1.932 (3) | C9A—C10A | 1.388 (5) |
Cu1—N1A | 2.039 (3) | C9A—H9A | 0.9300 |
Cu1—N3A | 2.046 (3) | C10A—C11A | 1.481 (4) |
Cu1—O7A | 2.206 (2) | C11A—C12A | 1.389 (5) |
Cu2—O1B | 1.927 (2) | C12A—C13A | 1.381 (5) |
Cu2—N2B | 1.940 (3) | C12A—H12A | 0.9300 |
Cu2—N1B | 2.032 (3) | C13A—C14A | 1.394 (5) |
Cu2—N3B | 2.043 (3) | C13A—H13A | 0.9300 |
Cu2—O7B | 2.298 (2) | C14A—C15A | 1.379 (5) |
P1A—O3A | 1.483 (2) | C14A—H14A | 0.9300 |
P1A—O1A | 1.510 (2) | C15A—H15A | 0.9300 |
P1A—O2A | 1.564 (2) | N1B—C1B | 1.332 (4) |
P1A—O4A | 1.616 (2) | N1B—C5B | 1.356 (4) |
P2A—O7A | 1.488 (2) | N2B—C6B | 1.339 (4) |
P2A—O6A | 1.498 (2) | N2B—C10B | 1.343 (4) |
P2A—O5A | 1.568 (2) | N3B—C15B | 1.334 (4) |
P2A—O4A | 1.628 (2) | N3B—C11B | 1.354 (4) |
O2A—H2A | 0.84 (3) | C1B—C2B | 1.388 (5) |
O5A—H5A | 0.85 (3) | C1B—H1B | 0.9300 |
P1B—O1B | 1.503 (2) | C2B—C3B | 1.359 (6) |
P1B—O2B | 1.515 (3) | C2B—H2D | 0.9300 |
P1B—O3B | 1.523 (2) | C3B—C4B | 1.391 (6) |
P1B—O4B | 1.607 (2) | C3B—H3B | 0.9300 |
P2B—O7B | 1.488 (2) | C4B—C5B | 1.382 (5) |
P2B—O6B | 1.509 (2) | C4B—H4B | 0.9300 |
P2B—O5B | 1.564 (2) | C5B—C6B | 1.480 (5) |
P2B—O4B | 1.609 (2) | C6B—C7B | 1.398 (5) |
O2B—H2B | 0.86 (3) | C7B—C8B | 1.378 (5) |
O5B—H5B | 0.85 (3) | C7B—H7B | 0.9300 |
N1A—C1A | 1.333 (4) | C8B—C9B | 1.387 (5) |
N1A—C5A | 1.351 (4) | C8B—H8B | 0.9300 |
N2A—C10A | 1.341 (4) | C9B—C10B | 1.379 (4) |
N2A—C6A | 1.343 (4) | C9B—H9B | 0.9300 |
N3A—C15A | 1.345 (4) | C10B—C11B | 1.492 (5) |
N3A—C11A | 1.363 (4) | C11B—C12B | 1.389 (5) |
C1A—C2A | 1.379 (5) | C12B—C13B | 1.393 (5) |
C1A—H1A | 0.9300 | C12B—H12B | 0.9300 |
C2A—C3A | 1.387 (6) | C13B—C14B | 1.374 (6) |
C2A—H2C | 0.9300 | C13B—H13B | 0.9300 |
C3A—C4A | 1.386 (6) | C14B—C15B | 1.378 (5) |
C3A—H3C | 0.9300 | C14B—H14B | 0.9300 |
C4A—C5A | 1.381 (5) | C15B—H15B | 0.9300 |
C4A—H4A | 0.9300 | O1W—H1WA | 0.84 (3) |
C5A—C6A | 1.479 (5) | O1W—H1WB | 0.84 (3) |
C6A—C7A | 1.392 (4) | O2W—H2WA | 0.85 (3) |
C7A—C8A | 1.379 (5) | O2W—H2WB | 0.85 (3) |
C7A—H7A | 0.9300 | O3W—H3WB | 0.85 (3) |
C8A—C9A | 1.402 (5) | O3W—H3WA | 0.85 (3) |
| | | |
Cu1···Cu1i | 3.7720 (8) | Cu2···O1Bii | 2.910 (2) |
Cu2···Cu2ii | 3.6977 (8) | | |
| | | |
O1A—Cu1—N2A | 161.81 (10) | C6A—C7A—H7A | 120.8 |
O1A—Cu1—N1A | 99.04 (11) | C7A—C8A—C9A | 120.7 (3) |
N2A—Cu1—N1A | 79.99 (11) | C7A—C8A—H8A | 119.7 |
O1A—Cu1—N3A | 97.85 (11) | C9A—C8A—H8A | 119.7 |
N2A—Cu1—N3A | 79.90 (11) | C10A—C9A—C8A | 118.2 (3) |
N1A—Cu1—N3A | 158.67 (11) | C10A—C9A—H9A | 120.9 |
O1A—Cu1—O7A | 94.88 (9) | C8A—C9A—H9A | 120.9 |
N2A—Cu1—O7A | 103.29 (9) | N2A—C10A—C9A | 120.2 (3) |
N1A—Cu1—O7A | 91.27 (10) | N2A—C10A—C11A | 113.2 (3) |
N3A—Cu1—O7A | 100.19 (10) | C9A—C10A—C11A | 126.7 (3) |
O1B—Cu2—N2B | 163.48 (10) | N3A—C11A—C12A | 121.6 (3) |
O1B—Cu2—N1B | 100.79 (11) | N3A—C11A—C10A | 113.7 (3) |
N2B—Cu2—N1B | 79.92 (11) | C12A—C11A—C10A | 124.8 (3) |
O1B—Cu2—N3B | 97.87 (10) | C13A—C12A—C11A | 119.3 (3) |
N2B—Cu2—N3B | 79.74 (11) | C13A—C12A—H12A | 120.3 |
N1B—Cu2—N3B | 159.45 (11) | C11A—C12A—H12A | 120.3 |
O1B—Cu2—O7B | 91.24 (9) | C12A—C13A—C14A | 119.1 (3) |
N2B—Cu2—O7B | 105.28 (9) | C12A—C13A—H13A | 120.4 |
N1B—Cu2—O7B | 90.23 (10) | C14A—C13A—H13A | 120.4 |
N3B—Cu2—O7B | 97.93 (9) | C15A—C14A—C13A | 118.8 (3) |
O3A—P1A—O1A | 116.71 (14) | C15A—C14A—H14A | 120.6 |
O3A—P1A—O2A | 112.62 (14) | C13A—C14A—H14A | 120.6 |
O1A—P1A—O2A | 106.75 (14) | N3A—C15A—C14A | 122.8 (3) |
O3A—P1A—O4A | 106.32 (13) | N3A—C15A—H15A | 118.6 |
O1A—P1A—O4A | 108.20 (12) | C14A—C15A—H15A | 118.6 |
O2A—P1A—O4A | 105.63 (13) | C1B—N1B—C5B | 118.6 (3) |
O7A—P2A—O6A | 117.92 (14) | C1B—N1B—Cu2 | 126.9 (2) |
O7A—P2A—O5A | 109.05 (14) | C5B—N1B—Cu2 | 114.5 (2) |
O6A—P2A—O5A | 111.09 (14) | C6B—N2B—C10B | 121.7 (3) |
O7A—P2A—O4A | 108.80 (13) | C6B—N2B—Cu2 | 118.7 (2) |
O6A—P2A—O4A | 104.91 (13) | C10B—N2B—Cu2 | 119.4 (2) |
O5A—P2A—O4A | 104.08 (13) | C15B—N3B—C11B | 118.4 (3) |
P1A—O1A—Cu1 | 130.28 (14) | C15B—N3B—Cu2 | 127.2 (2) |
P1A—O2A—H2A | 114.1 (12) | C11B—N3B—Cu2 | 114.4 (2) |
P1A—O4A—P2A | 128.55 (14) | N1B—C1B—C2B | 121.9 (3) |
P2A—O5A—H5A | 112.1 (11) | N1B—C1B—H1B | 119.0 |
P2A—O7A—Cu1 | 125.43 (13) | C2B—C1B—H1B | 119.0 |
O1B—P1B—O2B | 111.15 (15) | C3B—C2B—C1B | 119.4 (4) |
O1B—P1B—O3B | 113.70 (14) | C3B—C2B—H2D | 120.3 |
O2B—P1B—O3B | 111.29 (15) | C1B—C2B—H2D | 120.3 |
O1B—P1B—O4B | 108.16 (13) | C2B—C3B—C4B | 119.8 (3) |
O2B—P1B—O4B | 108.84 (16) | C2B—C3B—H3B | 120.1 |
O3B—P1B—O4B | 103.26 (13) | C4B—C3B—H3B | 120.1 |
O7B—P2B—O6B | 117.84 (13) | C5B—C4B—C3B | 117.9 (3) |
O7B—P2B—O5B | 108.66 (13) | C5B—C4B—H4B | 121.1 |
O6B—P2B—O5B | 110.77 (13) | C3B—C4B—H4B | 121.1 |
O7B—P2B—O4B | 109.78 (13) | N1B—C5B—C4B | 122.4 (3) |
O6B—P2B—O4B | 103.81 (13) | N1B—C5B—C6B | 113.7 (3) |
O5B—P2B—O4B | 105.18 (14) | C4B—C5B—C6B | 124.0 (3) |
P1B—O1B—Cu2 | 135.88 (14) | N2B—C6B—C7B | 119.8 (3) |
P1B—O2B—H2B | 116.7 (12) | N2B—C6B—C5B | 113.2 (3) |
P1B—O4B—P2B | 134.50 (16) | C7B—C6B—C5B | 126.9 (3) |
P2B—O5B—H5B | 112.7 (11) | C8B—C7B—C6B | 118.4 (3) |
P2B—O7B—Cu2 | 128.32 (13) | C8B—C7B—H7B | 120.8 |
C1A—N1A—C5A | 119.0 (3) | C6B—C7B—H7B | 120.8 |
C1A—N1A—Cu1 | 126.6 (2) | C7B—C8B—C9B | 121.0 (3) |
C5A—N1A—Cu1 | 113.9 (2) | C7B—C8B—H8B | 119.5 |
C10A—N2A—C6A | 122.3 (3) | C9B—C8B—H8B | 119.5 |
C10A—N2A—Cu1 | 119.1 (2) | C10B—C9B—C8B | 117.9 (3) |
C6A—N2A—Cu1 | 118.7 (2) | C10B—C9B—H9B | 121.0 |
C15A—N3A—C11A | 118.3 (3) | C8B—C9B—H9B | 121.0 |
C15A—N3A—Cu1 | 127.6 (2) | N2B—C10B—C9B | 121.0 (3) |
C11A—N3A—Cu1 | 114.0 (2) | N2B—C10B—C11B | 112.3 (3) |
N1A—C1A—C2A | 122.5 (3) | C9B—C10B—C11B | 126.7 (3) |
N1A—C1A—H1A | 118.7 | N3B—C11B—C12B | 122.1 (3) |
C2A—C1A—H1A | 118.7 | N3B—C11B—C10B | 114.1 (3) |
C1A—C2A—C3A | 118.8 (4) | C12B—C11B—C10B | 123.7 (3) |
C1A—C2A—H2C | 120.6 | C11B—C12B—C13B | 118.3 (3) |
C3A—C2A—H2C | 120.6 | C11B—C12B—H12B | 120.9 |
C4A—C3A—C2A | 118.8 (4) | C13B—C12B—H12B | 120.9 |
C4A—C3A—H3C | 120.6 | C14B—C13B—C12B | 119.3 (3) |
C2A—C3A—H3C | 120.6 | C14B—C13B—H13B | 120.4 |
C5A—C4A—C3A | 119.2 (4) | C12B—C13B—H13B | 120.4 |
C5A—C4A—H4A | 120.4 | C13B—C14B—C15B | 119.2 (3) |
C3A—C4A—H4A | 120.4 | C13B—C14B—H14B | 120.4 |
N1A—C5A—C4A | 121.6 (3) | C15B—C14B—H14B | 120.4 |
N1A—C5A—C6A | 114.1 (3) | N3B—C15B—C14B | 122.7 (4) |
C4A—C5A—C6A | 124.3 (3) | N3B—C15B—H15B | 118.7 |
N2A—C6A—C7A | 120.3 (3) | C14B—C15B—H15B | 118.7 |
N2A—C6A—C5A | 112.9 (3) | H1WA—O1W—H1WB | 109 (3) |
C7A—C6A—C5A | 126.8 (3) | H2WA—O2W—H2WB | 107 (2) |
C8A—C7A—C6A | 118.4 (3) | H3WB—O3W—H3WA | 107 (2) |
C8A—C7A—H7A | 120.8 | | |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5A—H5A···O6B | 0.85 (2) | 1.83 (2) | 2.672 (3) | 174 (4) |
O5B—H5B···O6A | 0.85 (2) | 1.75 (2) | 2.601 (3) | 175 (2) |
O2A—H2A···O2W | 0.84 (3) | 1.76 (3) | 2.591 (4) | 171 (3) |
O2B—H2B···O4W | 0.85 (2) | 1.86 (2) | 2.716 (4) | 175 (3) |
O1W—H1WA···O3Aiii | 0.84 (3) | 1.88 (3) | 2.709 (5) | 167 (4) |
O1W—H1WB···O3B | 0.84 (3) | 1.87 (3) | 2.656 (5) | 156 (5) |
O2W—H2WA···O3Aiv | 0.85 (3) | 1.88 (3) | 2.716 (4) | 172 (3) |
O2W—H2WB···O6B | 0.85 (3) | 2.10 (3) | 2.883 (4) | 153 (4) |
O3W—H3WA···O1W | 0.85 (4) | 2.02 (4) | 2.687 (5) | 136 (3) |
O3W—H3WB···O6B | 0.85 (3) | 2.04 (3) | 2.885 (4) | 177 (5) |
C1B—H1B···O2B | 0.93 | 2.45 | 3.360 (5) | 165 |
C4B—H4B···O4Av | 0.93 | 2.53 | 3.409 (5) | 158 |
C9B—H9B···O7Avi | 0.93 | 2.40 | 3.280 (5) | 157 |
C15B—H15B···O1W | 0.93 | 2.57 | 3.430 (7) | 154 |
C7A—H7A···O3Wvii | 0.93 | 2.54 | 3.469 (5) | 173 |
C8A—H8A···O6Bviii | 0.93 | 2.48 | 3.407 (5) | 177 |
C9A—H9A···O5W | 0.93 | 2.40 | 3.319 (7) | 169 |
C12A—H12A···O5W | 0.93 | 2.57 | 3.478 (8) | 164 |
C14A—H14A···O3Bix | 0.93 | 2.51 | 3.355 (5) | 151 |
Symmetry codes: (iii) x−1, y, z; (iv) −x+2, −y, −z+2; (v) −x+2, −y, −z+1; (vi) x, y−1, z; (vii) −x+1, −y+1, −z+2; (viii) x, y+1, z; (ix) x+1, y, z. |
Experimental details
Crystal data |
Chemical formula | [Cu(H2P2O7)(C15H11N3)]2·4.5H2O |
Mr | 1026.60 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 11.2894 (17), 13.539 (2), 13.606 (2) |
α, β, γ (°) | 73.915 (13), 78.438 (14), 74.410 (12) |
V (Å3) | 1906.8 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.37 |
Crystal size (mm) | 0.32 × 0.30 × 0.26 |
|
Data collection |
Diffractometer | Rigaku AFC6 diffractometer |
Absorption correction | ψ scan North et al., 1968. |
Tmin, Tmax | 0.61, 0.70 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8505, 7493, 5449 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.101, 1.03 |
No. of reflections | 7493 |
No. of parameters | 581 |
No. of restraints | 18 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.58 |
Selected interatomic distances (Å) topCu1—O1A | 1.918 (2) | Cu2—O1B | 1.927 (2) |
Cu1—N2A | 1.932 (3) | Cu2—N2B | 1.940 (3) |
Cu1—N1A | 2.039 (3) | Cu2—N1B | 2.032 (3) |
Cu1—N3A | 2.046 (3) | Cu2—N3B | 2.043 (3) |
Cu1—O7A | 2.206 (2) | Cu2—O7B | 2.298 (2) |
| | | |
Cu1···Cu1i | 3.7720 (8) | Cu2···O1Bii | 2.910 (2) |
Cu2···Cu2ii | 3.6977 (8) | | |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5A—H5A···O6B | 0.85 (2) | 1.83 (2) | 2.672 (3) | 174 (4) |
O5B—H5B···O6A | 0.85 (2) | 1.75 (2) | 2.601 (3) | 175 (2) |
O2A—H2A···O2W | 0.84 (3) | 1.76 (3) | 2.591 (4) | 171 (3) |
O2B—H2B···O4W | 0.85 (2) | 1.86 (2) | 2.716 (4) | 175 (3) |
O1W—H1WA···O3Aiii | 0.84 (3) | 1.88 (3) | 2.709 (5) | 167 (4) |
O1W—H1WB···O3B | 0.84 (3) | 1.87 (3) | 2.656 (5) | 156 (5) |
O2W—H2WA···O3Aiv | 0.85 (3) | 1.88 (3) | 2.716 (4) | 172 (3) |
O2W—H2WB···O6B | 0.85 (3) | 2.10 (3) | 2.883 (4) | 153 (4) |
O3W—H3WA···O1W | 0.85 (4) | 2.02 (4) | 2.687 (5) | 136 (3) |
O3W—H3WB···O6B | 0.85 (3) | 2.04 (3) | 2.885 (4) | 177 (5) |
C1B—H1B···O2B | 0.93 | 2.45 | 3.360 (5) | 165 |
C4B—H4B···O4Av | 0.93 | 2.53 | 3.409 (5) | 158 |
C9B—H9B···O7Avi | 0.93 | 2.40 | 3.280 (5) | 157 |
C15B—H15B···O1W | 0.93 | 2.57 | 3.430 (7) | 154 |
C7A—H7A···O3Wvii | 0.93 | 2.54 | 3.469 (5) | 173 |
C8A—H8A···O6Bviii | 0.93 | 2.48 | 3.407 (5) | 177 |
C9A—H9A···O5W | 0.93 | 2.40 | 3.319 (7) | 169 |
C12A—H12A···O5W | 0.93 | 2.57 | 3.478 (8) | 164 |
C14A—H14A···O3Bix | 0.93 | 2.51 | 3.355 (5) | 151 |
Symmetry codes: (iii) x−1, y, z; (iv) −x+2, −y, −z+2; (v) −x+2, −y, −z+1; (vi) x, y−1, z; (vii) −x+1, −y+1, −z+2; (viii) x, y+1, z; (ix) x+1, y, z. |
π···π interactions (Å, °) for (I) topGroup 1/Group 2 | | ccd(Å) | ipd(Å) | sa(°) |
Cg1/Cg3i | | 3.629 (2) | 3.39 (2) | 20.7(1.0) |
Cg2/Cg6vi | | 3.674 (2) | 3.34 (1) | 24.4 (3) |
Cg3/Cg5vi | | 4.159 (2) | 3.42 (4) | 34.7(1.0) |
Symmetry codes: (i) 2 - x, 1 - y, 2 - z; (vi) x, -1 + y, z.
Centroids, as defined in Fig. 1. ccd: center-to-center distance (Distance
between ring centroids); ipd: mean interplanar distance (mean distance from one
plane to the neighbouring centroid); sa: mean slippage angle (mean angle
subtended by the intercentroid vector to the plane normal).
For details, see Janiak (2000). |
The pyrophosphate anion P2O74- ([O3P—O—PO3]4-) plays a key role in biochemistry and in applied material sciences. Inorganic pyrophosphate materials are obtained via high-temperature solid-state precursor methods or hydrothermal techniques. It is an interesting ligand because of its multidentate nature, and can give rise to many different coordination modes as it interacts with metal ions. In addition, it can be successively protonated to generate HP2O73-, H2P2O72- and H3P2O7- anions, and hence may result in an additional large variety of structural topologies.
The susceptibility of the tetra-anion to hydrolysis, particularly in the presence of MII cations, has prevented the isolation of CuII metallo-organic pyrophosphate complexes for investigation and the number of characterized structures remains limited. However, the use of chelating ligands in the synthetic route and precise control of the factors influencing the synthetic process have recently allowed a number of CuII pyrophosphate coordination complexes to be isolated and investigated for their biological, magnetic and catalytic properties (Ikotun et al., 2010). The CuII mononuclear pyrophosphate hydrate compounds H2en[Cu2(HP2O7)(en)(H2O)]2.2H2O (en = ethylenediamine), (II) (Gharbi et al., 1994), and {[(bipy)Cu(H2O)(P2O7)Na2(H2O)6].4H2O} (bipy = 2,2'-bipyridine), (III) (Doyle et al., 2005), have been reported, with each CuII atom in a similar distorted square-pyramidal coordination geometry, but quite different geometry of the pyrophosphate groups. In order to further study the versatility and bonding of the pyrophosphate anion, we extend here the search into copper-based pyrophosphate systems with the tridentate 2,2':6',2''-terpyridine (Tpy). Herein, we report the preparation and crystal structure of the first CuII pyrophosphate with Tpy as coligand, [Cu(Tpy)(P2O7H2)]2.4.5H2O, (I), obtained from the reaction of Cu2P2O7 and Tpy in phosphoric acid medium.
The asymmetric unit (Fig. 1) consists of two very similar, independent Cu(Tpy)(P2O7H2) monomeric units plus four and a half water molecules of hydration (see Refinement section for details on disorder). The Tpy units bind with their usual triple bite via the N atoms, and the P2O7H22- anions coordinate through two O atoms from two different phosphate units (Table 1).
Each independent CuN3O2 chromophore can be described as a slightly deformed square pyramid [τ parameters, as defined in Addison et al. (1984): (161.81–158.67)/60 = 0.05 for unit A; (163.48–159.45)/60 = 0.07 for unit B]. The polyhedra have one of the P2O7H2 O atoms, O7 (A/B), at the apex with the remaining four atoms N1, N2, N3 and O1 (A/B) defining a roughly planar square base (in what follows, pairs of values correspond to moieties A and B, respectively): r.m.s. deviation from planarity 0.0618 (3), 0.0864 (5) Å; maximum deviation 0.0718 (15) (N2A), 0.1010 (14) Å (N2B); copper cation 0.2428 (13), 0.1909 (13) Å above the plane towards the apices, which deviate 6.01 (2), 7.72 (2)° from the vertical. In unit B the coordination description is complicated because of the presence of a semicoordinated oxygen atom in a second apical position [Cu2···O1Bii: 2.910 (2) Å; symmetry code: (ii) -x + 1, -y, -z + 1] which could allow the Cu2 environment to be described as octahedral.
A search of the Cambridge Structural Database (CSD, version 5.3; Allen, 2002) disclosed a copper adenosine diphosphate complex [(adenosine 5'-diphosphato-O,O')(2,2':6',2''-terpyridine)copper(II)] (Cini & Pifferi, 1999) where the pyrophosphato (= diphosphato) anion is bound to a bulky adenosine group. The compound presents a very similar Cu + Tpy + P2O7 core as in (I), the copper environment being also square pyramidal with an identical N3O basal plane and an apical O, and a comparable τ descriptor, 0.09 [0.05/0.07 for (I)]. The fact that the distortions imposed by the substituted anion lead to only slightly larger deformation of the polyhedron seems to indicate that the atomic disposition is fairly robust.
The independent Tpy units in (I) are, as expected, basically planar [r.m.s. deviation from planarity: 0.0332 (7), 0.0413 (6) Å; maximum deviation: 0.065 (3), 0.073 (2) Å for C13A, N2B] and nearly parallel to each other [interpanar angle subtended: 6.11 (4)°]. The pyrophosphate anions are singly protonated at each phosphato end, balancing the CuII charges. As a result of chelation three loops build up around each copper cation: two smaller rings of the Cu—N—C—C—N– type, involving Tpy, and a much larger Cu—O—P—O—P—O– one mediated by the pyrophosphate group.
The two independent complex molecules interact with each other by way of two strong co-operative O—H···O hydrogen bonds between adjacent dihydrogen pyrophosphate ligands (Table 2, entries 1–2). This defines a classical R(8)22 ring (labelled A in Fig. 1; for graph-set notation see Bernstein et al., 1995), and which connects A and B molecules into a noncentrosymmetric dinuclear unit. Inspection of Fig. 1 shows the way in which both phosphate anions dispose at the centre of the group and the copper and Tpy units constitute the limiting outermost ends (hereafter the Cu1 and Cu2 ends). Further linkage is achieved by hydrogen bonds mediated by the hydration water molecules O1W, O2W and O3W (Table 2, entries 3, 6, 8–10) which give rise to another two large rings with graph-set codes R33(10) and R32(10) (labelled B and C, respectively, in Fig. 1). Tables 2 (hydrogen bonding) and 3 (π–π interactions) give account of the profuse nonbonding interactions linking monomers in the crystal structure. The distribution of packing interactions is rather even in space, allowing many possible descriptions, from which we chose the one shown in Fig. 2. In this description, each dinuclear unit is connected head-to-head with its centrosymmetric images at both Cu1 and Cu2 ends, to form columns parallel to [111]. At the Cu1 side, the interaction is basically of a π–π nature (Fig. 3a and Table 3, first entry) connecting symmetry-related Tpy rings and bringing symmetry-related Cu1 centres close enough to be within an interacting distance (Table 1). The Cu2 end, in turn, connects with its symmetry-related image via a weak Cu2···O1BII contact, leading to the formation of a closed four-membered loop (Table 1 and Fig. 3b)
Interconnection between columns is achieved via the collective action of the non-depleted hydration water molecules O1W to O4W, which in addition to contributing to the dinuclear stability are crucial in the formation of the final three-dimensional structure (entries 5 and 7 in Table 2). In the process they give rise to two types of centrosymmetric rings [graph-set codes R(20)610 (D) and R(12)44 (E)] threading a line of inversion centres along [100] (Fig. 4). Further linkage between columns is provided by a large number of weaker interactions, viz. non-classical C—H···O bonds having (C—H)Tpy as donors and Ophos as acceptors (entries 11–19 in Table 2) as well as extra π···π interactions between neighbouring Tpy groups, in addition to those involved in the column formation process already described (Table 3, entries 2–3).
In spite of its disordered nature (see Refinement section for details), the O4W···O4Wx interaction [symmetry code: (x) -x+1, -y+1, -z+1] effectively serves as a real link between the two centrosymmetrically related dinuclear units to which the water molecules are attached via Tpy. The O5W···O7Bviii [symmetry code: (viii) x, y+1, z] contact, by contrast, does not because of its `terminal' character with no further interactions involving O5W.
A validation run made with the PLATON program (Spek, 2009) revealed some short interatomic contacts in the structure concerning water molecules O4W and O5W; these are either artifacts (due to disorder) or hydrogen-bonding interactions obscured by the absence in the model of the intervening H atoms (see Refinement section for details). However, and in spite of its disordered nature, the O4W···O4Wxii [symmetry code: (xii) 1 - x, 1 - y, 1 - z] interaction effectively serves as a real link between the two centrosymmetrically related dinuclear units to which the water molecules are attached via Tpy. The O5W···O7Bviii [symmetry code: (viii) x, 1 + y, z] contact, by contrast, does not because of its `terminal' character with no further interactions involving O5W.
There are few copper pyrophosphates reported in the literature (ten entries in the 5.32 version of the CSD; Allen, 2002) and only two of them are mononuclear [compounds (II) and (III) mentioned above]. In the mononuclear coordination compounds (I), (II) and (III) the pyrophosphate ligands show different degrees of protonation: P2O7H22- in (I), P2O7H3- in (II) and P2O74- in (III), depending upon reaction conditions. As a result (I) is a neutral complex, (II) is ionic (with complex units presenting a single negative charge balanced by H2en2+ counter ions) and (III) presents a centrosymmetric `zwitterionic' structure with a central Na4(H2O)124+ core, to which two (2-) complex units attach at each side to produce a neutral cluster. Also, the way in which individual phosphate groups dispose relative to one another upon chelation is notably different: in compound (II) they bind in almost eclipsed geometry, with an O—P···P—O torsion angle of 4.9 (1)° (where O represents the coordinated oxygen); in (III), instead, the groups appear almost staggered [O—P···P—O: 51.0 (1)°]; while (I) presents an intermediate position, with equivalent torsion angles of 15.6 (1) and 15.9 (1)° for units A and B, respectively.