The title compounds, tetrakis(
-benzoato-
O:
O')bis(2,6-diaminopyridine)-1
N,2
N-dicopper(II)-acetonitrile (1/2), [Cu
2(C
7H
5O
2)
4(C
5H
7N
3)
2]·2C
2H
3N, (I), and bis(acetonitrile)-1
N,2
N-tetrakis(
-benzoato-
O:
O')dicopper(II)-acetonitrile (1/1.5), [Cu
2(C
7H
5O
2)
4(C
2H
3N)
2]·1.5C
2H
3N, (II), crystallize as acetonitrile solvates exhibiting different stability. They have similar molecular structures with discrete dimeric units located at crystallographic inversion centres. The copper ions are bridged by four benzoate groups and neutral N-donor ligands,
viz. 2,6-diaminopyridine in (I) and acetonitrile in (II), are coordinated at apical positions. The diverse stability is probably due to hydrogen-bond interactions of the solvated acetonitrile molecules with neighbouring dimers in compound (I).
Supporting information
CCDC references: 164634; 164635
Complex (I) was obtained by mixing acetonitrile solutions of copper benzoate and
2,6-diaminopyridine in 1:2 molar ratio. Crystals were deposited at room
temperature from the saturated solution. Crystals of compound (II) were
obtained from saturated solution of copper benzoate in acetonitrile after
standing in the refrigerator for 2 d.
For compound (II) one solvated acetonitrile molecule was found to be disordered
through an inversion center with methyl C atom from one disordered molecule
and cyano C atom from the other one sharing the same site. H atoms were
included at calculated positions in both structures using SHELXL97
(Sheldrick, 1997) and refined as a riding model with isotropic displacement
parameters taken from the attached heavy atoms and multiplied by 1.2 for
aromatic and amino H atoms and by 1.5 for methyl H atoms.
Data collection: CAD-4 Software (Enraf-Nonius, 1994) for (I); Collect Software (Nonius, 1998) for (II). Cell refinement: PARAM in X-RAY76 (Stewart et al., 1976) for (I); DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (II). Data reduction: XCAD4 (Harms & Wocadlo, 1995) for (I); DENZO and SCALEPACK for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(I) 'tetrakis(benzoato-
O,
O')bis(2,6-diaminopyridine-
N)dicopper(II)acetonitrile solvat'
top
Crystal data top
[Cu2(C7H5O2)4(C5H7N3)2]·2C2H3N | Z = 2 |
Mr = 911.92 | F(000) = 940 |
Triclinic, P1 | Dx = 1.422 Mg m−3 |
a = 10.690 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.822 (3) Å | Cell parameters from 75 reflections |
c = 16.485 (2) Å | θ = 8.1–14.6° |
α = 85.24 (1)° | µ = 1.06 mm−1 |
β = 71.24 (1)° | T = 293 K |
γ = 85.87 (1)° | Prismatic, green |
V = 2129.7 (6) Å3 | 0.40 × 0.19 × 0.11 mm |
Data collection top
NONIUS CAD-4 diffractometer | 4333 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 26.0°, θmin = 1.3° |
ω/θ scans | h = −13→0 |
Absorption correction: gaussian (PLATON; Spek, 1998) | k = −15→15 |
Tmin = 0.61, Tmax = 0.88 | l = −20→19 |
8494 measured reflections | 3 standard reflections every 600 reflections |
8365 independent reflections | intensity decay: 17% |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0852P)2] where P = (Fo2 + 2Fc2)/3 |
8365 reflections | (Δ/σ)max = 0.001 |
543 parameters | Δρmax = 0.68 e Å−3 |
0 restraints | Δρmin = −0.75 e Å−3 |
Crystal data top
[Cu2(C7H5O2)4(C5H7N3)2]·2C2H3N | γ = 85.87 (1)° |
Mr = 911.92 | V = 2129.7 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.690 (1) Å | Mo Kα radiation |
b = 12.822 (3) Å | µ = 1.06 mm−1 |
c = 16.485 (2) Å | T = 293 K |
α = 85.24 (1)° | 0.40 × 0.19 × 0.11 mm |
β = 71.24 (1)° | |
Data collection top
NONIUS CAD-4 diffractometer | 4333 reflections with I > 2σ(I) |
Absorption correction: gaussian (PLATON; Spek, 1998) | Rint = 0.017 |
Tmin = 0.61, Tmax = 0.88 | 3 standard reflections every 600 reflections |
8494 measured reflections | intensity decay: 17% |
8365 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.68 e Å−3 |
8365 reflections | Δρmin = −0.75 e Å−3 |
543 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.94096 (5) | 0.41611 (5) | 0.48619 (4) | 0.03578 (18) | |
N1 | 0.8649 (4) | 0.2719 (3) | 0.4507 (3) | 0.0399 (10) | |
N11 | 0.8314 (5) | 0.3610 (4) | 0.3323 (3) | 0.0634 (14) | |
H11A | 0.8265 | 0.4184 | 0.3569 | 0.076* | |
H11B | 0.8228 | 0.3624 | 0.2821 | 0.076* | |
N12 | 0.8697 (6) | 0.1834 (4) | 0.5776 (3) | 0.0756 (17) | |
H12A | 0.8655 | 0.2429 | 0.5991 | 0.091* | |
H12B | 0.8732 | 0.1263 | 0.6083 | 0.091* | |
C2 | 0.8524 (5) | 0.2687 (4) | 0.3724 (4) | 0.0455 (13) | |
C3 | 0.8581 (6) | 0.1755 (5) | 0.3339 (4) | 0.0616 (17) | |
H3 | 0.8536 | 0.1755 | 0.2785 | 0.074* | |
C4 | 0.8706 (6) | 0.0839 (5) | 0.3794 (5) | 0.0699 (19) | |
H4 | 0.8767 | 0.0206 | 0.3544 | 0.084* | |
C5 | 0.8742 (5) | 0.0842 (5) | 0.4614 (4) | 0.0608 (16) | |
H5 | 0.8789 | 0.0217 | 0.4935 | 0.073* | |
C6 | 0.8706 (5) | 0.1795 (4) | 0.4955 (4) | 0.0468 (13) | |
O11 | 1.1953 (3) | 0.4791 (3) | 0.5284 (2) | 0.0510 (10) | |
O12 | 1.0959 (3) | 0.3415 (3) | 0.5067 (2) | 0.0484 (9) | |
C10 | 1.1894 (5) | 0.3843 (4) | 0.5208 (3) | 0.0393 (12) | |
C11 | 1.3022 (5) | 0.3120 (4) | 0.5284 (3) | 0.0400 (12) | |
C12 | 1.4192 (5) | 0.3545 (5) | 0.5272 (3) | 0.0533 (14) | |
H12 | 1.4254 | 0.4269 | 0.5232 | 0.064* | |
C13 | 1.5262 (6) | 0.2899 (6) | 0.5320 (4) | 0.0676 (18) | |
H13 | 1.6046 | 0.3183 | 0.5304 | 0.081* | |
C14 | 1.5153 (6) | 0.1831 (7) | 0.5390 (4) | 0.076 (2) | |
H14 | 1.5873 | 0.1392 | 0.5416 | 0.092* | |
C15 | 1.3987 (7) | 0.1399 (5) | 0.5422 (4) | 0.0713 (19) | |
H15 | 1.3914 | 0.0677 | 0.5486 | 0.086* | |
C16 | 1.2933 (5) | 0.2052 (5) | 0.5358 (4) | 0.0568 (15) | |
H16 | 1.2155 | 0.1764 | 0.5366 | 0.068* | |
O21 | 0.9484 (4) | 0.5444 (3) | 0.6319 (2) | 0.0497 (9) | |
O22 | 0.8491 (3) | 0.4071 (3) | 0.6112 (2) | 0.0484 (9) | |
C20 | 0.8727 (5) | 0.4703 (4) | 0.6577 (3) | 0.0373 (11) | |
C21 | 0.8064 (5) | 0.4558 (4) | 0.7533 (3) | 0.0442 (12) | |
C22 | 0.7047 (6) | 0.3894 (4) | 0.7870 (4) | 0.0569 (15) | |
H22 | 0.6774 | 0.3518 | 0.7503 | 0.068* | |
C23 | 0.6424 (7) | 0.3774 (5) | 0.8743 (4) | 0.0719 (19) | |
H23 | 0.5745 | 0.3313 | 0.8964 | 0.086* | |
C24 | 0.6811 (9) | 0.4340 (6) | 0.9284 (5) | 0.096 (3) | |
H24 | 0.6369 | 0.4291 | 0.9871 | 0.116* | |
C25 | 0.7856 (10) | 0.4978 (7) | 0.8953 (4) | 0.118 (4) | |
H25 | 0.8148 | 0.5335 | 0.9321 | 0.142* | |
C26 | 0.8480 (8) | 0.5096 (5) | 0.8075 (4) | 0.082 (2) | |
H26 | 0.9179 | 0.5539 | 0.7855 | 0.099* | |
Cu2 | 0.54701 (6) | 0.92077 (5) | 0.04365 (4) | 0.03689 (18) | |
N2 | 0.6355 (4) | 0.7889 (3) | 0.1091 (3) | 0.0424 (10) | |
N21 | 0.4889 (5) | 0.8312 (4) | 0.2406 (3) | 0.0738 (16) | |
H21A | 0.4627 | 0.8860 | 0.2155 | 0.089* | |
H21B | 0.4541 | 0.8186 | 0.2950 | 0.089* | |
N22 | 0.7886 (6) | 0.7491 (4) | −0.0213 (3) | 0.0848 (19) | |
H22A | 0.7603 | 0.8043 | −0.0447 | 0.102* | |
H22B | 0.8515 | 0.7096 | −0.0519 | 0.102* | |
C2' | 0.5845 (6) | 0.7650 (4) | 0.1945 (4) | 0.0509 (14) | |
C3' | 0.6272 (7) | 0.6769 (5) | 0.2360 (4) | 0.0702 (19) | |
H3' | 0.5902 | 0.6629 | 0.2948 | 0.084* | |
C4' | 0.7234 (8) | 0.6128 (5) | 0.1882 (5) | 0.081 (2) | |
H4' | 0.7506 | 0.5521 | 0.2141 | 0.097* | |
C5' | 0.7816 (7) | 0.6356 (5) | 0.1022 (5) | 0.0709 (19) | |
H5' | 0.8511 | 0.5932 | 0.0700 | 0.085* | |
C6' | 0.7337 (6) | 0.7243 (5) | 0.0642 (4) | 0.0560 (15) | |
O31 | 0.5267 (4) | 0.8394 (3) | −0.0468 (2) | 0.0534 (10) | |
O32 | 0.4508 (4) | 0.9701 (3) | −0.1197 (2) | 0.0522 (10) | |
C30 | 0.4837 (4) | 0.8764 (4) | −0.1069 (3) | 0.0391 (12) | |
C31 | 0.4755 (4) | 0.8002 (4) | −0.1692 (3) | 0.0403 (12) | |
C32 | 0.4466 (5) | 0.8353 (5) | −0.2435 (3) | 0.0511 (14) | |
H32 | 0.4311 | 0.9064 | −0.2549 | 0.061* | |
C33 | 0.4411 (6) | 0.7633 (6) | −0.3005 (4) | 0.0665 (18) | |
H33 | 0.4216 | 0.7866 | −0.3503 | 0.080* | |
C34 | 0.4638 (6) | 0.6585 (6) | −0.2845 (4) | 0.0701 (19) | |
H34 | 0.4605 | 0.6111 | −0.3234 | 0.084* | |
C35 | 0.4918 (6) | 0.6230 (5) | −0.2104 (4) | 0.0650 (17) | |
H35 | 0.5065 | 0.5517 | −0.1990 | 0.078* | |
C36 | 0.4976 (5) | 0.6938 (4) | −0.1534 (3) | 0.0498 (14) | |
H36 | 0.5167 | 0.6699 | −0.1037 | 0.060* | |
O41 | 0.3588 (3) | 0.9016 (3) | 0.1077 (2) | 0.0493 (9) | |
O42 | 0.2826 (3) | 1.0316 (3) | 0.0357 (3) | 0.0570 (10) | |
C40 | 0.2668 (5) | 0.9574 (4) | 0.0915 (3) | 0.0404 (12) | |
C41 | 0.1277 (5) | 0.9297 (4) | 0.1401 (3) | 0.0415 (12) | |
C42 | 0.1015 (6) | 0.8504 (5) | 0.2046 (4) | 0.0569 (15) | |
H42 | 0.1707 | 0.8157 | 0.2200 | 0.068* | |
C43 | −0.0271 (7) | 0.8227 (6) | 0.2462 (4) | 0.0743 (19) | |
H43 | −0.0440 | 0.7694 | 0.2897 | 0.089* | |
C44 | −0.1293 (6) | 0.8728 (6) | 0.2241 (4) | 0.073 (2) | |
H44 | −0.2155 | 0.8539 | 0.2526 | 0.088* | |
C45 | −0.1053 (6) | 0.9513 (6) | 0.1598 (5) | 0.077 (2) | |
H45 | −0.1749 | 0.9847 | 0.1439 | 0.093* | |
C46 | 0.0232 (5) | 0.9805 (5) | 0.1186 (4) | 0.0594 (16) | |
H46 | 0.0392 | 1.0349 | 0.0762 | 0.071* | |
N7 | 0.8933 (7) | 0.3528 (6) | 0.1247 (4) | 0.098 (2) | |
C71 | 0.8799 (7) | 0.3018 (6) | 0.0770 (5) | 0.077 (2) | |
C72 | 0.8684 (9) | 0.2333 (7) | 0.0139 (5) | 0.109 (3) | |
H72A | 0.9499 | 0.2307 | −0.0328 | 0.164* | |
H72B | 0.7979 | 0.2599 | −0.0074 | 0.164* | |
H72C | 0.8498 | 0.1641 | 0.0403 | 0.164* | |
C81 | 0.7720 (7) | −0.1034 (6) | 0.6867 (5) | 0.083 (2) | |
C82 | 0.7989 (7) | −0.2138 (6) | 0.6855 (6) | 0.113 (3) | |
H82A | 0.7172 | −0.2487 | 0.7020 | 0.169* | |
H82B | 0.8463 | −0.2358 | 0.7250 | 0.169* | |
H82C | 0.8515 | −0.2313 | 0.6286 | 0.169* | |
N8 | 0.7485 (8) | −0.0191 (6) | 0.6864 (6) | 0.132 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0327 (3) | 0.0390 (4) | 0.0391 (4) | −0.0047 (3) | −0.0154 (3) | −0.0031 (3) |
N1 | 0.037 (2) | 0.042 (3) | 0.045 (3) | −0.0042 (18) | −0.0183 (19) | −0.007 (2) |
N11 | 0.086 (4) | 0.064 (3) | 0.063 (3) | −0.017 (3) | −0.052 (3) | −0.003 (3) |
N12 | 0.126 (5) | 0.052 (3) | 0.068 (4) | −0.029 (3) | −0.056 (4) | 0.016 (3) |
C2 | 0.038 (3) | 0.054 (3) | 0.054 (3) | −0.003 (2) | −0.025 (3) | −0.014 (3) |
C3 | 0.061 (4) | 0.072 (4) | 0.064 (4) | 0.000 (3) | −0.031 (3) | −0.028 (4) |
C4 | 0.067 (4) | 0.054 (4) | 0.100 (6) | 0.002 (3) | −0.034 (4) | −0.040 (4) |
C5 | 0.053 (4) | 0.049 (4) | 0.087 (5) | 0.000 (3) | −0.028 (3) | −0.016 (3) |
C6 | 0.039 (3) | 0.045 (3) | 0.060 (4) | −0.007 (2) | −0.021 (3) | −0.005 (3) |
O11 | 0.049 (2) | 0.047 (2) | 0.067 (3) | 0.0029 (18) | −0.032 (2) | −0.012 (2) |
O12 | 0.041 (2) | 0.047 (2) | 0.065 (2) | 0.0005 (17) | −0.0273 (18) | −0.0043 (19) |
C10 | 0.036 (3) | 0.047 (3) | 0.034 (3) | −0.002 (2) | −0.010 (2) | −0.004 (2) |
C11 | 0.033 (3) | 0.054 (3) | 0.031 (3) | 0.007 (2) | −0.009 (2) | −0.003 (2) |
C12 | 0.041 (3) | 0.071 (4) | 0.047 (3) | 0.003 (3) | −0.014 (3) | −0.006 (3) |
C13 | 0.040 (3) | 0.101 (6) | 0.063 (4) | 0.010 (3) | −0.018 (3) | −0.018 (4) |
C14 | 0.049 (4) | 0.121 (7) | 0.056 (4) | 0.035 (4) | −0.020 (3) | −0.010 (4) |
C15 | 0.071 (4) | 0.062 (4) | 0.072 (5) | 0.022 (4) | −0.018 (4) | 0.006 (3) |
C16 | 0.043 (3) | 0.065 (4) | 0.061 (4) | 0.001 (3) | −0.016 (3) | −0.002 (3) |
O21 | 0.055 (2) | 0.055 (2) | 0.039 (2) | −0.0204 (19) | −0.0127 (17) | −0.0007 (18) |
O22 | 0.050 (2) | 0.053 (2) | 0.040 (2) | −0.0165 (18) | −0.0073 (17) | −0.0092 (18) |
C20 | 0.033 (3) | 0.037 (3) | 0.042 (3) | 0.002 (2) | −0.013 (2) | −0.002 (2) |
C21 | 0.049 (3) | 0.039 (3) | 0.042 (3) | −0.003 (2) | −0.010 (2) | 0.001 (2) |
C22 | 0.057 (3) | 0.057 (4) | 0.050 (4) | −0.013 (3) | −0.006 (3) | 0.002 (3) |
C23 | 0.073 (4) | 0.063 (4) | 0.061 (4) | −0.019 (3) | 0.003 (4) | 0.015 (4) |
C24 | 0.137 (7) | 0.081 (5) | 0.046 (4) | −0.019 (5) | 0.005 (4) | 0.012 (4) |
C25 | 0.193 (10) | 0.113 (7) | 0.037 (4) | −0.082 (7) | −0.007 (5) | −0.001 (4) |
C26 | 0.116 (6) | 0.082 (5) | 0.047 (4) | −0.055 (4) | −0.015 (4) | 0.006 (3) |
Cu2 | 0.0368 (3) | 0.0442 (4) | 0.0313 (3) | 0.0028 (3) | −0.0146 (3) | 0.0000 (3) |
N2 | 0.044 (2) | 0.044 (3) | 0.042 (3) | 0.008 (2) | −0.020 (2) | −0.003 (2) |
N21 | 0.093 (4) | 0.090 (4) | 0.032 (3) | 0.024 (3) | −0.018 (3) | 0.000 (3) |
N22 | 0.086 (4) | 0.090 (4) | 0.057 (4) | 0.046 (3) | −0.007 (3) | 0.003 (3) |
C2' | 0.063 (4) | 0.054 (4) | 0.043 (3) | −0.004 (3) | −0.027 (3) | 0.004 (3) |
C3' | 0.100 (5) | 0.059 (4) | 0.059 (4) | 0.004 (4) | −0.042 (4) | 0.015 (3) |
C4' | 0.111 (6) | 0.064 (4) | 0.077 (5) | 0.020 (4) | −0.052 (5) | 0.007 (4) |
C5' | 0.082 (5) | 0.052 (4) | 0.083 (5) | 0.023 (3) | −0.039 (4) | 0.001 (4) |
C6' | 0.060 (4) | 0.056 (4) | 0.059 (4) | 0.003 (3) | −0.031 (3) | 0.001 (3) |
O31 | 0.074 (3) | 0.050 (2) | 0.045 (2) | 0.0092 (19) | −0.033 (2) | −0.0084 (18) |
O32 | 0.069 (3) | 0.051 (2) | 0.047 (2) | 0.006 (2) | −0.034 (2) | −0.0038 (19) |
C30 | 0.029 (2) | 0.054 (3) | 0.034 (3) | −0.004 (2) | −0.009 (2) | −0.003 (3) |
C31 | 0.031 (3) | 0.055 (3) | 0.034 (3) | −0.002 (2) | −0.009 (2) | −0.008 (2) |
C32 | 0.050 (3) | 0.065 (4) | 0.043 (3) | −0.002 (3) | −0.021 (3) | −0.004 (3) |
C33 | 0.066 (4) | 0.097 (5) | 0.050 (4) | −0.012 (4) | −0.034 (3) | −0.013 (4) |
C34 | 0.064 (4) | 0.086 (5) | 0.068 (4) | −0.009 (4) | −0.022 (3) | −0.034 (4) |
C35 | 0.069 (4) | 0.062 (4) | 0.064 (4) | −0.007 (3) | −0.018 (3) | −0.016 (3) |
C36 | 0.054 (3) | 0.055 (4) | 0.040 (3) | −0.004 (3) | −0.013 (3) | −0.007 (3) |
O41 | 0.0386 (19) | 0.064 (2) | 0.042 (2) | −0.0027 (18) | −0.0106 (16) | 0.0078 (18) |
O42 | 0.039 (2) | 0.066 (3) | 0.059 (2) | 0.0008 (19) | −0.0117 (18) | 0.015 (2) |
C40 | 0.043 (3) | 0.044 (3) | 0.033 (3) | −0.001 (2) | −0.011 (2) | −0.005 (3) |
C41 | 0.036 (3) | 0.055 (3) | 0.034 (3) | −0.004 (2) | −0.009 (2) | −0.008 (3) |
C42 | 0.049 (3) | 0.068 (4) | 0.052 (4) | −0.007 (3) | −0.013 (3) | 0.001 (3) |
C43 | 0.065 (4) | 0.085 (5) | 0.060 (4) | −0.024 (4) | −0.002 (3) | 0.012 (4) |
C44 | 0.048 (4) | 0.100 (6) | 0.067 (5) | −0.023 (4) | −0.005 (3) | −0.013 (4) |
C45 | 0.041 (3) | 0.116 (6) | 0.079 (5) | 0.000 (4) | −0.024 (3) | −0.009 (5) |
C46 | 0.042 (3) | 0.077 (4) | 0.058 (4) | 0.000 (3) | −0.016 (3) | 0.002 (3) |
N7 | 0.103 (5) | 0.118 (6) | 0.081 (5) | 0.006 (4) | −0.033 (4) | −0.036 (4) |
C71 | 0.068 (4) | 0.099 (6) | 0.063 (4) | 0.024 (4) | −0.022 (4) | −0.021 (4) |
C72 | 0.113 (7) | 0.125 (7) | 0.105 (7) | 0.013 (6) | −0.050 (6) | −0.048 (6) |
C81 | 0.061 (4) | 0.072 (5) | 0.095 (6) | −0.016 (4) | 0.011 (4) | −0.017 (5) |
C82 | 0.049 (4) | 0.091 (6) | 0.164 (9) | −0.004 (4) | 0.018 (5) | −0.024 (6) |
N8 | 0.128 (6) | 0.066 (5) | 0.151 (7) | −0.017 (5) | 0.031 (5) | −0.011 (5) |
Geometric parameters (Å, º) top
Cu1—O12 | 1.963 (3) | Cu2—Cu2ii | 2.7130 (12) |
Cu1—O11i | 1.968 (3) | N2—C6' | 1.347 (7) |
Cu1—O21i | 1.971 (4) | N2—C2' | 1.352 (7) |
Cu1—O22 | 1.975 (3) | N21—C2' | 1.351 (7) |
Cu1—N1 | 2.263 (4) | N21—H21A | 0.8600 |
Cu1—Cu1i | 2.7114 (12) | N21—H21B | 0.8600 |
N1—C2 | 1.345 (6) | N22—C6' | 1.360 (7) |
N1—C6 | 1.352 (7) | N22—H22A | 0.8600 |
N11—C2 | 1.346 (7) | N22—H22B | 0.8600 |
N11—H11A | 0.8600 | C2'—C3' | 1.397 (8) |
N11—H11B | 0.8600 | C3'—C4' | 1.349 (9) |
N12—C6 | 1.356 (7) | C3'—H3' | 0.9300 |
N12—H12A | 0.8600 | C4'—C5' | 1.368 (9) |
N12—H12B | 0.8600 | C4'—H4' | 0.9300 |
C2—C3 | 1.388 (7) | C5'—C6' | 1.398 (8) |
C3—C4 | 1.362 (9) | C5'—H5' | 0.9300 |
C3—H3 | 0.9300 | O31—C30 | 1.266 (6) |
C4—C5 | 1.364 (9) | O32—C30 | 1.248 (6) |
C4—H4 | 0.9300 | O32—Cu2ii | 1.961 (3) |
C5—C6 | 1.380 (7) | C30—C31 | 1.502 (7) |
C5—H5 | 0.9300 | C31—C36 | 1.385 (7) |
O11—C10 | 1.240 (6) | C31—C32 | 1.388 (7) |
O11—Cu1i | 1.968 (3) | C32—C33 | 1.389 (8) |
O12—C10 | 1.265 (6) | C32—H32 | 0.9300 |
C10—C11 | 1.499 (7) | C33—C34 | 1.367 (9) |
C11—C16 | 1.373 (8) | C33—H33 | 0.9300 |
C11—C12 | 1.394 (7) | C34—C35 | 1.383 (9) |
C12—C13 | 1.382 (8) | C34—H34 | 0.9300 |
C12—H12 | 0.9300 | C35—C36 | 1.378 (7) |
C13—C14 | 1.375 (9) | C35—H35 | 0.9300 |
C13—H13 | 0.9300 | C36—H36 | 0.9300 |
C14—C15 | 1.384 (9) | O41—C40 | 1.259 (6) |
C14—H14 | 0.9300 | O42—C40 | 1.248 (6) |
C15—C16 | 1.380 (8) | O42—Cu2ii | 1.974 (4) |
C15—H15 | 0.9300 | C40—C41 | 1.497 (7) |
C16—H16 | 0.9300 | C41—C46 | 1.382 (7) |
O21—C20 | 1.250 (6) | C41—C42 | 1.382 (7) |
O21—Cu1i | 1.971 (4) | C42—C43 | 1.383 (8) |
O22—C20 | 1.251 (5) | C42—H42 | 0.9300 |
C20—C21 | 1.507 (7) | C43—C44 | 1.362 (9) |
C21—C26 | 1.369 (8) | C43—H43 | 0.9300 |
C21—C22 | 1.371 (7) | C44—C45 | 1.374 (10) |
C22—C23 | 1.380 (8) | C44—H44 | 0.9300 |
C22—H22 | 0.9300 | C45—C46 | 1.385 (8) |
C23—C24 | 1.371 (10) | C45—H45 | 0.9300 |
C23—H23 | 0.9300 | C46—H46 | 0.9300 |
C24—C25 | 1.371 (11) | N7—C71 | 1.113 (8) |
C24—H24 | 0.9300 | C71—C72 | 1.454 (9) |
C25—C26 | 1.386 (9) | C72—H72A | 0.9600 |
C25—H25 | 0.9300 | C72—H72B | 0.9600 |
C26—H26 | 0.9300 | C72—H72C | 0.9600 |
Cu2—O32ii | 1.961 (3) | C81—N8 | 1.092 (9) |
Cu2—O31 | 1.964 (3) | C81—C82 | 1.425 (10) |
Cu2—O41 | 1.971 (3) | C82—H82A | 0.9600 |
Cu2—O42ii | 1.974 (4) | C82—H82B | 0.9600 |
Cu2—N2 | 2.245 (4) | C82—H82C | 0.9600 |
| | | |
O12—Cu1—O11i | 165.98 (14) | O31—Cu2—N2 | 96.62 (15) |
O12—Cu1—O21i | 89.16 (16) | O41—Cu2—N2 | 98.67 (15) |
O11i—Cu1—O21i | 88.83 (16) | O42ii—Cu2—N2 | 95.58 (16) |
O12—Cu1—O22 | 89.13 (15) | O32ii—Cu2—Cu2ii | 84.13 (11) |
O11i—Cu1—O22 | 89.41 (15) | O31—Cu2—Cu2ii | 81.97 (11) |
O21i—Cu1—O22 | 165.74 (14) | O41—Cu2—Cu2ii | 84.37 (11) |
O12—Cu1—N1 | 94.48 (14) | O42ii—Cu2—Cu2ii | 81.38 (11) |
O11i—Cu1—N1 | 99.51 (14) | N2—Cu2—Cu2ii | 176.64 (12) |
O21i—Cu1—N1 | 94.97 (15) | C6'—N2—C2' | 116.9 (5) |
O22—Cu1—N1 | 99.28 (15) | C6'—N2—Cu2 | 121.5 (4) |
O12—Cu1—Cu1i | 81.77 (10) | C2'—N2—Cu2 | 121.4 (3) |
O11i—Cu1—Cu1i | 84.22 (11) | C2'—N21—H21A | 120.0 |
O21i—Cu1—Cu1i | 79.44 (10) | C2'—N21—H21B | 120.0 |
O22—Cu1—Cu1i | 86.31 (10) | H21A—N21—H21B | 120.0 |
N1—Cu1—Cu1i | 173.26 (11) | C6'—N22—H22A | 120.0 |
C2—N1—C6 | 117.3 (4) | C6'—N22—H22B | 120.0 |
C2—N1—Cu1 | 120.0 (4) | H22A—N22—H22B | 120.0 |
C6—N1—Cu1 | 119.6 (3) | N21—C2'—N2 | 117.4 (5) |
C2—N11—H11A | 120.0 | N21—C2'—C3' | 119.5 (6) |
C2—N11—H11B | 120.0 | N2—C2'—C3' | 123.1 (5) |
H11A—N11—H11B | 120.0 | C4'—C3'—C2' | 118.1 (6) |
C6—N12—H12A | 120.0 | C4'—C3'—H3' | 121.0 |
C6—N12—H12B | 120.0 | C2'—C3'—H3' | 121.0 |
H12A—N12—H12B | 120.0 | C3'—C4'—C5' | 121.0 (6) |
N1—C2—N11 | 117.0 (4) | C3'—C4'—H4' | 119.5 |
N1—C2—C3 | 122.5 (6) | C5'—C4'—H4' | 119.5 |
N11—C2—C3 | 120.5 (5) | C4'—C5'—C6' | 118.2 (6) |
C4—C3—C2 | 118.3 (6) | C4'—C5'—H5' | 120.9 |
C4—C3—H3 | 120.9 | C6'—C5'—H5' | 120.9 |
C2—C3—H3 | 120.9 | N2—C6'—N22 | 117.5 (5) |
C3—C4—C5 | 120.7 (5) | N2—C6'—C5' | 122.6 (6) |
C3—C4—H4 | 119.7 | N22—C6'—C5' | 119.8 (6) |
C5—C4—H4 | 119.7 | C30—O31—Cu2 | 125.0 (3) |
C4—C5—C6 | 118.3 (6) | C30—O32—Cu2ii | 123.0 (3) |
C4—C5—H5 | 120.8 | O32—C30—O31 | 125.9 (5) |
C6—C5—H5 | 120.8 | O32—C30—C31 | 117.8 (4) |
N1—C6—N12 | 117.1 (5) | O31—C30—C31 | 116.3 (5) |
N1—C6—C5 | 122.7 (5) | C36—C31—C32 | 119.2 (5) |
N12—C6—C5 | 120.3 (6) | C36—C31—C30 | 120.2 (5) |
C10—O11—Cu1i | 122.6 (3) | C32—C31—C30 | 120.6 (5) |
C10—O12—Cu1 | 125.3 (3) | C31—C32—C33 | 119.4 (6) |
O11—C10—O12 | 126.0 (5) | C31—C32—H32 | 120.3 |
O11—C10—C11 | 118.2 (4) | C33—C32—H32 | 120.3 |
O12—C10—C11 | 115.8 (5) | C34—C33—C32 | 120.8 (6) |
C16—C11—C12 | 119.4 (5) | C34—C33—H33 | 119.6 |
C16—C11—C10 | 121.6 (5) | C32—C33—H33 | 119.6 |
C12—C11—C10 | 119.1 (5) | C33—C34—C35 | 120.0 (6) |
C13—C12—C11 | 120.5 (6) | C33—C34—H34 | 120.0 |
C13—C12—H12 | 119.8 | C35—C34—H34 | 120.0 |
C11—C12—H12 | 119.8 | C36—C35—C34 | 119.6 (6) |
C14—C13—C12 | 119.2 (6) | C36—C35—H35 | 120.2 |
C14—C13—H13 | 120.4 | C34—C35—H35 | 120.2 |
C12—C13—H13 | 120.4 | C35—C36—C31 | 120.9 (5) |
C13—C14—C15 | 120.9 (6) | C35—C36—H36 | 119.6 |
C13—C14—H14 | 119.5 | C31—C36—H36 | 119.6 |
C15—C14—H14 | 119.5 | C40—O41—Cu2 | 122.7 (3) |
C16—C15—C14 | 119.4 (6) | C40—O42—Cu2ii | 126.5 (3) |
C16—C15—H15 | 120.3 | O42—C40—O41 | 125.0 (5) |
C14—C15—H15 | 120.3 | O42—C40—C41 | 117.4 (5) |
C11—C16—C15 | 120.7 (6) | O41—C40—C41 | 117.6 (5) |
C11—C16—H16 | 119.7 | C46—C41—C42 | 118.8 (5) |
C15—C16—H16 | 119.7 | C46—C41—C40 | 120.2 (5) |
C20—O21—Cu1i | 128.7 (3) | C42—C41—C40 | 121.0 (5) |
C20—O22—Cu1 | 120.0 (3) | C41—C42—C43 | 120.2 (6) |
O21—C20—O22 | 125.5 (5) | C41—C42—H42 | 119.9 |
O21—C20—C21 | 116.6 (4) | C43—C42—H42 | 119.9 |
O22—C20—C21 | 117.9 (5) | C44—C43—C42 | 120.5 (7) |
C26—C21—C22 | 119.4 (5) | C44—C43—H43 | 119.8 |
C26—C21—C20 | 119.6 (5) | C42—C43—H43 | 119.8 |
C22—C21—C20 | 121.0 (5) | C43—C44—C45 | 120.2 (6) |
C21—C22—C23 | 121.0 (6) | C43—C44—H44 | 119.9 |
C21—C22—H22 | 119.5 | C45—C44—H44 | 119.9 |
C23—C22—H22 | 119.5 | C44—C45—C46 | 119.6 (6) |
C24—C23—C22 | 119.6 (6) | C44—C45—H45 | 120.2 |
C24—C23—H23 | 120.2 | C46—C45—H45 | 120.2 |
C22—C23—H23 | 120.2 | C41—C46—C45 | 120.7 (6) |
C25—C24—C23 | 119.6 (7) | C41—C46—H46 | 119.7 |
C25—C24—H24 | 120.2 | C45—C46—H46 | 119.7 |
C23—C24—H24 | 120.2 | N7—C71—C72 | 177.5 (8) |
C24—C25—C26 | 120.7 (7) | C71—C72—H72A | 109.5 |
C24—C25—H25 | 119.7 | C71—C72—H72B | 109.5 |
C26—C25—H25 | 119.7 | H72A—C72—H72B | 109.5 |
C21—C26—C25 | 119.7 (6) | C71—C72—H72C | 109.5 |
C21—C26—H26 | 120.2 | H72A—C72—H72C | 109.5 |
C25—C26—H26 | 120.2 | H72B—C72—H72C | 109.5 |
O32ii—Cu2—O31 | 166.09 (14) | N8—C81—C82 | 177.8 (11) |
O32ii—Cu2—O41 | 89.65 (16) | C81—C82—H82A | 109.5 |
O31—Cu2—O41 | 88.44 (16) | C81—C82—H82B | 109.5 |
O32ii—Cu2—O42ii | 88.87 (17) | H82A—C82—H82B | 109.5 |
O31—Cu2—O42ii | 89.59 (17) | C81—C82—H82C | 109.5 |
O41—Cu2—O42ii | 165.75 (15) | H82A—C82—H82C | 109.5 |
O32ii—Cu2—N2 | 97.29 (15) | H82B—C82—H82C | 109.5 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···O11i | 0.86 | 2.33 | 3.137 (6) | 156 |
N11—H11A···O21i | 0.86 | 2.55 | 2.964 (5) | 110 |
N11—H11B···N7 | 0.86 | 2.47 | 3.279 (8) | 157 |
N12—H12A···O22 | 0.86 | 2.12 | 2.946 (6) | 161 |
N12—H12B···N8 | 0.86 | 2.40 | 3.139 (9) | 144 |
N21—H21A···O32ii | 0.86 | 2.36 | 3.073 (7) | 140 |
N21—H21A···O41 | 0.86 | 2.37 | 3.000 (6) | 130 |
N22—H22A···O42ii | 0.86 | 2.13 | 2.871 (7) | 144 |
N22—H22A···O31 | 0.86 | 2.52 | 3.093 (6) | 125 |
N22—H22B···N7iii | 0.86 | 2.69 | 3.490 (8) | 154 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z; (iii) −x+2, −y+1, −z. |
(II) 'tetrakis(
ν-benzoato)bis(acetonitrile)dicopper(II) 1.5 acetonitrile solvat'
top
Crystal data top
[Cu2(C7H5O2)4(C2H3N)2]·1.5C2H3N | Z = 1 |
Mr = 755.21 | F(000) = 774 |
Triclinic, P1 | Dx = 1.466 Mg m−3 |
a = 9.875 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.707 (1) Å | Cell parameters from 13906 reflections |
c = 18.046 (2) Å | θ = 2.1–26.5° |
α = 75.86 (1)° | µ = 1.30 mm−1 |
β = 79.69 (1)° | T = 150 K |
γ = 68.28 (1)° | Prismatic, blue |
V = 1710.5 (3) Å3 | 0.22 × 0.20 × 0.20 mm |
Data collection top
Nonius Kappa-CCD diffractometer | 6315 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 26.5°, θmin = 2.1° |
ω scans | h = −12→12 |
13906 measured reflections | k = −13→13 |
7102 independent reflections | l = −22→22 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0398P)2 + 0.5602P] where P = (Fo2 + 2Fc2)/3 |
7102 reflections | (Δ/σ)max = 0.021 |
449 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
Crystal data top
[Cu2(C7H5O2)4(C2H3N)2]·1.5C2H3N | γ = 68.28 (1)° |
Mr = 755.21 | V = 1710.5 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.875 (1) Å | Mo Kα radiation |
b = 10.707 (1) Å | µ = 1.30 mm−1 |
c = 18.046 (2) Å | T = 150 K |
α = 75.86 (1)° | 0.22 × 0.20 × 0.20 mm |
β = 79.69 (1)° | |
Data collection top
Nonius Kappa-CCD diffractometer | 6315 reflections with I > 2σ(I) |
13906 measured reflections | Rint = 0.024 |
7102 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.40 e Å−3 |
7102 reflections | Δρmin = −0.50 e Å−3 |
449 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | 0.93988 (2) | −0.00009 (2) | 0.440550 (11) | 0.01761 (7) | |
Cu2 | 0.90105 (2) | 0.581996 (19) | −0.046085 (11) | 0.01559 (7) | |
O21 | 0.75920 (14) | 0.12300 (13) | 0.48684 (7) | 0.0247 (3) | |
O42 | 0.90078 (15) | 0.72169 (12) | 0.00693 (7) | 0.0251 (3) | |
O11 | 0.98958 (15) | 0.16265 (13) | 0.38755 (7) | 0.0259 (3) | |
O22 | 0.86099 (14) | 0.11654 (14) | 0.59002 (8) | 0.0292 (3) | |
O12 | 1.09087 (15) | 0.16178 (13) | 0.48947 (7) | 0.0275 (3) | |
O31 | 0.75672 (14) | 0.53332 (13) | 0.03430 (7) | 0.0256 (3) | |
O32 | 0.92551 (13) | 0.39655 (13) | 0.11416 (7) | 0.0245 (3) | |
C31 | 0.6785 (2) | 0.41420 (17) | 0.15267 (10) | 0.0212 (4) | |
C20 | 0.7553 (2) | 0.15746 (17) | 0.54962 (10) | 0.0219 (4) | |
N1 | 0.84266 (18) | −0.02986 (16) | 0.34995 (9) | 0.0277 (3) | |
C40 | 0.98722 (19) | 0.69851 (17) | 0.05615 (9) | 0.0196 (3) | |
C41 | 0.9858 (2) | 0.81891 (17) | 0.08525 (9) | 0.0208 (4) | |
C11 | 1.06734 (19) | 0.34737 (18) | 0.38505 (10) | 0.0214 (4) | |
C21 | 0.6146 (2) | 0.25514 (18) | 0.57919 (11) | 0.0225 (4) | |
C10 | 1.04897 (19) | 0.21286 (17) | 0.42338 (10) | 0.0205 (4) | |
C30 | 0.79576 (19) | 0.45091 (17) | 0.09625 (10) | 0.0196 (3) | |
N2 | 0.76428 (17) | 0.73733 (16) | −0.13225 (9) | 0.0252 (3) | |
C16 | 1.03628 (19) | 0.40496 (19) | 0.30943 (10) | 0.0232 (4) | |
H16 | 1.0077 | 0.3568 | 0.2808 | 0.028* | |
C32 | 0.7117 (2) | 0.33455 (18) | 0.22496 (11) | 0.0240 (4) | |
H32 | 0.8094 | 0.3013 | 0.2384 | 0.029* | |
C26 | 0.6019 (2) | 0.28483 (19) | 0.65150 (11) | 0.0261 (4) | |
H26 | 0.6815 | 0.2412 | 0.6822 | 0.031* | |
C42 | 1.0988 (2) | 0.80698 (19) | 0.12545 (10) | 0.0254 (4) | |
H42 | 1.1758 | 0.7216 | 0.1360 | 0.031* | |
C33 | 0.6018 (2) | 0.3040 (2) | 0.27733 (12) | 0.0307 (4) | |
H33 | 0.6241 | 0.2502 | 0.3268 | 0.037* | |
C46 | 0.8733 (2) | 0.94391 (19) | 0.07031 (11) | 0.0283 (4) | |
H46 | 0.7962 | 0.9529 | 0.0423 | 0.034* | |
C2 | 0.7388 (2) | 0.81910 (18) | −0.18641 (10) | 0.0233 (4) | |
C36 | 0.5355 (2) | 0.45991 (19) | 0.13301 (12) | 0.0272 (4) | |
H36 | 0.5128 | 0.5127 | 0.0834 | 0.033* | |
C43 | 1.0993 (2) | 0.9196 (2) | 0.15015 (11) | 0.0310 (4) | |
H43 | 1.1776 | 0.9114 | 0.1770 | 0.037* | |
C12 | 1.1098 (3) | 0.4182 (2) | 0.42617 (11) | 0.0327 (5) | |
H12 | 1.1339 | 0.3784 | 0.4773 | 0.039* | |
C34 | 0.4592 (2) | 0.3517 (2) | 0.25768 (13) | 0.0352 (5) | |
H34 | 0.3841 | 0.3314 | 0.2939 | 0.042* | |
C44 | 0.9865 (2) | 1.0438 (2) | 0.13589 (11) | 0.0321 (5) | |
H44 | 0.9868 | 1.1207 | 0.1532 | 0.038* | |
C14 | 1.0862 (2) | 0.6040 (2) | 0.31765 (11) | 0.0325 (4) | |
H14 | 1.0917 | 0.6921 | 0.2947 | 0.039* | |
C111 | 0.7873 (2) | −0.0675 (2) | 0.31477 (11) | 0.0276 (4) | |
C45 | 0.8735 (3) | 1.0555 (2) | 0.09626 (12) | 0.0337 (5) | |
H45 | 0.7956 | 1.1405 | 0.0867 | 0.040* | |
C22 | 0.4972 (2) | 0.3194 (2) | 0.53477 (13) | 0.0327 (4) | |
H22 | 0.5043 | 0.2991 | 0.4855 | 0.039* | |
C15 | 1.0469 (2) | 0.5322 (2) | 0.27582 (11) | 0.0278 (4) | |
H15 | 1.0271 | 0.5705 | 0.2239 | 0.033* | |
C35 | 0.4264 (2) | 0.4286 (2) | 0.18559 (13) | 0.0334 (5) | |
H35 | 0.3290 | 0.4601 | 0.1720 | 0.040* | |
C13 | 1.1173 (3) | 0.5475 (2) | 0.39271 (12) | 0.0394 (5) | |
H13 | 1.1437 | 0.5969 | 0.4215 | 0.047* | |
O41 | 1.07580 (14) | 0.58261 (12) | 0.08289 (7) | 0.0240 (3) | |
C25 | 0.4737 (2) | 0.3777 (2) | 0.67906 (13) | 0.0336 (5) | |
H25 | 0.4654 | 0.3971 | 0.7286 | 0.040* | |
C24 | 0.3584 (2) | 0.4418 (2) | 0.63435 (15) | 0.0409 (5) | |
H24 | 0.2707 | 0.5059 | 0.6530 | 0.049* | |
C2' | 0.7078 (3) | 0.9233 (2) | −0.25613 (11) | 0.0371 (5) | |
H21A | 0.7996 | 0.9335 | −0.2831 | 0.056* | |
H21B | 0.6426 | 1.0108 | −0.2427 | 0.056* | |
H21C | 0.6603 | 0.8956 | −0.2895 | 0.056* | |
C23 | 0.3700 (2) | 0.4129 (2) | 0.56225 (15) | 0.0425 (6) | |
H23 | 0.2903 | 0.4574 | 0.5315 | 0.051* | |
C3' | 0.4755 (3) | 0.8098 (3) | 0.01139 (15) | 0.0552 (7) | |
H31A | 0.3816 | 0.7946 | 0.0190 | 0.083* | |
H31B | 0.5550 | 0.7262 | 0.0011 | 0.083* | |
H31C | 0.4747 | 0.8853 | −0.0323 | 0.083* | |
C3 | 0.4979 (3) | 0.8444 (3) | 0.08014 (17) | 0.0530 (7) | |
C112 | 0.7148 (3) | −0.1165 (3) | 0.27021 (15) | 0.0544 (7) | |
H11A | 0.6543 | −0.1652 | 0.3051 | 0.082* | |
H11B | 0.7887 | −0.1790 | 0.2396 | 0.082* | |
H11C | 0.6527 | −0.0384 | 0.2360 | 0.082* | |
N3 | 0.5132 (3) | 0.8726 (3) | 0.13337 (18) | 0.0815 (8) | |
C4' | 0.488 (3) | 0.026 (3) | 0.4607 (15) | 0.0321 (18) | 0.50 |
H'1 | 0.3864 | 0.0896 | 0.4630 | 0.048* | 0.50 |
H'2 | 0.4970 | −0.0437 | 0.4320 | 0.048* | 0.50 |
H'3 | 0.5532 | 0.0772 | 0.4348 | 0.048* | 0.50 |
C4 | 0.527 (3) | −0.039 (3) | 0.5381 (16) | 0.0321 (18) | 0.50 |
N4 | 0.5503 (5) | −0.0798 (4) | 0.5992 (2) | 0.0457 (10) | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01659 (12) | 0.01807 (12) | 0.02080 (11) | −0.00800 (9) | −0.00137 (8) | −0.00557 (8) |
Cu2 | 0.01643 (11) | 0.01364 (11) | 0.01595 (11) | −0.00457 (8) | −0.00236 (8) | −0.00185 (8) |
O21 | 0.0200 (6) | 0.0263 (7) | 0.0283 (7) | −0.0068 (5) | 0.0000 (5) | −0.0100 (5) |
O42 | 0.0321 (7) | 0.0178 (6) | 0.0265 (6) | −0.0052 (5) | −0.0100 (5) | −0.0062 (5) |
O11 | 0.0314 (7) | 0.0285 (7) | 0.0251 (6) | −0.0195 (6) | −0.0009 (5) | −0.0052 (5) |
O22 | 0.0191 (7) | 0.0329 (7) | 0.0357 (7) | −0.0026 (6) | −0.0032 (5) | −0.0163 (6) |
O12 | 0.0345 (8) | 0.0233 (6) | 0.0299 (7) | −0.0160 (6) | −0.0100 (6) | 0.0002 (5) |
O31 | 0.0199 (6) | 0.0298 (7) | 0.0235 (6) | −0.0082 (5) | −0.0006 (5) | −0.0001 (5) |
O32 | 0.0190 (6) | 0.0254 (7) | 0.0251 (6) | −0.0078 (5) | 0.0006 (5) | 0.0005 (5) |
C31 | 0.0209 (9) | 0.0168 (8) | 0.0270 (9) | −0.0078 (7) | 0.0028 (7) | −0.0077 (7) |
C20 | 0.0204 (9) | 0.0169 (8) | 0.0301 (9) | −0.0102 (7) | 0.0017 (7) | −0.0046 (7) |
N1 | 0.0273 (9) | 0.0284 (8) | 0.0300 (8) | −0.0093 (7) | −0.0064 (7) | −0.0079 (7) |
C40 | 0.0241 (9) | 0.0190 (8) | 0.0166 (8) | −0.0108 (7) | 0.0034 (7) | −0.0035 (7) |
C41 | 0.0288 (10) | 0.0181 (8) | 0.0174 (8) | −0.0119 (7) | 0.0008 (7) | −0.0033 (6) |
C11 | 0.0192 (9) | 0.0222 (9) | 0.0240 (8) | −0.0096 (7) | 0.0011 (7) | −0.0050 (7) |
C21 | 0.0191 (9) | 0.0179 (8) | 0.0328 (9) | −0.0092 (7) | 0.0016 (7) | −0.0073 (7) |
C10 | 0.0167 (8) | 0.0195 (8) | 0.0256 (9) | −0.0073 (7) | 0.0025 (7) | −0.0067 (7) |
C30 | 0.0204 (9) | 0.0169 (8) | 0.0228 (8) | −0.0070 (7) | 0.0009 (7) | −0.0075 (7) |
N2 | 0.0239 (8) | 0.0245 (8) | 0.0260 (8) | −0.0063 (7) | −0.0060 (6) | −0.0035 (7) |
C16 | 0.0190 (9) | 0.0263 (9) | 0.0253 (9) | −0.0085 (7) | 0.0001 (7) | −0.0074 (7) |
C32 | 0.0221 (9) | 0.0192 (9) | 0.0285 (9) | −0.0058 (7) | 0.0023 (7) | −0.0060 (7) |
C26 | 0.0236 (9) | 0.0220 (9) | 0.0340 (10) | −0.0089 (8) | −0.0004 (8) | −0.0080 (8) |
C42 | 0.0318 (10) | 0.0206 (9) | 0.0255 (9) | −0.0115 (8) | −0.0035 (8) | −0.0027 (7) |
C33 | 0.0308 (11) | 0.0224 (9) | 0.0326 (10) | −0.0091 (8) | 0.0069 (8) | −0.0010 (8) |
C46 | 0.0320 (11) | 0.0215 (9) | 0.0314 (10) | −0.0072 (8) | −0.0053 (8) | −0.0067 (8) |
C2 | 0.0210 (9) | 0.0226 (9) | 0.0246 (9) | −0.0040 (7) | −0.0034 (7) | −0.0063 (8) |
C36 | 0.0249 (10) | 0.0238 (9) | 0.0346 (10) | −0.0119 (8) | −0.0005 (8) | −0.0050 (8) |
C43 | 0.0391 (12) | 0.0300 (10) | 0.0321 (10) | −0.0187 (9) | −0.0068 (9) | −0.0072 (8) |
C12 | 0.0490 (13) | 0.0332 (11) | 0.0246 (9) | −0.0259 (10) | −0.0064 (9) | −0.0002 (8) |
C34 | 0.0284 (11) | 0.0272 (10) | 0.0468 (12) | −0.0149 (9) | 0.0120 (9) | −0.0044 (9) |
C44 | 0.0480 (13) | 0.0238 (10) | 0.0312 (10) | −0.0193 (9) | 0.0005 (9) | −0.0097 (8) |
C14 | 0.0416 (12) | 0.0257 (10) | 0.0315 (10) | −0.0179 (9) | 0.0000 (9) | −0.0005 (8) |
C111 | 0.0273 (10) | 0.0310 (10) | 0.0248 (9) | −0.0109 (8) | −0.0040 (8) | −0.0037 (8) |
C45 | 0.0423 (12) | 0.0191 (9) | 0.0375 (11) | −0.0054 (9) | −0.0050 (9) | −0.0087 (8) |
C22 | 0.0277 (10) | 0.0316 (11) | 0.0415 (11) | −0.0074 (9) | −0.0071 (9) | −0.0137 (9) |
C15 | 0.0271 (10) | 0.0309 (10) | 0.0235 (9) | −0.0119 (8) | −0.0017 (7) | 0.0005 (8) |
C35 | 0.0212 (10) | 0.0269 (10) | 0.0526 (13) | −0.0113 (8) | 0.0005 (9) | −0.0069 (9) |
C13 | 0.0654 (16) | 0.0352 (11) | 0.0314 (11) | −0.0332 (11) | −0.0071 (10) | −0.0040 (9) |
O41 | 0.0308 (7) | 0.0165 (6) | 0.0256 (6) | −0.0065 (5) | −0.0075 (5) | −0.0047 (5) |
C25 | 0.0306 (11) | 0.0316 (11) | 0.0419 (11) | −0.0115 (9) | 0.0065 (9) | −0.0188 (9) |
C24 | 0.0215 (10) | 0.0363 (12) | 0.0667 (15) | −0.0049 (9) | 0.0050 (10) | −0.0276 (11) |
C2' | 0.0467 (13) | 0.0293 (11) | 0.0261 (10) | −0.0065 (9) | −0.0076 (9) | 0.0036 (8) |
C23 | 0.0235 (11) | 0.0387 (12) | 0.0657 (15) | −0.0001 (9) | −0.0144 (10) | −0.0203 (11) |
C3' | 0.0468 (15) | 0.0403 (14) | 0.0518 (15) | 0.0059 (11) | 0.0024 (12) | 0.0007 (11) |
C3 | 0.0411 (14) | 0.0441 (14) | 0.0588 (17) | −0.0079 (11) | 0.0091 (12) | −0.0034 (13) |
C112 | 0.0594 (17) | 0.0812 (19) | 0.0461 (14) | −0.0427 (15) | −0.0103 (12) | −0.0217 (13) |
N3 | 0.074 (2) | 0.092 (2) | 0.079 (2) | −0.0234 (17) | 0.0044 (16) | −0.0319 (17) |
C4' | 0.028 (5) | 0.039 (4) | 0.0326 (14) | −0.018 (4) | 0.000 (2) | −0.0049 (19) |
C4 | 0.028 (5) | 0.039 (4) | 0.0326 (14) | −0.018 (4) | 0.000 (2) | −0.0049 (19) |
N4 | 0.049 (2) | 0.057 (3) | 0.036 (2) | −0.030 (2) | −0.0034 (18) | 0.0000 (19) |
Geometric parameters (Å, º) top
Cu1—O11 | 1.9602 (13) | C46—C45 | 1.387 (3) |
Cu1—O22i | 1.9644 (13) | C46—H46 | 0.9500 |
Cu1—O12i | 1.9666 (13) | C2—C2' | 1.456 (3) |
Cu1—O21 | 1.9704 (13) | C36—C35 | 1.385 (3) |
Cu1—N1 | 2.1770 (16) | C36—H36 | 0.9500 |
Cu1—Cu1i | 2.6323 (5) | C43—C44 | 1.384 (3) |
Cu2—O41ii | 1.9542 (12) | C43—H43 | 0.9500 |
Cu2—O42 | 1.9615 (12) | C12—C13 | 1.392 (3) |
Cu2—O31 | 1.9616 (13) | C12—H12 | 0.9500 |
Cu2—O32ii | 1.9737 (13) | C34—C35 | 1.381 (3) |
Cu2—N2 | 2.1986 (15) | C34—H34 | 0.9500 |
Cu2—Cu2ii | 2.6202 (5) | C44—C45 | 1.382 (3) |
O21—C20 | 1.265 (2) | C44—H44 | 0.9500 |
O42—C40 | 1.259 (2) | C14—C13 | 1.381 (3) |
O11—C10 | 1.261 (2) | C14—C15 | 1.386 (3) |
O22—C20 | 1.261 (2) | C14—H14 | 0.9500 |
O22—Cu1i | 1.9643 (13) | C111—C112 | 1.458 (3) |
O12—C10 | 1.258 (2) | C45—H45 | 0.9500 |
O12—Cu1i | 1.9666 (13) | C22—C23 | 1.384 (3) |
O31—C30 | 1.264 (2) | C22—H22 | 0.9500 |
O32—C30 | 1.261 (2) | C15—H15 | 0.9500 |
O32—Cu2ii | 1.9737 (13) | C35—H35 | 0.9500 |
C31—C32 | 1.392 (3) | C13—H13 | 0.9500 |
C31—C36 | 1.394 (3) | O41—Cu2ii | 1.9542 (12) |
C31—C30 | 1.500 (2) | C25—C24 | 1.378 (3) |
C20—C21 | 1.497 (3) | C25—H25 | 0.9500 |
N1—C111 | 1.130 (2) | C24—C23 | 1.385 (3) |
C40—O41 | 1.262 (2) | C24—H24 | 0.9500 |
C40—C41 | 1.501 (2) | C2'—H21A | 0.9800 |
C41—C42 | 1.388 (3) | C2'—H21B | 0.9800 |
C41—C46 | 1.389 (3) | C2'—H21C | 0.9800 |
C11—C12 | 1.387 (3) | C23—H23 | 0.9500 |
C11—C16 | 1.391 (2) | C3'—C3 | 1.452 (4) |
C11—C10 | 1.499 (2) | C3'—H31A | 0.9800 |
C21—C22 | 1.390 (3) | C3'—H31B | 0.9800 |
C21—C26 | 1.391 (3) | C3'—H31C | 0.9800 |
N2—C2 | 1.137 (2) | C3—N3 | 1.124 (4) |
C16—C15 | 1.383 (3) | C112—H11A | 0.9800 |
C16—H16 | 0.9500 | C112—H11B | 0.9800 |
C32—C33 | 1.387 (3) | C112—H11C | 0.9800 |
C32—H32 | 0.9500 | C4'—C4 | 1.452 (4) |
C26—C25 | 1.387 (3) | C4'—H'1 | 0.9800 |
C26—H26 | 0.9500 | C4'—H'2 | 0.9800 |
C42—C43 | 1.385 (3) | C4'—H'3 | 0.9800 |
C33—C34 | 1.388 (3) | C4—N4 | 1.11 (3) |
C33—H33 | 0.9500 | | |
| | | |
O11—Cu1—O22i | 89.51 (6) | C43—C42—H42 | 120.0 |
O11—Cu1—O12i | 168.58 (5) | C41—C42—H42 | 120.0 |
O22i—Cu1—O12i | 88.99 (6) | C32—C33—C34 | 120.19 (19) |
O11—Cu1—O21 | 87.97 (6) | C32—C33—H33 | 119.9 |
O22i—Cu1—O21 | 168.45 (5) | C34—C33—H33 | 119.9 |
O12i—Cu1—O21 | 91.26 (6) | C45—C46—C41 | 119.94 (18) |
O11—Cu1—N1 | 99.99 (6) | C45—C46—H46 | 120.0 |
O22i—Cu1—N1 | 94.25 (6) | C41—C46—H46 | 120.0 |
O12i—Cu1—N1 | 91.41 (6) | N2—C2—C2' | 179.4 (2) |
O21—Cu1—N1 | 97.28 (6) | C35—C36—C31 | 120.22 (18) |
O11—Cu1—Cu1i | 87.80 (4) | C35—C36—H36 | 119.9 |
O22i—Cu1—Cu1i | 83.49 (4) | C31—C36—H36 | 119.9 |
O12i—Cu1—Cu1i | 80.78 (4) | C44—C43—C42 | 120.36 (19) |
O21—Cu1—Cu1i | 85.16 (4) | C44—C43—H43 | 119.8 |
N1—Cu1—Cu1i | 171.89 (4) | C42—C43—H43 | 119.8 |
O41ii—Cu2—O42 | 168.70 (5) | C11—C12—C13 | 120.23 (18) |
O41ii—Cu2—O31 | 86.96 (6) | C11—C12—H12 | 119.9 |
O42—Cu2—O31 | 90.19 (6) | C13—C12—H12 | 119.9 |
O41ii—Cu2—O32ii | 90.85 (6) | C35—C34—C33 | 120.18 (18) |
O42—Cu2—O32ii | 89.85 (6) | C35—C34—H34 | 119.9 |
O31—Cu2—O32ii | 168.86 (5) | C33—C34—H34 | 119.9 |
O41ii—Cu2—N2 | 99.23 (6) | C45—C44—C43 | 119.63 (18) |
O42—Cu2—N2 | 92.07 (6) | C45—C44—H44 | 120.2 |
O31—Cu2—N2 | 103.14 (6) | C43—C44—H44 | 120.2 |
O32ii—Cu2—N2 | 87.99 (6) | C13—C14—C15 | 119.97 (18) |
O41ii—Cu2—Cu2ii | 85.32 (4) | C13—C14—H14 | 120.0 |
O42—Cu2—Cu2ii | 83.58 (4) | C15—C14—H14 | 120.0 |
O31—Cu2—Cu2ii | 86.20 (4) | N1—C111—C112 | 179.3 (2) |
O32ii—Cu2—Cu2ii | 82.74 (4) | C44—C45—C46 | 120.39 (19) |
N2—Cu2—Cu2ii | 169.75 (4) | C44—C45—H45 | 119.8 |
C20—O21—Cu1 | 121.76 (12) | C46—C45—H45 | 119.8 |
C40—O42—Cu2 | 123.44 (11) | C23—C22—C21 | 120.0 (2) |
C10—O11—Cu1 | 118.73 (11) | C23—C22—H22 | 120.0 |
C20—O22—Cu1i | 124.04 (12) | C21—C22—H22 | 120.0 |
C10—O12—Cu1i | 126.71 (11) | C16—C15—C14 | 120.21 (17) |
C30—O31—Cu2 | 121.17 (12) | C16—C15—H15 | 119.9 |
C30—O32—Cu2ii | 124.63 (11) | C14—C15—H15 | 119.9 |
C32—C31—C36 | 119.60 (17) | C34—C35—C36 | 119.99 (19) |
C32—C31—C30 | 120.29 (16) | C34—C35—H35 | 120.0 |
C36—C31—C30 | 120.11 (16) | C36—C35—H35 | 120.0 |
O22—C20—O21 | 125.39 (17) | C14—C13—C12 | 119.95 (19) |
O22—C20—C21 | 116.50 (16) | C14—C13—H13 | 120.0 |
O21—C20—C21 | 118.11 (16) | C12—C13—H13 | 120.0 |
C111—N1—Cu1 | 165.21 (16) | C40—O41—Cu2ii | 121.81 (11) |
O42—C40—O41 | 125.60 (16) | C24—C25—C26 | 119.8 (2) |
O42—C40—C41 | 117.38 (15) | C24—C25—H25 | 120.1 |
O41—C40—C41 | 117.02 (15) | C26—C25—H25 | 120.1 |
C42—C41—C46 | 119.66 (16) | C25—C24—C23 | 120.1 (2) |
C42—C41—C40 | 120.24 (16) | C25—C24—H24 | 119.9 |
C46—C41—C40 | 120.08 (16) | C23—C24—H24 | 119.9 |
C12—C11—C16 | 119.43 (17) | C2—C2'—H21A | 109.5 |
C12—C11—C10 | 119.86 (16) | C2—C2'—H21B | 109.5 |
C16—C11—C10 | 120.66 (16) | H21A—C2'—H21B | 109.5 |
C22—C21—C26 | 119.27 (18) | C2—C2'—H21C | 109.5 |
C22—C21—C20 | 121.05 (17) | H21A—C2'—H21C | 109.5 |
C26—C21—C20 | 119.67 (17) | H21B—C2'—H21C | 109.5 |
O12—C10—O11 | 125.74 (16) | C22—C23—C24 | 120.2 (2) |
O12—C10—C11 | 116.92 (15) | C22—C23—H23 | 119.9 |
O11—C10—C11 | 117.31 (15) | C24—C23—H23 | 119.9 |
O32—C30—O31 | 125.16 (16) | C3—C3'—H31A | 109.5 |
O32—C30—C31 | 117.45 (15) | C3—C3'—H31B | 109.5 |
O31—C30—C31 | 117.40 (15) | H31A—C3'—H31B | 109.5 |
C2—N2—Cu2 | 156.97 (15) | C3—C3'—H31C | 109.5 |
C15—C16—C11 | 120.17 (17) | H31A—C3'—H31C | 109.5 |
C15—C16—H16 | 119.9 | H31B—C3'—H31C | 109.5 |
C11—C16—H16 | 119.9 | N3—C3—C3' | 178.9 (3) |
C33—C32—C31 | 119.80 (18) | C111—C112—H11A | 109.5 |
C33—C32—H32 | 120.1 | C111—C112—H11B | 109.5 |
C31—C32—H32 | 120.1 | H11A—C112—H11B | 109.5 |
C25—C26—C21 | 120.48 (19) | C111—C112—H11C | 109.5 |
C25—C26—H26 | 119.8 | H11A—C112—H11C | 109.5 |
C21—C26—H26 | 119.8 | H11B—C112—H11C | 109.5 |
C43—C42—C41 | 120.02 (18) | N4—C4—C4' | 174.3 (16) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Cu2(C7H5O2)4(C5H7N3)2]·2C2H3N | [Cu2(C7H5O2)4(C2H3N)2]·1.5C2H3N |
Mr | 911.92 | 755.21 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 150 |
a, b, c (Å) | 10.690 (1), 12.822 (3), 16.485 (2) | 9.875 (1), 10.707 (1), 18.046 (2) |
α, β, γ (°) | 85.24 (1), 71.24 (1), 85.87 (1) | 75.86 (1), 79.69 (1), 68.28 (1) |
V (Å3) | 2129.7 (6) | 1710.5 (3) |
Z | 2 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.06 | 1.30 |
Crystal size (mm) | 0.40 × 0.19 × 0.11 | 0.22 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | NONIUS CAD-4 diffractometer | Nonius Kappa-CCD diffractometer |
Absorption correction | Gaussian (PLATON; Spek, 1998) | – |
Tmin, Tmax | 0.61, 0.88 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8494, 8365, 4333 | 13906, 7102, 6315 |
Rint | 0.017 | 0.024 |
(sin θ/λ)max (Å−1) | 0.617 | 0.628 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.154, 0.99 | 0.025, 0.079, 1.11 |
No. of reflections | 8365 | 7102 |
No. of parameters | 543 | 449 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.68, −0.75 | 0.40, −0.50 |
Selected bond lengths (Å) for (I) topCu1—O12 | 1.963 (3) | Cu2—O32ii | 1.961 (3) |
Cu1—O11i | 1.968 (3) | Cu2—O31 | 1.964 (3) |
Cu1—O21i | 1.971 (4) | Cu2—O41 | 1.971 (3) |
Cu1—O22 | 1.975 (3) | Cu2—O42ii | 1.974 (4) |
Cu1—N1 | 2.263 (4) | Cu2—N2 | 2.245 (4) |
Cu1—Cu1i | 2.7114 (12) | Cu2—Cu2ii | 2.7130 (12) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···O11i | 0.86 | 2.33 | 3.137 (6) | 156 |
N11—H11A···O21i | 0.86 | 2.55 | 2.964 (5) | 110 |
N11—H11B···N7 | 0.86 | 2.47 | 3.279 (8) | 157 |
N12—H12A···O22 | 0.86 | 2.12 | 2.946 (6) | 161 |
N12—H12B···N8 | 0.86 | 2.40 | 3.139 (9) | 144 |
N21—H21A···O32ii | 0.86 | 2.36 | 3.073 (7) | 140 |
N21—H21A···O41 | 0.86 | 2.37 | 3.000 (6) | 130 |
N22—H22A···O42ii | 0.86 | 2.13 | 2.871 (7) | 144 |
N22—H22A···O31 | 0.86 | 2.52 | 3.093 (6) | 125 |
N22—H22B···N7iii | 0.86 | 2.69 | 3.490 (8) | 154 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z; (iii) −x+2, −y+1, −z. |
Selected bond lengths (Å) for (II) topCu1—O11 | 1.9602 (13) | Cu2—O41ii | 1.9542 (12) |
Cu1—O22i | 1.9644 (13) | Cu2—O42 | 1.9615 (12) |
Cu1—O12i | 1.9666 (13) | Cu2—O31 | 1.9616 (13) |
Cu1—O21 | 1.9704 (13) | Cu2—O32ii | 1.9737 (13) |
Cu1—N1 | 2.1770 (16) | Cu2—N2 | 2.1986 (15) |
Cu1—Cu1i | 2.6323 (5) | Cu2—Cu2ii | 2.6202 (5) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z. |
Copper carboxylate complexes have properties of importance in various areas and accordingly have been extensively studied (Sundberg et al., 1996, and references therein). In this series mononuclear, dinuclear as well as polymeric complexes are known. In continuation of our research on metal carboxylates with increased fungicidal activity two dimeric forms of CuII benzoates with 2,6 diaminopyridine and acetonitrile as axially coordinated ligands were prepared. Both compounds crystallize as acetonitrile solvates with markedly different stability. While compound (I) is stable on air, crystals of compound (II) decompose rapidly when taken from the mother liquor. In this context, the crystal structures of the title compounds are presented here. \sch
In the unit cell, two crystallographically independent dimeric units are present in both structures with an inversion center located between the copper ions. The Cu atom is five coordinated in square pyramidal fashion: four equatorial O atoms belong to bridging carboxyl groups and nitrogen atom on apical position belongs to 2,6-diaminopyridine in (I) (Fig. 1) and to acetonitrile in (II) (Fig. 2). Geometrical parameters are comparable to the values reported previously for similar type of compounds (Speier et al., 1989; Kawata et al., 1992; Leban et al., 1997; Marsh, 1999). As reported by Sundberg et al. (1996), the longer the Cu—Cu distance within the dimer, the higher the Cu out-of-plane deviation. The Cu—Cu separations for (I) are 2.711 (1) and 2.713 (1) Å with the deviations of Cu from the basal plane of 0.244 (2) Å for both dimeric units. In compound (II), the corresponding values are 2.6323 (5) and 2.6202 (5) Å for the Cu—Cu separations and 0.1958 (7), 0.1901 (6) Å for out of plane displacement, respectively.
The main reason for quite different stability of the two solvates could be ascribed to hydrogen bonds present in compound (I). Due to the presence of hydrogen donors (amino groups) the extensive hydrogen bonding was expected. Beside the intramolecular contacts of N—H···O type the solvated acetonitrile molecules are held in the crystal by N—H···N hydrogen bonds. One acetonitrile molecule is hydrogen bonded to one amino group of 2,6-diaminopyridine [N12···N8 3.139 (9) Å] while the other one is linked to two NH2 groups of the different neighbouring dimers [N11···N7 3.2798 Å and N22···N7 at -x + 2, -y + 1, -z, 3.490 (8) Å]. Detailed geometrical parameters for hydrogen bonds in (I) are presented in Table 2. For compound (II) no classic hydrogen bonds were detected.