The title compound, [Cu
2(C
9H
10NO
3)
2(NO
3)
2(C
10H
8N
2)(H
2O)
2]
n, contains Cu
II atoms and
L-tyrosinate (
L-tyr) and 4,4′-bipyridine (4,4′-bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two
L-tyr ligands, one N atom from a 4,4′-bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4′-bipy ligands, forming an undulated chiral two-dimensional sheet. O—H
O and N—H
O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4′-bipy ligands by considering the ratios of the metal ion and organic components.
Supporting information
CCDC reference: 718101
Cu(NO3)2.3H2O (0.096 g, 0.4 mmol) and L-tyrosine (0.072 g, 0.4 mmol) were dissolved in hot water (20 ml) with stirring. To this solution was
added 4,4'-bipyridine (0.031 g, 0.2 mmol) in methanol (10 ml). The resulting
solution was allowed to stand at room temperature and blue crystals of (I)
suitable for X-ray diffraction analysis were obtained after two weeks.
H atoms bonded to O atoms were located in a difference Fourier map and fixed in
the refinement, with Uiso(H) = 1.2Ueq(O). Other H atoms were
positioned geometrically and refined using a riding model, with C—H = 0.93
(aromatic), 0.97 (CH2) or 0.98 (CH) Å and N—H = 0.90 Å, and with
Uiso(H) = 1.2Ueq(C,N). The highest residual electron
density is 0.94 Å from atom Cu2 and the deepest hole 0.93 Å from atom Cu1.
Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL.
Poly[[diaqua-µ-4,4'-bipyridine-dinitratodi-µ-L-tyrosinato-diaquadicopper(II)]
top
Crystal data top
[Cu2(C9H10NO3)2(NO3)2(C10H8N2)(H2O)2] | F(000) = 824 |
Mr = 803.68 | Dx = 1.687 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4737 reflections |
a = 7.6075 (13) Å | θ = 2.4–26.1° |
b = 22.281 (4) Å | µ = 1.43 mm−1 |
c = 9.8205 (16) Å | T = 293 K |
β = 108.150 (2)° | Prism, blue |
V = 1581.8 (5) Å3 | 0.33 × 0.19 × 0.17 mm |
Z = 2 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 5584 independent reflections |
Radiation source: fine-focus sealed tube | 5003 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 25.8°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.652, Tmax = 0.791 | k = −27→24 |
8422 measured reflections | l = −12→9 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.137 | w = 1/[σ2(Fo2) + (0.0889P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.006 |
5584 reflections | Δρmax = 1.23 e Å−3 |
439 parameters | Δρmin = −0.87 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 2506 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.010 (18) |
Crystal data top
[Cu2(C9H10NO3)2(NO3)2(C10H8N2)(H2O)2] | V = 1581.8 (5) Å3 |
Mr = 803.68 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.6075 (13) Å | µ = 1.43 mm−1 |
b = 22.281 (4) Å | T = 293 K |
c = 9.8205 (16) Å | 0.33 × 0.19 × 0.17 mm |
β = 108.150 (2)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 5584 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5003 reflections with I > 2σ(I) |
Tmin = 0.652, Tmax = 0.791 | Rint = 0.032 |
8422 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.137 | Δρmax = 1.23 e Å−3 |
S = 1.08 | Δρmin = −0.87 e Å−3 |
5584 reflections | Absolute structure: Flack (1983), with 2506 Friedel pairs |
439 parameters | Absolute structure parameter: 0.010 (18) |
1 restraint | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.65447 (8) | −0.074095 (19) | 0.03002 (6) | 0.03088 (18) | |
Cu2 | 0.64748 (9) | −0.14898 (2) | 0.52764 (6) | 0.03256 (19) | |
O1W | 0.3519 (6) | −0.0347 (2) | 0.0291 (5) | 0.0537 (11) | |
H1W | 0.2866 | −0.0516 | 0.0860 | 0.064* | |
H2W | 0.2708 | −0.0306 | −0.0534 | 0.064* | |
O2W | 0.3137 (7) | −0.1796 (2) | 0.5268 (6) | 0.0606 (13) | |
H3W | 0.2491 | −0.1625 | 0.5734 | 0.073* | |
H4W | 0.2502 | −0.1749 | 0.4368 | 0.073* | |
O1 | 0.6762 (5) | −0.10763 (18) | 0.2227 (4) | 0.0334 (8) | |
O2 | 0.5688 (5) | −0.18057 (17) | 0.3307 (4) | 0.0333 (8) | |
O3 | 1.0203 (7) | −0.4124 (2) | 0.2408 (6) | 0.0641 (13) | |
H3 | 0.9791 | −0.4493 | 0.2326 | 0.077* | |
O4 | 0.6594 (6) | −0.11945 (16) | 0.7187 (4) | 0.0341 (9) | |
O5 | 0.6068 (6) | −0.04034 (17) | 0.8366 (4) | 0.0352 (9) | |
O6 | 0.5628 (7) | 0.22702 (19) | 0.2812 (5) | 0.0599 (11) | |
H6A | 0.6072 | 0.2557 | 0.3403 | 0.072* | |
O7 | 0.9706 (6) | −0.1209 (3) | 0.0535 (5) | 0.0673 (15) | |
O8 | 1.1001 (8) | −0.1743 (3) | 0.2412 (8) | 0.0839 (19) | |
O9 | 1.1833 (7) | −0.0821 (2) | 0.2309 (6) | 0.0644 (13) | |
O10 | 0.9665 (9) | −0.0804 (3) | 0.5561 (7) | 0.0867 (12) | |
O11 | 1.0682 (9) | −0.0326 (3) | 0.7594 (7) | 0.0867 (12) | |
O12 | 1.1989 (8) | −0.1120 (4) | 0.7213 (7) | 0.099 (2) | |
N1 | 0.7849 (6) | 0.0017 (2) | 0.1148 (5) | 0.0325 (10) | |
N2 | 1.2032 (7) | 0.2784 (2) | 0.3938 (5) | 0.0371 (11) | |
N3 | 0.5382 (6) | −0.1539 (2) | −0.0360 (5) | 0.0310 (9) | |
H3A | 0.4461 | −0.1496 | −0.1192 | 0.037* | |
H3B | 0.6229 | −0.1791 | −0.0508 | 0.037* | |
N4 | 0.5479 (7) | −0.0687 (2) | 0.4656 (4) | 0.0370 (10) | |
H4A | 0.6038 | −0.0536 | 0.4048 | 0.044* | |
H4B | 0.4261 | −0.0716 | 0.4184 | 0.044* | |
N5 | 1.0848 (7) | −0.1252 (3) | 0.1757 (7) | 0.0527 (15) | |
N6 | 1.0791 (7) | −0.0751 (3) | 0.6782 (6) | 0.0542 (14) | |
C1 | 0.7881 (13) | 0.0209 (3) | 0.2439 (8) | 0.076 (2) | |
H1 | 0.7375 | −0.0038 | 0.2983 | 0.092* | |
C2 | 0.8616 (13) | 0.0753 (3) | 0.3024 (8) | 0.076 (2) | |
H2 | 0.8581 | 0.0865 | 0.3927 | 0.092* | |
C3 | 0.9385 (7) | 0.1119 (3) | 0.2273 (6) | 0.0333 (12) | |
C4 | 0.9382 (11) | 0.0923 (3) | 0.0942 (6) | 0.0544 (19) | |
H4 | 0.9902 | 0.1160 | 0.0388 | 0.065* | |
C5 | 0.8613 (10) | 0.0378 (3) | 0.0432 (6) | 0.0524 (17) | |
H5 | 0.8632 | 0.0257 | −0.0469 | 0.063* | |
C6 | 1.1788 (10) | 0.2348 (3) | 0.4811 (7) | 0.0469 (15) | |
H6 | 1.2239 | 0.2407 | 0.5797 | 0.056* | |
C7 | 1.0896 (10) | 0.1815 (3) | 0.4301 (7) | 0.0459 (15) | |
H7 | 1.0761 | 0.1525 | 0.4942 | 0.055* | |
C8 | 1.0201 (8) | 0.1711 (2) | 0.2842 (6) | 0.0319 (11) | |
C9 | 1.0389 (8) | 0.2170 (2) | 0.1946 (6) | 0.0421 (13) | |
H9 | 0.9921 | 0.2125 | 0.0957 | 0.050* | |
C10 | 1.1284 (8) | 0.2700 (2) | 0.2533 (6) | 0.0373 (12) | |
H10 | 1.1361 | 0.3008 | 0.1916 | 0.045* | |
C11 | 0.5793 (7) | −0.1544 (3) | 0.2209 (5) | 0.0273 (10) | |
C12 | 0.4648 (7) | −0.1786 (2) | 0.0739 (5) | 0.0295 (10) | |
H12 | 0.3428 | −0.1600 | 0.0550 | 0.035* | |
C13 | 0.4278 (8) | −0.2456 (3) | 0.0658 (6) | 0.0355 (13) | |
H13A | 0.3535 | −0.2544 | 0.1276 | 0.043* | |
H13B | 0.3527 | −0.2548 | −0.0314 | 0.043* | |
C14 | 0.5901 (7) | −0.2881 (2) | 0.1050 (5) | 0.0347 (11) | |
C15 | 0.5558 (8) | −0.3495 (3) | 0.1026 (6) | 0.0401 (14) | |
H15 | 0.4336 | −0.3626 | 0.0722 | 0.048* | |
C16 | 0.6930 (9) | −0.3917 (3) | 0.1429 (6) | 0.0446 (13) | |
H16 | 0.6638 | −0.4323 | 0.1370 | 0.054* | |
C17 | 0.8755 (9) | −0.3732 (3) | 0.1924 (6) | 0.0461 (13) | |
C18 | 0.9170 (9) | −0.3136 (3) | 0.1911 (7) | 0.0477 (14) | |
H18 | 1.0398 | −0.3011 | 0.2195 | 0.057* | |
C19 | 0.7735 (7) | −0.2710 (2) | 0.1467 (6) | 0.0383 (11) | |
H19 | 0.8030 | −0.2306 | 0.1455 | 0.046* | |
C20 | 0.6144 (7) | −0.0656 (3) | 0.7252 (5) | 0.0292 (11) | |
C21 | 0.5769 (7) | −0.0273 (2) | 0.5900 (5) | 0.0295 (10) | |
H21 | 0.6911 | −0.0051 | 0.5987 | 0.035* | |
C22 | 0.4230 (9) | 0.0195 (3) | 0.5660 (7) | 0.0388 (14) | |
H22A | 0.3063 | 0.0015 | 0.5115 | 0.047* | |
H22B | 0.4129 | 0.0318 | 0.6581 | 0.047* | |
C23 | 0.4578 (8) | 0.0741 (2) | 0.4873 (6) | 0.0388 (12) | |
C24 | 0.5572 (10) | 0.1221 (3) | 0.5660 (6) | 0.0493 (16) | |
H24 | 0.6009 | 0.1195 | 0.6655 | 0.059* | |
C25 | 0.5922 (10) | 0.1736 (3) | 0.4995 (7) | 0.0515 (15) | |
H25 | 0.6569 | 0.2054 | 0.5536 | 0.062* | |
C26 | 0.5290 (9) | 0.1770 (2) | 0.3501 (6) | 0.0446 (13) | |
C27 | 0.4357 (9) | 0.1295 (3) | 0.2729 (6) | 0.0483 (14) | |
H27 | 0.3966 | 0.1314 | 0.1734 | 0.058* | |
C28 | 0.3982 (8) | 0.0787 (2) | 0.3395 (6) | 0.0427 (13) | |
H28 | 0.3322 | 0.0472 | 0.2845 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0475 (4) | 0.0299 (4) | 0.0149 (3) | −0.0067 (3) | 0.0092 (3) | −0.0019 (3) |
Cu2 | 0.0539 (4) | 0.0284 (4) | 0.0141 (3) | 0.0070 (3) | 0.0088 (3) | 0.0014 (3) |
O1W | 0.050 (2) | 0.058 (3) | 0.053 (3) | −0.0001 (19) | 0.015 (2) | 0.003 (2) |
O2W | 0.076 (3) | 0.054 (3) | 0.049 (3) | 0.007 (2) | 0.015 (2) | −0.005 (2) |
O1 | 0.045 (2) | 0.036 (2) | 0.0181 (18) | −0.0086 (17) | 0.0068 (16) | −0.0040 (16) |
O2 | 0.050 (2) | 0.0305 (18) | 0.0195 (19) | −0.0014 (16) | 0.0107 (15) | 0.0016 (15) |
O3 | 0.064 (3) | 0.052 (3) | 0.081 (4) | 0.012 (2) | 0.029 (3) | 0.007 (3) |
O4 | 0.059 (2) | 0.0252 (19) | 0.0195 (18) | 0.0058 (16) | 0.0135 (17) | 0.0007 (15) |
O5 | 0.061 (2) | 0.0299 (18) | 0.0149 (18) | −0.0008 (16) | 0.0117 (15) | −0.0028 (15) |
O6 | 0.092 (3) | 0.051 (2) | 0.036 (2) | −0.010 (2) | 0.020 (2) | 0.0082 (19) |
O7 | 0.051 (3) | 0.113 (4) | 0.030 (2) | 0.009 (3) | 0.001 (2) | −0.009 (3) |
O8 | 0.069 (3) | 0.071 (4) | 0.094 (5) | −0.014 (3) | −0.001 (3) | 0.009 (3) |
O9 | 0.064 (3) | 0.065 (3) | 0.053 (3) | −0.015 (3) | 0.004 (2) | 0.000 (3) |
O10 | 0.094 (3) | 0.105 (3) | 0.056 (2) | 0.012 (2) | 0.016 (2) | 0.002 (2) |
O11 | 0.094 (3) | 0.105 (3) | 0.056 (2) | 0.012 (2) | 0.016 (2) | 0.002 (2) |
O12 | 0.080 (4) | 0.116 (5) | 0.076 (4) | 0.049 (4) | −0.012 (3) | −0.033 (4) |
N1 | 0.046 (3) | 0.029 (2) | 0.027 (2) | −0.005 (2) | 0.017 (2) | −0.001 (2) |
N2 | 0.047 (3) | 0.042 (3) | 0.018 (2) | −0.010 (2) | 0.005 (2) | −0.007 (2) |
N3 | 0.044 (2) | 0.031 (2) | 0.018 (2) | −0.006 (2) | 0.0098 (17) | −0.007 (2) |
N4 | 0.063 (3) | 0.035 (2) | 0.012 (2) | 0.009 (2) | 0.0101 (19) | 0.000 (2) |
N5 | 0.035 (3) | 0.078 (4) | 0.047 (3) | 0.004 (3) | 0.015 (2) | 0.001 (3) |
N6 | 0.050 (3) | 0.079 (4) | 0.030 (3) | 0.004 (3) | 0.008 (2) | −0.005 (3) |
C1 | 0.138 (5) | 0.064 (3) | 0.057 (3) | −0.057 (3) | 0.071 (4) | −0.034 (3) |
C2 | 0.138 (5) | 0.064 (3) | 0.057 (3) | −0.057 (3) | 0.071 (4) | −0.034 (3) |
C3 | 0.032 (3) | 0.041 (3) | 0.028 (3) | −0.002 (2) | 0.011 (2) | −0.002 (2) |
C4 | 0.091 (5) | 0.049 (4) | 0.027 (3) | −0.035 (3) | 0.024 (3) | −0.006 (3) |
C5 | 0.076 (4) | 0.064 (4) | 0.018 (3) | −0.025 (3) | 0.017 (3) | −0.013 (3) |
C6 | 0.083 (4) | 0.035 (3) | 0.024 (3) | −0.024 (3) | 0.019 (3) | −0.003 (2) |
C7 | 0.069 (4) | 0.045 (3) | 0.024 (3) | −0.017 (3) | 0.014 (3) | −0.002 (3) |
C8 | 0.040 (3) | 0.030 (3) | 0.026 (3) | −0.006 (2) | 0.012 (2) | −0.003 (2) |
C9 | 0.054 (3) | 0.041 (3) | 0.024 (3) | −0.009 (2) | 0.002 (2) | −0.002 (2) |
C10 | 0.049 (3) | 0.037 (3) | 0.021 (2) | −0.007 (2) | 0.004 (2) | 0.003 (2) |
C11 | 0.037 (2) | 0.028 (2) | 0.017 (2) | 0.001 (2) | 0.0077 (19) | −0.004 (2) |
C12 | 0.037 (3) | 0.036 (2) | 0.014 (2) | −0.0042 (19) | 0.0062 (19) | 0.0007 (18) |
C13 | 0.040 (3) | 0.047 (4) | 0.018 (3) | −0.011 (2) | 0.008 (2) | −0.001 (2) |
C14 | 0.056 (3) | 0.035 (2) | 0.016 (2) | −0.005 (2) | 0.016 (2) | −0.001 (2) |
C15 | 0.054 (3) | 0.038 (3) | 0.031 (3) | −0.013 (3) | 0.016 (3) | −0.003 (2) |
C16 | 0.066 (4) | 0.040 (3) | 0.035 (3) | −0.001 (3) | 0.026 (3) | 0.004 (2) |
C17 | 0.066 (4) | 0.049 (3) | 0.029 (3) | 0.010 (3) | 0.022 (3) | 0.005 (2) |
C18 | 0.054 (4) | 0.048 (3) | 0.041 (4) | −0.003 (3) | 0.014 (3) | −0.002 (3) |
C19 | 0.050 (3) | 0.031 (2) | 0.034 (3) | −0.006 (2) | 0.014 (2) | −0.005 (2) |
C20 | 0.032 (2) | 0.034 (3) | 0.020 (2) | −0.003 (2) | 0.0060 (19) | 0.001 (2) |
C21 | 0.045 (3) | 0.026 (2) | 0.020 (2) | 0.0045 (19) | 0.013 (2) | 0.0011 (18) |
C22 | 0.058 (4) | 0.033 (3) | 0.031 (3) | 0.007 (2) | 0.023 (3) | 0.009 (2) |
C23 | 0.053 (3) | 0.036 (2) | 0.028 (3) | 0.016 (2) | 0.013 (2) | 0.005 (2) |
C24 | 0.079 (4) | 0.047 (3) | 0.018 (3) | 0.010 (3) | 0.009 (3) | 0.007 (2) |
C25 | 0.075 (4) | 0.038 (3) | 0.034 (3) | −0.002 (3) | 0.008 (3) | 0.001 (2) |
C26 | 0.062 (4) | 0.041 (3) | 0.034 (3) | 0.003 (3) | 0.019 (3) | 0.009 (2) |
C27 | 0.072 (4) | 0.053 (3) | 0.020 (3) | 0.001 (3) | 0.014 (2) | 0.007 (2) |
C28 | 0.064 (4) | 0.036 (3) | 0.027 (3) | 0.005 (2) | 0.013 (2) | 0.000 (2) |
Geometric parameters (Å, º) top
Cu1—O5i | 1.968 (4) | C3—C4 | 1.378 (8) |
Cu1—O1 | 1.993 (4) | C3—C8 | 1.489 (6) |
Cu1—N3 | 2.002 (5) | C4—C5 | 1.372 (9) |
Cu1—N1 | 2.004 (4) | C4—H4 | 0.9300 |
Cu1—O1W | 2.461 (4) | C5—H5 | 0.9300 |
Cu1—O7 | 2.565 (5) | C6—C7 | 1.381 (8) |
Cu2—N4 | 1.964 (5) | C6—H6 | 0.9300 |
Cu2—O4 | 1.964 (4) | C7—C8 | 1.383 (8) |
Cu2—O2 | 1.968 (4) | C7—H7 | 0.9300 |
Cu2—N2ii | 1.989 (5) | C8—C9 | 1.386 (8) |
Cu2—O2W | 2.627 (5) | C9—C10 | 1.394 (7) |
Cu2—O10 | 2.808 (7) | C9—H9 | 0.9300 |
O1W—H1W | 0.9347 | C10—H10 | 0.9300 |
O1W—H2W | 0.8568 | C11—C12 | 1.532 (6) |
O2W—H3W | 0.8582 | C12—C13 | 1.516 (8) |
O2W—H4W | 0.8712 | C12—H12 | 0.9800 |
O1—C11 | 1.274 (7) | C13—C14 | 1.508 (8) |
O2—C11 | 1.251 (6) | C13—H13A | 0.9700 |
O3—C17 | 1.369 (7) | C13—H13B | 0.9700 |
O3—H3 | 0.8749 | C14—C19 | 1.379 (7) |
O4—C20 | 1.255 (7) | C14—C15 | 1.393 (8) |
O5—C20 | 1.248 (6) | C15—C16 | 1.367 (9) |
O5—Cu1iii | 1.968 (4) | C15—H15 | 0.9300 |
O6—C26 | 1.369 (7) | C16—C17 | 1.383 (9) |
O6—H6A | 0.8586 | C16—H16 | 0.9300 |
O7—N5 | 1.247 (7) | C17—C18 | 1.368 (9) |
O8—N5 | 1.256 (8) | C18—C19 | 1.409 (8) |
O9—N5 | 1.235 (8) | C18—H18 | 0.9300 |
O10—N6 | 1.243 (8) | C19—H19 | 0.9300 |
O11—N6 | 1.257 (9) | C20—C21 | 1.529 (7) |
O12—N6 | 1.202 (8) | C21—C22 | 1.530 (7) |
N1—C5 | 1.316 (8) | C21—H21 | 0.9800 |
N1—C1 | 1.332 (8) | C22—C23 | 1.508 (8) |
N2—C10 | 1.332 (7) | C22—H22A | 0.9700 |
N2—C6 | 1.347 (8) | C22—H22B | 0.9700 |
N2—Cu2iv | 1.989 (5) | C23—C28 | 1.383 (7) |
N3—C12 | 1.468 (6) | C23—C24 | 1.396 (9) |
N3—H3A | 0.9000 | C24—C25 | 1.386 (9) |
N3—H3B | 0.9000 | C24—H24 | 0.9300 |
N4—C21 | 1.492 (6) | C25—C26 | 1.396 (8) |
N4—H4A | 0.9000 | C25—H25 | 0.9300 |
N4—H4B | 0.9000 | C26—C27 | 1.365 (8) |
C1—C2 | 1.382 (9) | C27—C28 | 1.381 (8) |
C1—H1 | 0.9300 | C27—H27 | 0.9300 |
C2—C3 | 1.350 (8) | C28—H28 | 0.9300 |
C2—H2 | 0.9300 | | |
| | | |
O5i—Cu1—O1 | 174.40 (16) | C7—C6—H6 | 118.7 |
O5i—Cu1—N3 | 95.56 (17) | C6—C7—C8 | 120.4 (6) |
O1—Cu1—N3 | 82.66 (17) | C6—C7—H7 | 119.8 |
O5i—Cu1—N1 | 89.84 (17) | C8—C7—H7 | 119.8 |
O1—Cu1—N1 | 92.16 (17) | C7—C8—C9 | 116.8 (5) |
N3—Cu1—N1 | 174.20 (19) | C7—C8—C3 | 121.2 (5) |
O5i—Cu1—O1W | 88.24 (17) | C9—C8—C3 | 121.9 (5) |
O1—Cu1—O1W | 86.45 (16) | C10—C9—C8 | 119.7 (5) |
N3—Cu1—O1W | 89.85 (17) | C10—C9—H9 | 120.1 |
N1—Cu1—O1W | 92.44 (17) | C8—C9—H9 | 120.1 |
O5i—Cu1—O7 | 97.35 (16) | N2—C10—C9 | 123.0 (5) |
O1—Cu1—O7 | 87.93 (16) | N2—C10—H10 | 118.5 |
N3—Cu1—O7 | 88.59 (19) | C9—C10—H10 | 118.5 |
N1—Cu1—O7 | 88.62 (18) | O2—C11—O1 | 124.2 (4) |
O1W—Cu1—O7 | 174.32 (17) | O2—C11—C12 | 118.6 (5) |
N4—Cu2—O4 | 83.68 (16) | O1—C11—C12 | 117.2 (4) |
N4—Cu2—O2 | 92.92 (16) | N3—C12—C13 | 115.9 (4) |
O4—Cu2—O2 | 165.53 (17) | N3—C12—C11 | 109.1 (4) |
N4—Cu2—N2ii | 168.4 (2) | C13—C12—C11 | 115.9 (4) |
O4—Cu2—N2ii | 92.94 (17) | N3—C12—H12 | 104.9 |
O2—Cu2—N2ii | 92.99 (18) | C13—C12—H12 | 104.9 |
N4—Cu2—O2W | 87.51 (19) | C11—C12—H12 | 104.9 |
O4—Cu2—O2W | 81.20 (16) | C14—C13—C12 | 118.8 (5) |
O2—Cu2—O2W | 84.61 (16) | C14—C13—H13A | 107.6 |
N2ii—Cu2—O2W | 102.99 (19) | C12—C13—H13A | 107.6 |
N4—Cu2—O10 | 76.9 (2) | C14—C13—H13B | 107.6 |
O4—Cu2—O10 | 86.63 (17) | C12—C13—H13B | 107.6 |
O2—Cu2—O10 | 106.35 (17) | H13A—C13—H13B | 107.1 |
N2ii—Cu2—O10 | 91.9 (2) | C19—C14—C15 | 116.3 (5) |
O2W—Cu2—O10 | 161.19 (17) | C19—C14—C13 | 125.1 (5) |
H1W—O1W—H2W | 104.4 | C15—C14—C13 | 118.6 (5) |
H3W—O2W—H4W | 105.0 | C16—C15—C14 | 123.2 (6) |
C11—O1—Cu1 | 114.6 (3) | C16—C15—H15 | 118.4 |
C11—O2—Cu2 | 126.8 (3) | C14—C15—H15 | 118.4 |
C17—O3—H3 | 109.9 | C15—C16—C17 | 119.4 (5) |
C20—O4—Cu2 | 115.9 (3) | C15—C16—H16 | 120.3 |
C20—O5—Cu1iii | 129.0 (4) | C17—C16—H16 | 120.3 |
C26—O6—H6A | 111.5 | C18—C17—O3 | 117.3 (6) |
C5—N1—C1 | 115.6 (5) | C18—C17—C16 | 119.7 (6) |
C5—N1—Cu1 | 122.5 (4) | O3—C17—C16 | 123.0 (5) |
C1—N1—Cu1 | 121.8 (4) | C17—C18—C19 | 119.9 (6) |
C10—N2—C6 | 117.2 (5) | C17—C18—H18 | 120.1 |
C10—N2—Cu2iv | 121.7 (4) | C19—C18—H18 | 120.1 |
C6—N2—Cu2iv | 121.1 (4) | C14—C19—C18 | 121.4 (5) |
C12—N3—Cu1 | 109.0 (3) | C14—C19—H19 | 119.3 |
C12—N3—H3A | 109.9 | C18—C19—H19 | 119.3 |
Cu1—N3—H3A | 109.9 | O4—C20—O5 | 124.3 (5) |
C12—N3—H3B | 109.9 | O4—C20—C21 | 118.0 (5) |
Cu1—N3—H3B | 109.9 | O5—C20—C21 | 117.6 (5) |
H3A—N3—H3B | 108.3 | N4—C21—C22 | 112.6 (4) |
C21—N4—Cu2 | 111.4 (3) | N4—C21—C20 | 107.8 (4) |
C21—N4—H4A | 109.3 | C22—C21—C20 | 116.2 (4) |
Cu2—N4—H4A | 109.3 | N4—C21—H21 | 106.5 |
C21—N4—H4B | 109.3 | C22—C21—H21 | 106.5 |
Cu2—N4—H4B | 109.3 | C20—C21—H21 | 106.5 |
H4A—N4—H4B | 108.0 | C23—C22—C21 | 112.4 (5) |
O9—N5—O8 | 120.4 (6) | C23—C22—H22A | 109.1 |
O9—N5—O7 | 120.5 (6) | C21—C22—H22A | 109.1 |
O8—N5—O7 | 119.0 (7) | C23—C22—H22B | 109.1 |
O12—N6—O10 | 119.6 (7) | C21—C22—H22B | 109.1 |
O12—N6—O11 | 119.0 (6) | H22A—C22—H22B | 107.9 |
O10—N6—O11 | 121.4 (7) | C28—C23—C24 | 118.0 (5) |
N1—C1—C2 | 124.2 (6) | C28—C23—C22 | 123.0 (5) |
N1—C1—H1 | 117.9 | C24—C23—C22 | 119.0 (5) |
C2—C1—H1 | 117.9 | C25—C24—C23 | 121.5 (5) |
C3—C2—C1 | 119.4 (6) | C25—C24—H24 | 119.2 |
C3—C2—H2 | 120.3 | C23—C24—H24 | 119.2 |
C1—C2—H2 | 120.3 | C24—C25—C26 | 119.1 (6) |
C2—C3—C4 | 116.9 (5) | C24—C25—H25 | 120.4 |
C2—C3—C8 | 122.1 (5) | C26—C25—H25 | 120.4 |
C4—C3—C8 | 121.0 (5) | O6—C26—C27 | 120.2 (5) |
C5—C4—C3 | 120.1 (6) | O6—C26—C25 | 120.5 (5) |
C5—C4—H4 | 119.9 | C27—C26—C25 | 119.3 (5) |
C3—C4—H4 | 119.9 | C26—C27—C28 | 121.4 (5) |
N1—C5—C4 | 123.7 (6) | C26—C27—H27 | 119.3 |
N1—C5—H5 | 118.1 | C28—C27—H27 | 119.3 |
C4—C5—H5 | 118.1 | C27—C28—C23 | 120.5 (5) |
N2—C6—C7 | 122.6 (6) | C27—C28—H28 | 119.7 |
N2—C6—H6 | 118.7 | C23—C28—H28 | 119.7 |
Symmetry codes: (i) x, y, z−1; (ii) −x+2, y−1/2, −z+1; (iii) x, y, z+1; (iv) −x+2, y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O11ii | 0.87 | 1.90 | 2.761 (9) | 169 |
O6—H6A···O2Wv | 0.86 | 1.91 | 2.768 (7) | 175 |
O1W—H1W···O9vi | 0.93 | 1.95 | 2.876 (7) | 171 |
O1W—H2W···O11vii | 0.86 | 2.00 | 2.849 (8) | 172 |
O2W—H4W···O8vi | 0.87 | 1.90 | 2.772 (8) | 173 |
O2W—H3W···O12vi | 0.86 | 1.97 | 2.779 (8) | 157 |
N3—H3A···O12vii | 0.90 | 2.20 | 3.063 (7) | 159 |
N4—H4A···O1 | 0.90 | 2.36 | 2.974 (6) | 126 |
N4—H4B···O9vi | 0.90 | 2.18 | 3.018 (7) | 155 |
Symmetry codes: (ii) −x+2, y−1/2, −z+1; (v) −x+1, y+1/2, −z+1; (vi) x−1, y, z; (vii) x−1, y, z−1. |
Experimental details
Crystal data |
Chemical formula | [Cu2(C9H10NO3)2(NO3)2(C10H8N2)(H2O)2] |
Mr | 803.68 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 7.6075 (13), 22.281 (4), 9.8205 (16) |
β (°) | 108.150 (2) |
V (Å3) | 1581.8 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.43 |
Crystal size (mm) | 0.33 × 0.19 × 0.17 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.652, 0.791 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8422, 5584, 5003 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.611 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.137, 1.08 |
No. of reflections | 5584 |
No. of parameters | 439 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.23, −0.87 |
Absolute structure | Flack (1983), with 2506 Friedel pairs |
Absolute structure parameter | 0.010 (18) |
Selected bond lengths (Å) topCu1—O5i | 1.968 (4) | Cu2—N4 | 1.964 (5) |
Cu1—O1 | 1.993 (4) | Cu2—O4 | 1.964 (4) |
Cu1—N3 | 2.002 (5) | Cu2—O2 | 1.968 (4) |
Cu1—N1 | 2.004 (4) | Cu2—N2ii | 1.989 (5) |
Cu1—O1W | 2.461 (4) | Cu2—O2W | 2.627 (5) |
Cu1—O7 | 2.565 (5) | Cu2—O10 | 2.808 (7) |
Symmetry codes: (i) x, y, z−1; (ii) −x+2, y−1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O11ii | 0.87 | 1.90 | 2.761 (9) | 169 |
O6—H6A···O2Wiii | 0.86 | 1.91 | 2.768 (7) | 175 |
O1W—H1W···O9iv | 0.93 | 1.95 | 2.876 (7) | 171 |
O1W—H2W···O11v | 0.86 | 2.00 | 2.849 (8) | 172 |
O2W—H4W···O8iv | 0.87 | 1.90 | 2.772 (8) | 173 |
O2W—H3W···O12iv | 0.86 | 1.97 | 2.779 (8) | 157 |
N3—H3A···O12v | 0.90 | 2.20 | 3.063 (7) | 159 |
N4—H4A···O1 | 0.90 | 2.36 | 2.974 (6) | 126 |
N4—H4B···O9iv | 0.90 | 2.18 | 3.018 (7) | 155 |
Symmetry codes: (ii) −x+2, y−1/2, −z+1; (iii) −x+1, y+1/2, −z+1; (iv) x−1, y, z; (v) x−1, y, z−1. |
There is considerable interest in chiral coordination polymers, owing to their potential application in asymmetric catalysis and chiral separation (Kesanli & Lin, 2003). Although these materials can be synthesized from single chiral or achiral organic components, self-assembly based on a mixed-ligand system containing both chiral and achiral ligands is an attractive approach to the construction of chiral framework materials since it allows for facile tuning of structural, topological and functional features derived from different molecular components (Dai et al., 2005; Wang et al., 2008; Zaworotko, 2001). The 4,4'-bipyridine (4,4'-bipy) molecule is a common building block, which has been used extensively as a rigid linear linker between metal centres (Biradha et al., 2006). Amino acids such as L-tyrosine (L-tyr) are good candidates as chiral building blocks, with their amino and carboxylate groups being capable of binding to metal ions in flexible modes (Vaidhyanathan et al., 2006). We report here the title chiral two-dimensional coordination polymer, (I), which is assembled by connecting Cu–L-tyr units with 4,4'-bipy linkers.
The asymmetric unit of (I) consists of two CuII atoms, two deprotonated L-tyr ligands, one 4,4'-bipy ligand, two nitrate ions and two coordinated water molecules (Fig. 1). Each Cu atom is coordinated by one N atom and two carboxylate O atoms from two L-tyr ligands and one N atom from a 4,4'-bipy ligand in the equatorial plane, and by a monodentate nitrate ion and a water molecule in the axial positions. The nitrate ions and water molecules are weakly bonded to the Cu atoms, with Cu—Onitrate distances of 2.565 (5) and 2.808 (7) Å, and Cu—Owater distances of 2.461 (4) and 2.627 (5) Å (Table 1). These axial Cu—O distances are longer than the sum of the ionic radii (Reference?), but they are still within the range of 2.2–2.9 Å known for axial Cu—O bond lengths (Zhang et al., 1996), thus displaying an elongated octahedral geometry around each Cu atom. The L-tyr ligand binds to the Cu atom in a µ-(κ3N,O:O') mode, that is, one carboxylate O atom chelates a Cu atom together with the amino N atom, and the other carboxylate O atom coordinates to another Cu atom. The hydroxyl O atom of the phenol group is uncoordinated. In this way, the L-tyr ligands bridge adjacent Cu atoms to form a chiral [Cu(L-tyr)(NO3)(H2O)]n chain extending in the [001] direction. The separations between the Cu atoms in the chain are 5.180 (1) and 5.193 (1) Å. As shown in Fig. 2, these chains are further connected by the 4,4'-bipy linkers into a two-dimensional undulating sheet. Fig. 3 shows a schematic depiction of the sheet, which has a (6,3) topology (Batten & Robson, 1998), with Cu atoms as the three-connected nodes and with meshes of dimensions 9.82 × 11.06 Å. Moreover, these sheets are arranged in the [100] direction and connected by three types of hydrogen bonds (Table 2). One is formed between a hydroxyl group and a water O atom [O6—H6A···O2Wiii; symmetry code: (iii) 1 - x, 1/2 + y, 1 - z], the second involves the coordinated water molecules and nitrate ions, and the third involves the amino groups and nitrate ions.
It has been observed in the structures of [Cu(L-tyr)(1,10-phenanthroline)(H2O)](ClO4).H2O (Sugimori et al., 1997) and [Cu(L-I2tyr)(2,2'-bipyridine)(NO3)].CH3OH (Zhang et al., 1996) that the phenol ring of the L-tyr ligand folds back to be located over the Cu atom with an intramolecular phenol ring···Cu coordination plane interaction, whereas the two phenol rings in (I) each extend away from the Cu atoms. The phenol ring with hydroxyl atom O3 inserts itself into the mesh of the sheet to form a hydrogen bond between atom O3 and nitrate atom O11(2 - x, y - 1/2, 1 - z) of the opposite chain, while the phenol ring with hydroxyl atom O6 lies between two sheets, stabilized by a π–π interaction with a pyridyl ring of a neighbouring sheet [centroid-to-centroid distance = 3.56 (1) Å]. As a result, the channels along the [100] direction formed by the aligned meshes of the sheets are blocked by the side chains of the L-tyr ligands.
The rational design and controlled synthesis of coordination frameworks have been a challenging subject in crystal engineering. Small changes in the variables of reaction such as stoichiometry, pH value, temperature, solvent and metal source can have a profound influence on the structures of the products. For the CuII–amino acid–4,4'-bipy system, it seems that the ratio of CuII to amino acid to 4,4'-bipy is related to structural architecture. We note that a zero-dimensional dinuclear complex is formed for an L-valinate complex when the ratio is 2:2:3 (Lou & Hong, 2008), while one-dimensional helical chains have been found in L-threoninate and L-alaninate complexes with a ratio of 1:1:1, regardless of a polar or non-polar side chain (Lou et al., 2005). Two-dimensional frameworks are observed in (I), with the polar L-tyr ligand, and in a non-polar L-valinate complex (Lou et al., 2007), both of which have a ratio of 2:2:1. Clearly, despite the observed structural relevance to component ratios, further work is needed for understanding the factors affecting these structural architectures.
In conclusion, we have synthesized a two-dimensional chiral coordination polymer based on a mixed-ligand system, in which the L-tyr ligand provides a chiral source and the 4,4'-bipy ligand is used to extend the framework. This study offers helpful information for engineering this type of chiral coordination polymer by considering the ratios of metal ion and organic components.