The two title mononuclear compounds are four-coordinate bis[
N-(5-oxo-4,4-diphenyl-4,5-dihydro-1
H-imidazolidin-2-ylidene)glycinato]copper(II) dimethylformamide disolvate, [Cu(C
17H
14N
3O
3)
2]·2C
3H
7NO, (I), and five-coordinate aquabis[
N-(5-oxo-4,4-diphenyl-4,5-dihydro-1
H-imidazolidin-2-ylidene)glycinato]copper(II) dimethylformamide disolvate, [Cu(C
17H
14N
3O
3)
2(H
2O)]·2C
3H
7NO, (II). In (I), the Cu
II ion lies on an inversion centre with one-half of the complex molecule in the asymmetric unit, while in (II) there are two independent ligand molecules in the asymmetric unit, with the Cu
II ion and coordinated water molecule located on a general position. In both crystal structures, the complex molecules assemble in ribbons
via N—H
O hydrogen-bond networks.
Supporting information
CCDC references: 681522; 681523
To obtain crystals of these complexes, the method described by
Dziemidowicz-Borys (2006) was adapted for our compounds. Locally synthesized
N-[(5,5-diphenyl)-4-oxo-imidazolidinyl]glycine (Kieć-Kononowicz et
al., 1995) was used as the ligand for complex formation. A solution of
CuCl2·2H2O (9 mg, 0.052 mmol) in DMF (2 ml) was added to
N-[(5,5-diphenyl)-4-oxo-imidazolidinyl]glycine (16 mg, 0.052 mmol)
dissolved in warmed DMF (2 ml). The resulting green–blue solution was left at
room temperature for a couple of days with limited air contact. After two
weeks, violet crystals [Of (I)?] appeared, which were carefully filtered out.
From the filtrate left in contact with air, a few blue crystals [Of (II)?]
were obtained after a further two weeks. [Was the air thus the source of the
coordinated water in (II)?]
In (I), the H atoms attached to atoms N1 and N3 were located in a difference
Fourier map and their positions and displacement parameters were refined
freely. In (II), H atoms attached to N atoms were placed in idealized
positions and constrained to ride on their parent atoms, with N—H = 0.86 Å
and with Uiso(H) = 1.2Ueq(N). For both compounds, phenylene
and methylene H atoms were placed in idealized positions and constrained to
ride on their parent atoms, with C—H = 0.93 and 0.97 Å and
Uiso(H) = 1.2Ueq(C). The methyl H atoms in the DMF molecules
were found in a difference Fourier map and were included using an AFIX 137
command (SHELXTL; Bruker, 2003), with C—H = 0.96 Å and
Uiso(H) = 1.5Ueq(C). One of the DMF molecules in (II) showed
disorder; the occupancies of the disordered positions were initially refined,
and later fixed at 0.65 and 0.35.
Data collection: SMART (Bruker, 2002) for (I); CrysAlis CCD (Oxford Diffraction, 2006) for (II). Cell refinement: SAINT-Plus (Bruker, 2003) for (I); CrysAlis RED (Oxford Diffraction, 2006) for (II). Data reduction: SAINT-Plus (Bruker, 2003) for (I); CrysAlis RED (Oxford Diffraction, 2006) for (II). For both compounds, program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL (Bruker, 2003); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2003).
(I) bis[
N-(4,4-diphenyl-5-oxo-4,5-dihydro-1
H-imidazol-2-
yl)glycinato]copper(II) dimethylformamide disolvate
top
Crystal data top
[Cu(C17H14N3O3)2]·2C3H7NO | F(000) = 862 |
Mr = 826.37 | Dx = 1.346 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1580 reflections |
a = 8.987 (4) Å | θ = 2.5–21.5° |
b = 14.075 (6) Å | µ = 0.60 mm−1 |
c = 16.208 (7) Å | T = 291 K |
β = 95.913 (6)° | Prism, violet |
V = 2039.3 (15) Å3 | 0.2 × 0.1 × 0.05 mm |
Z = 2 | |
Data collection top
Bruker SMART APEXII CCD diffractometer | 3590 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 2815 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.924, Tmax = 0.979 | k = −16→16 |
28748 measured reflections | l = −19→19 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0553P)2 + 1.7037P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
3590 reflections | Δρmax = 0.67 e Å−3 |
269 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | |
Crystal data top
[Cu(C17H14N3O3)2]·2C3H7NO | V = 2039.3 (15) Å3 |
Mr = 826.37 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.987 (4) Å | µ = 0.60 mm−1 |
b = 14.075 (6) Å | T = 291 K |
c = 16.208 (7) Å | 0.2 × 0.1 × 0.05 mm |
β = 95.913 (6)° | |
Data collection top
Bruker SMART APEXII CCD diffractometer | 3590 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2815 reflections with I > 2σ(I) |
Tmin = 0.924, Tmax = 0.979 | Rint = 0.052 |
28748 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.67 e Å−3 |
3590 reflections | Δρmin = −0.27 e Å−3 |
269 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted R-factors wR and all
goodnesses of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The observed criterion of F2 > σ(F2)
is used only for calculating -R-factor-obs 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 | 0.00000 | 0.00000 | 0.00000 | 0.0299 (2) | |
O4 | 0.1398 (3) | 0.0524 (2) | 0.33959 (14) | 0.0562 (9) | |
O9 | 0.1134 (2) | −0.02151 (17) | −0.09254 (13) | 0.0419 (8) | |
O10 | 0.3414 (3) | −0.0211 (2) | −0.13303 (14) | 0.0528 (9) | |
N1 | 0.3722 (3) | 0.0238 (2) | 0.18148 (16) | 0.0352 (9) | |
N3 | 0.1325 (3) | 0.0316 (2) | 0.19893 (16) | 0.0360 (9) | |
N6 | 0.1959 (3) | 0.01488 (18) | 0.06272 (15) | 0.0332 (8) | |
C2 | 0.2349 (3) | 0.0228 (2) | 0.14118 (18) | 0.0287 (9) | |
C4 | 0.2010 (4) | 0.0403 (2) | 0.2778 (2) | 0.0380 (10) | |
C5 | 0.3714 (3) | 0.0298 (2) | 0.27167 (18) | 0.0335 (10) | |
C7 | 0.3184 (3) | 0.0053 (2) | 0.00944 (18) | 0.0353 (10) | |
C8 | 0.2571 (3) | −0.0141 (2) | −0.07912 (19) | 0.0343 (10) | |
C11 | 0.4220 (4) | −0.0635 (2) | 0.3153 (2) | 0.0381 (11) | |
C12 | 0.4645 (5) | −0.1423 (3) | 0.2728 (2) | 0.0551 (14) | |
C13 | 0.5081 (6) | −0.2244 (3) | 0.3161 (3) | 0.0751 (18) | |
C14 | 0.5078 (6) | −0.2292 (3) | 0.4003 (3) | 0.081 (2) | |
C15 | 0.4644 (6) | −0.1517 (3) | 0.4425 (3) | 0.0722 (18) | |
C16 | 0.4225 (5) | −0.0689 (3) | 0.4012 (2) | 0.0528 (14) | |
C21 | 0.4634 (4) | 0.1150 (2) | 0.30572 (19) | 0.0367 (10) | |
C22 | 0.6178 (4) | 0.1068 (3) | 0.3171 (2) | 0.0485 (12) | |
C23 | 0.7063 (5) | 0.1836 (3) | 0.3428 (3) | 0.0671 (17) | |
C24 | 0.6425 (7) | 0.2681 (4) | 0.3579 (3) | 0.0803 (19) | |
C25 | 0.4910 (7) | 0.2778 (3) | 0.3476 (3) | 0.079 (2) | |
C26 | 0.3995 (5) | 0.2015 (3) | 0.3208 (2) | 0.0548 (14) | |
O31 | 0.0365 (6) | 0.2951 (3) | 0.4520 (3) | 0.1166 (19) | |
N32 | 0.0603 (5) | 0.1811 (3) | 0.5500 (2) | 0.0734 (17) | |
C31 | 0.0867 (7) | 0.2210 (4) | 0.4799 (4) | 0.090 (3) | |
C33 | −0.0323 (12) | 0.2286 (6) | 0.6028 (5) | 0.180 (5) | |
C34 | 0.1268 (8) | 0.0929 (5) | 0.5783 (5) | 0.135 (3) | |
H1 | 0.442 (4) | 0.019 (2) | 0.157 (2) | 0.038 (10)* | |
H3 | 0.042 (4) | 0.033 (2) | 0.182 (2) | 0.031 (9)* | |
H71 | 0.38370 | −0.04640 | 0.02960 | 0.0420* | |
H72 | 0.37700 | 0.06330 | 0.01190 | 0.0420* | |
H12 | 0.46390 | −0.14030 | 0.21550 | 0.0660* | |
H13 | 0.53810 | −0.27710 | 0.28740 | 0.0900* | |
H14 | 0.53680 | −0.28470 | 0.42860 | 0.0970* | |
H15 | 0.46310 | −0.15480 | 0.49980 | 0.0870* | |
H16 | 0.39440 | −0.01630 | 0.43070 | 0.0640* | |
H22 | 0.66230 | 0.04880 | 0.30740 | 0.0580* | |
H23 | 0.80980 | 0.17720 | 0.34980 | 0.0810* | |
H24 | 0.70240 | 0.31970 | 0.37530 | 0.0970* | |
H25 | 0.44810 | 0.33600 | 0.35860 | 0.0950* | |
H26 | 0.29610 | 0.20880 | 0.31320 | 0.0660* | |
H31 | 0.15110 | 0.18870 | 0.44840 | 0.1070* | |
H331 | −0.01800 | 0.29600 | 0.59880 | 0.2710* | |
H332 | −0.00640 | 0.20860 | 0.65900 | 0.2710* | |
H333 | −0.13520 | 0.21340 | 0.58620 | 0.2710* | |
H341 | 0.20050 | 0.07440 | 0.54250 | 0.2020* | |
H342 | 0.05090 | 0.04480 | 0.57740 | 0.2020* | |
H343 | 0.17370 | 0.10030 | 0.63380 | 0.2020* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0176 (3) | 0.0453 (3) | 0.0269 (3) | −0.0004 (2) | 0.0022 (2) | −0.0033 (2) |
O4 | 0.0419 (15) | 0.097 (2) | 0.0316 (13) | −0.0012 (14) | 0.0135 (11) | −0.0108 (13) |
O9 | 0.0184 (11) | 0.0754 (17) | 0.0321 (11) | −0.0024 (10) | 0.0031 (9) | −0.0093 (11) |
O10 | 0.0246 (12) | 0.102 (2) | 0.0327 (12) | −0.0028 (12) | 0.0070 (10) | −0.0106 (12) |
N1 | 0.0223 (14) | 0.0595 (19) | 0.0238 (13) | −0.0013 (12) | 0.0023 (11) | −0.0031 (11) |
N3 | 0.0204 (14) | 0.0571 (18) | 0.0309 (14) | −0.0004 (12) | 0.0043 (11) | −0.0054 (12) |
N6 | 0.0200 (12) | 0.0514 (17) | 0.0280 (13) | 0.0002 (11) | 0.0018 (10) | −0.0026 (11) |
C2 | 0.0226 (15) | 0.0368 (18) | 0.0267 (15) | −0.0006 (12) | 0.0032 (12) | −0.0026 (12) |
C4 | 0.0327 (18) | 0.0499 (19) | 0.0319 (17) | −0.0004 (15) | 0.0059 (14) | −0.0007 (14) |
C5 | 0.0296 (17) | 0.0469 (19) | 0.0242 (15) | −0.0027 (13) | 0.0034 (12) | −0.0040 (13) |
C7 | 0.0270 (16) | 0.0505 (19) | 0.0277 (15) | 0.0000 (15) | −0.0005 (12) | −0.0023 (15) |
C8 | 0.0247 (16) | 0.049 (2) | 0.0296 (15) | 0.0016 (14) | 0.0042 (12) | −0.0018 (14) |
C11 | 0.0321 (18) | 0.047 (2) | 0.0342 (17) | −0.0075 (15) | −0.0010 (14) | −0.0013 (14) |
C12 | 0.067 (3) | 0.051 (2) | 0.047 (2) | −0.0025 (19) | 0.0052 (19) | −0.0105 (18) |
C13 | 0.103 (4) | 0.044 (2) | 0.080 (3) | 0.008 (2) | 0.018 (3) | −0.005 (2) |
C14 | 0.109 (4) | 0.052 (3) | 0.082 (4) | 0.001 (3) | 0.004 (3) | 0.019 (2) |
C15 | 0.099 (4) | 0.071 (3) | 0.046 (2) | −0.001 (3) | 0.004 (2) | 0.017 (2) |
C16 | 0.067 (3) | 0.056 (2) | 0.0346 (19) | 0.0009 (19) | 0.0011 (18) | −0.0001 (16) |
C21 | 0.041 (2) | 0.0450 (19) | 0.0239 (15) | −0.0073 (15) | 0.0020 (14) | 0.0017 (13) |
C22 | 0.038 (2) | 0.061 (2) | 0.046 (2) | −0.0099 (17) | 0.0014 (16) | −0.0052 (17) |
C23 | 0.060 (3) | 0.082 (3) | 0.058 (3) | −0.032 (2) | 0.000 (2) | −0.006 (2) |
C24 | 0.101 (4) | 0.066 (3) | 0.071 (3) | −0.039 (3) | −0.005 (3) | −0.002 (2) |
C25 | 0.119 (5) | 0.042 (2) | 0.073 (3) | −0.003 (3) | −0.003 (3) | −0.005 (2) |
C26 | 0.061 (3) | 0.049 (2) | 0.052 (2) | 0.0059 (19) | −0.0059 (19) | −0.0006 (17) |
O31 | 0.165 (4) | 0.083 (3) | 0.097 (3) | −0.011 (3) | −0.009 (3) | 0.011 (2) |
N32 | 0.077 (3) | 0.073 (3) | 0.072 (3) | −0.002 (2) | 0.016 (2) | 0.001 (2) |
C31 | 0.116 (5) | 0.075 (4) | 0.079 (4) | −0.007 (3) | 0.017 (3) | −0.013 (3) |
C33 | 0.270 (12) | 0.139 (7) | 0.154 (7) | 0.056 (7) | 0.128 (8) | 0.011 (6) |
C34 | 0.115 (6) | 0.113 (5) | 0.180 (7) | 0.017 (4) | 0.030 (5) | 0.058 (5) |
Geometric parameters (Å, º) top
Cu1—O9 | 1.922 (2) | C15—C16 | 1.377 (6) |
Cu1—N6 | 1.951 (3) | C21—C26 | 1.379 (5) |
O4—C4 | 1.203 (4) | C21—C22 | 1.386 (5) |
O9—C8 | 1.292 (3) | C22—C23 | 1.381 (6) |
O10—C8 | 1.218 (4) | C23—C24 | 1.354 (7) |
O31—C31 | 1.206 (7) | C24—C25 | 1.361 (9) |
N1—C2 | 1.335 (4) | C25—C26 | 1.395 (7) |
N1—C5 | 1.465 (4) | C7—H72 | 0.97 |
N3—C4 | 1.366 (4) | C7—H71 | 0.97 |
N3—C2 | 1.384 (4) | C12—H12 | 0.93 |
N6—C2 | 1.289 (4) | C13—H13 | 0.93 |
N6—C7 | 1.474 (4) | C14—H14 | 0.93 |
N1—H1 | 0.78 (4) | C15—H15 | 0.93 |
N3—H3 | 0.83 (4) | C16—H16 | 0.93 |
N32—C34 | 1.433 (8) | C22—H22 | 0.93 |
N32—C31 | 1.311 (7) | C23—H23 | 0.93 |
N32—C33 | 1.421 (10) | C24—H24 | 0.93 |
C4—C5 | 1.552 (5) | C25—H25 | 0.93 |
C5—C11 | 1.538 (4) | C26—H26 | 0.93 |
C5—C21 | 1.527 (4) | C31—H31 | 0.93 |
C7—C8 | 1.509 (4) | C33—H331 | 0.96 |
C11—C12 | 1.380 (5) | C33—H332 | 0.96 |
C11—C16 | 1.394 (5) | C33—H333 | 0.96 |
C12—C13 | 1.387 (6) | C34—H341 | 0.96 |
C13—C14 | 1.367 (7) | C34—H342 | 0.96 |
C14—C15 | 1.366 (6) | C34—H343 | 0.96 |
| | | |
O9—Cu1—N6 | 84.32 (9) | C23—C24—C25 | 120.2 (5) |
O9—Cu1—N6i | 95.68 (9) | C24—C25—C26 | 120.7 (5) |
Cu1—O9—C8 | 117.21 (19) | C21—C26—C25 | 119.5 (4) |
C2—N1—C5 | 112.9 (2) | N6—C7—H71 | 109 |
C2—N3—C4 | 112.0 (3) | N6—C7—H72 | 110 |
Cu1—N6—C2 | 131.5 (2) | C8—C7—H71 | 109 |
Cu1—N6—C7 | 111.92 (18) | C8—C7—H72 | 110 |
C2—N6—C7 | 116.3 (3) | H71—C7—H72 | 108 |
C2—N1—H1 | 120 (2) | C13—C12—H12 | 120 |
C5—N1—H1 | 127 (2) | C11—C12—H12 | 120 |
C2—N3—H3 | 118 (2) | C12—C13—H13 | 120 |
C4—N3—H3 | 130 (2) | C14—C13—H13 | 119 |
C33—N32—C34 | 117.8 (5) | C13—C14—H14 | 120 |
C31—N32—C33 | 119.3 (5) | C15—C14—H14 | 120 |
C31—N32—C34 | 122.8 (5) | C16—C15—H15 | 120 |
N1—C2—N6 | 128.9 (3) | C14—C15—H15 | 120 |
N1—C2—N3 | 108.3 (3) | C15—C16—H16 | 120 |
N3—C2—N6 | 122.9 (3) | C11—C16—H16 | 120 |
O4—C4—C5 | 127.3 (3) | C21—C22—H22 | 120 |
O4—C4—N3 | 126.2 (3) | C23—C22—H22 | 120 |
N3—C4—C5 | 106.5 (3) | C22—C23—H23 | 120 |
N1—C5—C11 | 112.2 (2) | C24—C23—H23 | 120 |
C4—C5—C21 | 113.8 (2) | C25—C24—H24 | 120 |
N1—C5—C21 | 110.4 (2) | C23—C24—H24 | 120 |
N1—C5—C4 | 100.1 (2) | C24—C25—H25 | 120 |
C11—C5—C21 | 112.4 (2) | C26—C25—H25 | 120 |
C4—C5—C11 | 107.4 (2) | C21—C26—H26 | 120 |
N6—C7—C8 | 110.6 (2) | C25—C26—H26 | 120 |
O9—C8—C7 | 115.8 (2) | O31—C31—N32 | 127.0 (6) |
O9—C8—O10 | 123.9 (3) | O31—C31—H31 | 117 |
O10—C8—C7 | 120.3 (3) | N32—C31—H31 | 116 |
C5—C11—C12 | 122.7 (3) | N32—C33—H331 | 109 |
C5—C11—C16 | 118.4 (3) | N32—C33—H332 | 110 |
C12—C11—C16 | 118.8 (3) | N32—C33—H333 | 109 |
C11—C12—C13 | 119.7 (3) | H331—C33—H332 | 109 |
C12—C13—C14 | 121.1 (4) | H331—C33—H333 | 109 |
C13—C14—C15 | 119.4 (4) | H332—C33—H333 | 109 |
C14—C15—C16 | 120.7 (4) | N32—C34—H341 | 109 |
C11—C16—C15 | 120.3 (4) | N32—C34—H342 | 110 |
C5—C21—C26 | 122.5 (3) | N32—C34—H343 | 110 |
C22—C21—C26 | 118.7 (3) | H341—C34—H342 | 109 |
C5—C21—C22 | 118.7 (3) | H341—C34—H343 | 109 |
C21—C22—C23 | 120.9 (4) | H342—C34—H343 | 109 |
C22—C23—C24 | 120.1 (4) | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O10ii | 0.78 (4) | 2.02 (4) | 2.768 (4) | 160 (3) |
N3—H3···O9i | 0.83 (4) | 1.91 (3) | 2.663 (3) | 149 (3) |
C7—H71···O31iii | 0.97 | 2.35 | 3.268 (5) | 157 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) −x+1/2, y−1/2, −z+1/2. |
(II) aquabis[
N-(4,4-diphenyl-5-oxo-4,5-dihydro-1
H-imidazol-2-
yl)glycinato]copper(II) dimethylformamide disolvate
top
Crystal data top
[Cu(C20H21N4O4)2(H2O)]·2C3H7NO | F(000) = 882 |
Mr = 844.38 | Dx = 1.341 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 14141 reflections |
a = 8.7305 (3) Å | θ = 2.7–28.0° |
b = 30.0213 (5) Å | µ = 0.59 mm−1 |
c = 9.0447 (2) Å | T = 293 K |
β = 118.102 (4)° | Prism, blue |
V = 2091.15 (12) Å3 | 0.30 × 0.25 × 0.22 mm |
Z = 2 | |
Data collection top
Kuma KM-4 CCD diffractometer | 7171 independent reflections |
Radiation source: CX-Mo12x0.4-S Seifert Mo tube | 6447 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 8.2356 pixels mm-1 | θmax = 25.0°, θmin = 2.6° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | k = −35→35 |
Tmin = 0.825, Tmax = 0.882 | l = −10→10 |
21287 measured reflections | |
Refinement top
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0437P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.026 | (Δ/σ)max = 0.001 |
wR(F2) = 0.066 | Δρmax = 0.20 e Å−3 |
S = 1.00 | Δρmin = −0.17 e Å−3 |
7171 reflections | Extinction correction: SHELXTL (Bruker, 2003), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
545 parameters | Extinction coefficient: 0.0024 (5) |
0 restraints | Absolute structure: Flack (1983), with 1462 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (1) |
Hydrogen site location: inferred from neighbouring sites | |
Crystal data top
[Cu(C20H21N4O4)2(H2O)]·2C3H7NO | V = 2091.15 (12) Å3 |
Mr = 844.38 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.7305 (3) Å | µ = 0.59 mm−1 |
b = 30.0213 (5) Å | T = 293 K |
c = 9.0447 (2) Å | 0.30 × 0.25 × 0.22 mm |
β = 118.102 (4)° | |
Data collection top
Kuma KM-4 CCD diffractometer | 7171 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 6447 reflections with I > 2σ(I) |
Tmin = 0.825, Tmax = 0.882 | Rint = 0.016 |
21287 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | Δρmax = 0.20 e Å−3 |
S = 1.00 | Δρmin = −0.17 e Å−3 |
7171 reflections | Absolute structure: Flack (1983), with 1462 Friedel pairs |
545 parameters | Absolute structure parameter: 0.00 (1) |
0 restraints | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted R-factors wR and all
goodnesses of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The observed criterion of F2 > σ(F2)
is used only for calculating -R-factor-obs 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 | 0.23376 (4) | 0.73110 (1) | 0.96070 (3) | 0.0410 (1) | |
O1 | 0.5298 (3) | 0.71475 (8) | 1.0725 (3) | 0.0800 (8) | |
O4 | 0.4293 (2) | 0.90778 (5) | 0.9854 (2) | 0.0514 (6) | |
O9 | 0.1622 (3) | 0.68377 (5) | 0.79326 (19) | 0.0537 (6) | |
O10 | 0.1085 (3) | 0.66750 (5) | 0.5345 (2) | 0.0633 (7) | |
O44 | 0.0452 (2) | 0.55349 (5) | 0.94614 (19) | 0.0517 (6) | |
O49 | 0.2791 (2) | 0.78043 (5) | 1.11801 (18) | 0.0492 (5) | |
O50 | 0.3073 (3) | 0.79813 (5) | 1.3663 (2) | 0.0606 (6) | |
N1 | 0.3273 (2) | 0.82801 (5) | 0.6714 (2) | 0.0384 (5) | |
N3 | 0.3387 (2) | 0.83549 (5) | 0.9181 (2) | 0.0394 (5) | |
N6 | 0.2350 (2) | 0.76765 (6) | 0.7797 (2) | 0.0393 (6) | |
N41 | 0.0931 (2) | 0.63795 (5) | 1.2317 (2) | 0.0383 (6) | |
N43 | 0.1086 (2) | 0.62767 (5) | 0.9974 (2) | 0.0381 (5) | |
N46 | 0.1770 (3) | 0.69893 (6) | 1.1186 (2) | 0.0420 (6) | |
C2 | 0.2965 (3) | 0.80705 (6) | 0.7852 (2) | 0.0337 (6) | |
C4 | 0.3932 (3) | 0.87584 (7) | 0.8932 (3) | 0.0364 (7) | |
C5 | 0.4032 (3) | 0.87201 (6) | 0.7283 (2) | 0.0330 (6) | |
C7 | 0.1964 (3) | 0.74098 (7) | 0.6300 (2) | 0.0446 (7) | |
C8 | 0.1523 (3) | 0.69381 (8) | 0.6523 (3) | 0.0444 (7) | |
C11 | 0.5969 (3) | 0.87405 (8) | 0.7785 (3) | 0.0433 (7) | |
C12 | 0.6920 (3) | 0.83617 (11) | 0.7925 (3) | 0.0693 (10) | |
C13 | 0.8748 (5) | 0.84057 (17) | 0.8500 (5) | 0.1082 (18) | |
C14 | 0.9483 (5) | 0.88226 (19) | 0.8873 (5) | 0.1075 (18) | |
C15 | 0.8551 (4) | 0.91867 (15) | 0.8749 (5) | 0.0957 (15) | |
C16 | 0.6799 (3) | 0.91488 (10) | 0.8198 (3) | 0.0641 (10) | |
C21 | 0.3020 (3) | 0.90749 (7) | 0.5964 (3) | 0.0402 (7) | |
C22 | 0.3055 (3) | 0.90600 (9) | 0.4442 (3) | 0.0549 (8) | |
C23 | 0.2139 (5) | 0.93693 (11) | 0.3226 (3) | 0.0793 (10) | |
C24 | 0.1245 (5) | 0.96959 (11) | 0.3485 (5) | 0.1063 (14) | |
C25 | 0.1212 (5) | 0.97158 (12) | 0.4960 (5) | 0.1120 (16) | |
C26 | 0.2088 (4) | 0.94048 (9) | 0.6234 (4) | 0.0760 (11) | |
C42 | 0.1288 (3) | 0.65827 (7) | 1.1198 (2) | 0.0342 (6) | |
C44 | 0.0665 (3) | 0.58626 (7) | 1.0298 (2) | 0.0365 (6) | |
C45 | 0.0474 (3) | 0.59098 (7) | 1.1910 (2) | 0.0352 (6) | |
C47 | 0.1962 (3) | 0.72663 (8) | 1.2590 (2) | 0.0468 (7) | |
C48 | 0.2657 (3) | 0.77214 (7) | 1.2508 (3) | 0.0421 (7) | |
C51 | −0.1418 (3) | 0.58053 (7) | 1.1470 (2) | 0.0376 (7) | |
C52 | −0.2528 (3) | 0.61316 (9) | 1.1457 (3) | 0.0555 (8) | |
C53 | −0.4240 (4) | 0.60250 (11) | 1.1013 (4) | 0.0721 (11) | |
C54 | −0.4832 (4) | 0.55945 (12) | 1.0574 (4) | 0.0692 (10) | |
C55 | −0.3729 (4) | 0.52759 (10) | 1.0605 (3) | 0.0640 (9) | |
C56 | −0.2025 (3) | 0.53757 (8) | 1.1055 (3) | 0.0519 (8) | |
C61 | 0.1750 (3) | 0.56119 (7) | 1.3347 (3) | 0.0390 (7) | |
C62 | 0.1678 (4) | 0.56138 (9) | 1.4826 (3) | 0.0587 (9) | |
C63 | 0.2828 (4) | 0.53717 (12) | 1.6178 (4) | 0.0775 (11) | |
C64 | 0.4050 (5) | 0.51109 (11) | 1.6046 (4) | 0.0914 (13) | |
C65 | 0.4139 (6) | 0.51080 (15) | 1.4600 (4) | 0.1214 (16) | |
C66 | 0.2965 (4) | 0.53544 (12) | 1.3241 (4) | 0.0868 (15) | |
O31 | 0.6205 (7) | 0.71035 (17) | 0.8111 (6) | 0.196 (3) | |
N32 | 0.6511 (4) | 0.66366 (13) | 0.6355 (4) | 0.1047 (14) | |
C31A | 0.6041 (9) | 0.6702 (3) | 0.7518 (8) | 0.115 (3) | 0.650 |
C33A | 0.6699 (14) | 0.6199 (3) | 0.5799 (12) | 0.189 (6) | 0.650 |
C34A | 0.6876 (10) | 0.6985 (3) | 0.5494 (11) | 0.155 (5) | 0.650 |
C31B | 0.6802 (17) | 0.7036 (3) | 0.7054 (17) | 0.119 (4)* | 0.350 |
C33B | 0.680 (3) | 0.6558 (7) | 0.4947 (17) | 0.163 (7)* | 0.350 |
C34B | 0.5725 (14) | 0.6344 (4) | 0.7057 (15) | 0.100 (3)* | 0.350 |
O71 | 0.7665 (5) | 0.76973 (13) | 0.3193 (6) | 0.200 (2) | |
N72 | 0.7741 (3) | 0.84430 (11) | 0.3386 (3) | 0.0828 (10) | |
C71 | 0.7215 (7) | 0.8061 (2) | 0.3681 (7) | 0.144 (3) | |
C73 | 0.7303 (8) | 0.88511 (19) | 0.3974 (7) | 0.164 (3) | |
C74 | 0.8666 (6) | 0.8464 (2) | 0.2544 (6) | 0.167 (3) | |
H1 | 0.30490 | 0.81680 | 0.57580 | 0.0460* | |
H1W | 0.560 (4) | 0.7134 (11) | 0.997 (4) | 0.084 (12)* | |
H2W | 0.597 (5) | 0.7355 (16) | 1.141 (5) | 0.137 (17)* | |
H3 | 0.33150 | 0.82850 | 1.00680 | 0.0470* | |
H7A | 0.29640 | 0.74100 | 0.61020 | 0.0540* | |
H7B | 0.09950 | 0.75410 | 0.53320 | 0.0540* | |
H12 | 0.63870 | 0.80840 | 0.76520 | 0.0830* | |
H13 | 0.94260 | 0.81560 | 0.86200 | 0.1290* | |
H14 | 1.06640 | 0.88520 | 0.92210 | 0.1290* | |
H15 | 0.90870 | 0.94640 | 0.90350 | 0.1150* | |
H16 | 0.61540 | 0.94040 | 0.81010 | 0.0770* | |
H22 | 0.36960 | 0.88420 | 0.42510 | 0.0660* | |
H23 | 0.21380 | 0.93520 | 0.21980 | 0.0950* | |
H24 | 0.06540 | 0.99070 | 0.26560 | 0.1280* | |
H25 | 0.05900 | 0.99430 | 0.51330 | 0.1340* | |
H26 | 0.20420 | 0.94210 | 0.72390 | 0.0910* | |
H41 | 0.09660 | 0.65100 | 1.31790 | 0.0460* | |
H43 | 0.12120 | 0.63400 | 0.91100 | 0.0460* | |
H47A | 0.27500 | 0.71230 | 1.36360 | 0.0560* | |
H47B | 0.08450 | 0.72980 | 1.25650 | 0.0560* | |
H52 | −0.21350 | 0.64230 | 1.17450 | 0.0670* | |
H53 | −0.49900 | 0.62450 | 1.10110 | 0.0860* | |
H54 | −0.59820 | 0.55250 | 1.02600 | 0.0830* | |
H55 | −0.41240 | 0.49850 | 1.03180 | 0.0770* | |
H56 | −0.12790 | 0.51510 | 1.10790 | 0.0620* | |
H62 | 0.08320 | 0.57830 | 1.49150 | 0.0700* | |
H63 | 0.27810 | 0.53840 | 1.71840 | 0.0930* | |
H64 | 0.48100 | 0.49380 | 1.69480 | 0.1100* | |
H65 | 0.49890 | 0.49400 | 1.45120 | 0.1450* | |
H66 | 0.30140 | 0.53420 | 1.22360 | 0.1040* | |
H33C | 0.58560 | 0.61600 | 0.46450 | 0.2270* | 0.650 |
H34A | 0.62440 | 0.69340 | 0.43080 | 0.1860* | 0.650 |
H34B | 0.80980 | 0.69910 | 0.58420 | 0.1860* | 0.650 |
H34C | 0.65300 | 0.72660 | 0.57530 | 0.1860* | 0.650 |
H31A | 0.56090 | 0.64710 | 0.79010 | 0.1380* | 0.650 |
H33A | 0.65210 | 0.59770 | 0.64680 | 0.2270* | 0.650 |
H33B | 0.78450 | 0.61680 | 0.59160 | 0.2270* | 0.650 |
H31B | 0.73980 | 0.72550 | 0.68060 | 0.1420* | 0.350 |
H33D | 0.70790 | 0.68350 | 0.45930 | 0.1960* | 0.350 |
H33E | 0.57710 | 0.64350 | 0.40440 | 0.1960* | 0.350 |
H33F | 0.77480 | 0.63540 | 0.52580 | 0.1960* | 0.350 |
H34D | 0.60740 | 0.64300 | 0.81930 | 0.1200* | 0.350 |
H34E | 0.60910 | 0.60440 | 0.70350 | 0.1200* | 0.350 |
H34F | 0.44840 | 0.63630 | 0.64110 | 0.1200* | 0.350 |
H71 | 0.65390 | 0.80480 | 0.42240 | 0.1740* | |
H73A | 0.63610 | 0.87940 | 0.42140 | 0.1970* | |
H73B | 0.69640 | 0.90760 | 0.31230 | 0.1970* | |
H73C | 0.82960 | 0.89520 | 0.49730 | 0.1970* | |
H74A | 0.98820 | 0.84720 | 0.33270 | 0.2000* | |
H74B | 0.83530 | 0.87290 | 0.18670 | 0.2000* | |
H74C | 0.84210 | 0.82070 | 0.18370 | 0.2000* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0781 (2) | 0.0272 (1) | 0.0321 (1) | −0.0105 (1) | 0.0379 (1) | −0.0062 (1) |
O1 | 0.0912 (15) | 0.0761 (15) | 0.0757 (14) | 0.0113 (12) | 0.0417 (13) | −0.0035 (12) |
O4 | 0.0815 (11) | 0.0337 (9) | 0.0460 (9) | −0.0115 (8) | 0.0359 (8) | −0.0115 (7) |
O9 | 0.1097 (13) | 0.0320 (8) | 0.0404 (8) | −0.0187 (8) | 0.0527 (9) | −0.0093 (6) |
O10 | 0.1257 (16) | 0.0407 (9) | 0.0455 (9) | −0.0273 (9) | 0.0584 (10) | −0.0177 (8) |
O44 | 0.0831 (12) | 0.0355 (9) | 0.0478 (9) | −0.0116 (8) | 0.0401 (9) | −0.0151 (7) |
O49 | 0.0979 (12) | 0.0286 (8) | 0.0398 (8) | −0.0129 (8) | 0.0480 (8) | −0.0076 (6) |
O50 | 0.1205 (14) | 0.0384 (9) | 0.0470 (9) | −0.0277 (9) | 0.0594 (10) | −0.0192 (8) |
N1 | 0.0666 (11) | 0.0261 (9) | 0.0307 (8) | −0.0085 (8) | 0.0296 (8) | −0.0034 (7) |
N3 | 0.0673 (11) | 0.0303 (9) | 0.0320 (8) | −0.0048 (8) | 0.0327 (8) | −0.0035 (7) |
N6 | 0.0732 (12) | 0.0265 (9) | 0.0303 (8) | −0.0077 (8) | 0.0345 (8) | −0.0048 (7) |
N41 | 0.0671 (11) | 0.0274 (9) | 0.0350 (9) | −0.0085 (8) | 0.0361 (9) | −0.0059 (7) |
N43 | 0.0645 (11) | 0.0302 (9) | 0.0326 (8) | −0.0098 (8) | 0.0337 (8) | −0.0057 (7) |
N46 | 0.0764 (12) | 0.0284 (10) | 0.0351 (9) | −0.0136 (9) | 0.0377 (9) | −0.0093 (7) |
C2 | 0.0505 (11) | 0.0259 (11) | 0.0300 (9) | 0.0009 (9) | 0.0233 (9) | −0.0014 (8) |
C4 | 0.0481 (12) | 0.0297 (11) | 0.0352 (11) | −0.0018 (9) | 0.0227 (10) | −0.0017 (9) |
C5 | 0.0441 (11) | 0.0272 (10) | 0.0321 (10) | −0.0036 (9) | 0.0215 (9) | −0.0016 (8) |
C7 | 0.0786 (14) | 0.0376 (15) | 0.0292 (9) | −0.0102 (10) | 0.0349 (10) | −0.0061 (9) |
C8 | 0.0759 (15) | 0.0331 (11) | 0.0386 (12) | −0.0136 (11) | 0.0388 (11) | −0.0103 (10) |
C11 | 0.0463 (12) | 0.0513 (13) | 0.0339 (11) | 0.0024 (10) | 0.0203 (10) | 0.0026 (10) |
C12 | 0.0627 (17) | 0.0790 (19) | 0.0685 (17) | 0.0161 (15) | 0.0328 (14) | −0.0077 (15) |
C13 | 0.073 (2) | 0.148 (4) | 0.103 (3) | 0.041 (3) | 0.041 (2) | −0.016 (3) |
C14 | 0.058 (2) | 0.159 (4) | 0.107 (3) | −0.011 (3) | 0.040 (2) | −0.028 (3) |
C15 | 0.0561 (19) | 0.117 (3) | 0.109 (3) | −0.027 (2) | 0.0347 (18) | −0.019 (2) |
C16 | 0.0508 (15) | 0.0731 (19) | 0.0654 (16) | −0.0125 (13) | 0.0248 (13) | −0.0026 (14) |
C21 | 0.0469 (12) | 0.0285 (11) | 0.0376 (12) | −0.0052 (10) | 0.0136 (9) | 0.0021 (9) |
C22 | 0.0661 (16) | 0.0513 (15) | 0.0399 (13) | −0.0117 (12) | 0.0189 (12) | 0.0047 (11) |
C23 | 0.102 (2) | 0.0614 (19) | 0.0422 (14) | −0.0271 (18) | 0.0073 (15) | 0.0167 (14) |
C24 | 0.122 (3) | 0.056 (2) | 0.074 (2) | 0.004 (2) | −0.009 (2) | 0.0303 (17) |
C25 | 0.132 (3) | 0.062 (2) | 0.101 (3) | 0.050 (2) | 0.021 (2) | 0.019 (2) |
C26 | 0.085 (2) | 0.0554 (17) | 0.0666 (18) | 0.0255 (15) | 0.0184 (15) | 0.0017 (14) |
C42 | 0.0492 (11) | 0.0327 (11) | 0.0274 (9) | −0.0053 (9) | 0.0237 (9) | −0.0040 (8) |
C44 | 0.0488 (12) | 0.0308 (11) | 0.0344 (10) | −0.0045 (9) | 0.0233 (9) | −0.0055 (9) |
C45 | 0.0525 (12) | 0.0262 (10) | 0.0329 (10) | −0.0062 (9) | 0.0250 (9) | −0.0031 (8) |
C47 | 0.0847 (14) | 0.0375 (12) | 0.0366 (9) | −0.0175 (13) | 0.0438 (10) | −0.0091 (10) |
C48 | 0.0743 (15) | 0.0303 (11) | 0.0364 (11) | −0.0070 (10) | 0.0382 (11) | −0.0052 (9) |
C51 | 0.0484 (12) | 0.0360 (12) | 0.0329 (10) | −0.0004 (9) | 0.0229 (9) | 0.0043 (8) |
C52 | 0.0595 (15) | 0.0490 (14) | 0.0629 (15) | −0.0009 (12) | 0.0329 (12) | −0.0014 (12) |
C53 | 0.0624 (17) | 0.078 (2) | 0.084 (2) | 0.0096 (15) | 0.0411 (15) | −0.0057 (16) |
C54 | 0.0541 (16) | 0.092 (2) | 0.0640 (17) | −0.0164 (16) | 0.0300 (14) | −0.0016 (16) |
C55 | 0.0653 (17) | 0.0629 (17) | 0.0580 (15) | −0.0232 (14) | 0.0242 (13) | −0.0039 (12) |
C56 | 0.0564 (15) | 0.0380 (13) | 0.0596 (14) | −0.0087 (11) | 0.0260 (11) | −0.0018 (11) |
C61 | 0.0471 (12) | 0.0305 (11) | 0.0396 (12) | −0.0063 (9) | 0.0206 (10) | −0.0033 (9) |
C62 | 0.0666 (16) | 0.0686 (17) | 0.0397 (13) | 0.0045 (14) | 0.0241 (13) | 0.0062 (12) |
C63 | 0.089 (2) | 0.096 (2) | 0.0395 (15) | 0.002 (2) | 0.0237 (15) | 0.0117 (16) |
C64 | 0.106 (3) | 0.075 (2) | 0.0586 (18) | 0.0315 (19) | 0.0103 (17) | 0.0112 (16) |
C65 | 0.137 (3) | 0.133 (3) | 0.072 (2) | 0.086 (3) | 0.031 (2) | 0.012 (2) |
C66 | 0.106 (3) | 0.109 (3) | 0.0491 (16) | 0.059 (2) | 0.0397 (17) | 0.0129 (16) |
O31 | 0.261 (5) | 0.220 (5) | 0.170 (4) | 0.088 (4) | 0.154 (4) | 0.013 (3) |
N32 | 0.088 (2) | 0.146 (3) | 0.081 (2) | −0.007 (2) | 0.0406 (17) | −0.015 (2) |
C31A | 0.133 (5) | 0.137 (6) | 0.087 (4) | −0.006 (5) | 0.062 (4) | 0.029 (4) |
C33A | 0.232 (11) | 0.196 (11) | 0.106 (6) | 0.002 (9) | 0.053 (7) | −0.026 (7) |
C34A | 0.137 (6) | 0.228 (10) | 0.148 (7) | 0.015 (6) | 0.107 (6) | 0.056 (7) |
O71 | 0.152 (3) | 0.125 (3) | 0.223 (5) | −0.020 (3) | 0.007 (3) | −0.050 (3) |
N72 | 0.0697 (15) | 0.100 (2) | 0.0762 (17) | −0.0162 (15) | 0.0323 (13) | −0.0059 (15) |
C71 | 0.131 (4) | 0.168 (5) | 0.147 (4) | −0.055 (4) | 0.076 (3) | −0.033 (4) |
C73 | 0.185 (6) | 0.152 (5) | 0.121 (4) | 0.020 (4) | 0.043 (4) | −0.024 (4) |
C74 | 0.109 (3) | 0.311 (9) | 0.098 (3) | 0.021 (4) | 0.063 (3) | 0.036 (4) |
Geometric parameters (Å, º) top
Cu1—O1 | 2.341 (3) | C45—C61 | 1.538 (3) |
Cu1—O9 | 1.9523 (15) | C47—C48 | 1.511 (3) |
Cu1—O49 | 1.9606 (15) | C51—C56 | 1.378 (3) |
Cu1—N6 | 1.9751 (17) | C51—C52 | 1.374 (4) |
Cu1—N46 | 1.971 (2) | C52—C53 | 1.390 (5) |
O4—C4 | 1.211 (3) | C53—C54 | 1.379 (5) |
O9—C8 | 1.273 (3) | C54—C55 | 1.348 (5) |
O10—C8 | 1.234 (3) | C55—C56 | 1.378 (5) |
O44—C44 | 1.201 (2) | C61—C66 | 1.352 (5) |
O49—C48 | 1.285 (3) | C61—C62 | 1.369 (4) |
O50—C48 | 1.214 (3) | C62—C63 | 1.369 (4) |
O1—H2W | 0.88 (5) | C63—C64 | 1.373 (6) |
O1—H1W | 0.84 (4) | C64—C65 | 1.346 (5) |
O31—C31A | 1.300 (10) | C65—C66 | 1.386 (5) |
O31—C31B | 1.302 (16) | C7—H7A | 0.97 |
O71—C71 | 1.306 (7) | C7—H7B | 0.97 |
N1—C5 | 1.459 (2) | C12—H12 | 0.93 |
N1—C2 | 1.337 (3) | C13—H13 | 0.93 |
N3—C4 | 1.359 (3) | C14—H14 | 0.93 |
N3—C2 | 1.376 (2) | C15—H15 | 0.93 |
N6—C7 | 1.469 (2) | C16—H16 | 0.93 |
N6—C2 | 1.290 (3) | C22—H22 | 0.93 |
N41—C42 | 1.338 (3) | C23—H23 | 0.93 |
N41—C45 | 1.465 (3) | C24—H24 | 0.93 |
N43—C42 | 1.384 (2) | C25—H25 | 0.93 |
N43—C44 | 1.367 (3) | C26—H26 | 0.93 |
N46—C42 | 1.293 (3) | C47—H47A | 0.97 |
N46—C47 | 1.460 (3) | C47—H47B | 0.97 |
N1—H1 | 0.86 | C52—H52 | 0.93 |
N3—H3 | 0.86 | C53—H53 | 0.93 |
N41—H41 | 0.86 | C54—H54 | 0.93 |
N43—H43 | 0.86 | C55—H55 | 0.93 |
N32—C33B | 1.43 (2) | C56—H56 | 0.93 |
N32—C31A | 1.312 (8) | C62—H62 | 0.93 |
N32—C33A | 1.443 (10) | C63—H63 | 0.93 |
N32—C34A | 1.427 (10) | C64—H64 | 0.93 |
N32—C31B | 1.323 (11) | C65—H65 | 0.93 |
N32—C34B | 1.434 (13) | C66—H66 | 0.93 |
N72—C73 | 1.457 (7) | C31A—H31A | 0.93 |
N72—C74 | 1.347 (6) | C31B—H31B | 0.93 |
N72—C71 | 1.309 (7) | C33A—H33C | 0.96 |
C4—C5 | 1.539 (3) | C33A—H33A | 0.96 |
C5—C11 | 1.532 (4) | C33A—H33B | 0.96 |
C5—C21 | 1.532 (3) | C33B—H33D | 0.96 |
C7—C8 | 1.506 (3) | C33B—H33E | 0.96 |
C11—C16 | 1.383 (4) | C33B—H33F | 0.96 |
C11—C12 | 1.378 (4) | C34A—H34C | 0.96 |
C12—C13 | 1.433 (6) | C34A—H34A | 0.96 |
C13—C14 | 1.374 (7) | C34A—H34B | 0.96 |
C14—C15 | 1.336 (7) | C34B—H34E | 0.96 |
C15—C16 | 1.372 (5) | C34B—H34F | 0.96 |
C21—C22 | 1.392 (4) | C34B—H34D | 0.96 |
C21—C26 | 1.375 (4) | C71—H71 | 0.93 |
C22—C23 | 1.372 (4) | C73—H73A | 0.96 |
C23—C24 | 1.341 (6) | C73—H73B | 0.96 |
C24—C25 | 1.349 (6) | C73—H73C | 0.96 |
C25—C26 | 1.398 (5) | C74—H74A | 0.96 |
C44—C45 | 1.550 (3) | C74—H74B | 0.96 |
C45—C51 | 1.538 (4) | C74—H74C | 0.96 |
| | | |
O1—Cu1—O9 | 93.86 (10) | C61—C62—C63 | 121.3 (3) |
O1—Cu1—O49 | 92.32 (8) | C62—C63—C64 | 119.9 (3) |
O1—Cu1—N6 | 92.21 (8) | C63—C64—C65 | 119.4 (3) |
O1—Cu1—N46 | 100.81 (9) | C64—C65—C66 | 120.1 (4) |
O9—Cu1—O49 | 173.81 (9) | C61—C66—C65 | 121.3 (3) |
O9—Cu1—N6 | 83.46 (7) | C8—C7—H7A | 110.00 |
O9—Cu1—N46 | 96.18 (8) | N6—C7—H7A | 110.00 |
O49—Cu1—N6 | 95.96 (7) | N6—C7—H7B | 110.00 |
O49—Cu1—N46 | 82.99 (7) | H7A—C7—H7B | 108.00 |
N6—Cu1—N46 | 166.97 (9) | C8—C7—H7B | 109.00 |
Cu1—O9—C8 | 116.78 (15) | C11—C12—H12 | 121.00 |
Cu1—O49—C48 | 117.13 (14) | C13—C12—H12 | 121.00 |
H1W—O1—H2W | 104 (4) | C12—C13—H13 | 120.00 |
Cu1—O1—H1W | 111 (2) | C14—C13—H13 | 121.00 |
Cu1—O1—H2W | 113 (3) | C13—C14—H14 | 119.00 |
C2—N1—C5 | 112.16 (15) | C15—C14—H14 | 119.00 |
C2—N3—C4 | 112.28 (18) | C16—C15—H15 | 120.00 |
Cu1—N6—C2 | 129.94 (13) | C14—C15—H15 | 120.00 |
Cu1—N6—C7 | 111.88 (13) | C15—C16—H16 | 119.00 |
C2—N6—C7 | 116.48 (17) | C11—C16—H16 | 119.00 |
C42—N41—C45 | 112.44 (16) | C21—C22—H22 | 120.00 |
C42—N43—C44 | 112.21 (17) | C23—C22—H22 | 120.00 |
Cu1—N46—C42 | 131.50 (15) | C22—C23—H23 | 119.00 |
Cu1—N46—C47 | 112.71 (15) | C24—C23—H23 | 119.00 |
C42—N46—C47 | 115.8 (2) | C23—C24—H24 | 120.00 |
C2—N1—H1 | 124.00 | C25—C24—H24 | 120.00 |
C5—N1—H1 | 124.00 | C24—C25—H25 | 119.00 |
C4—N3—H3 | 124.00 | C26—C25—H25 | 119.00 |
C2—N3—H3 | 124.00 | C21—C26—H26 | 121.00 |
C42—N41—H41 | 124.00 | C25—C26—H26 | 121.00 |
C45—N41—H41 | 124.00 | C48—C47—H47A | 109.00 |
C42—N43—H43 | 124.00 | C48—C47—H47B | 109.00 |
C44—N43—H43 | 124.00 | H47A—C47—H47B | 108.00 |
C33A—N32—C34A | 112.7 (6) | N46—C47—H47B | 109.00 |
C31B—N32—C34B | 111.6 (8) | N46—C47—H47A | 110.00 |
C33B—N32—C34B | 128.0 (10) | C53—C52—H52 | 120.00 |
C31A—N32—C34A | 124.2 (6) | C51—C52—H52 | 120.00 |
C31B—N32—C33B | 120.0 (11) | C52—C53—H53 | 120.00 |
C31A—N32—C33A | 123.1 (7) | C54—C53—H53 | 120.00 |
C73—N72—C74 | 119.8 (4) | C53—C54—H54 | 120.00 |
C71—N72—C74 | 121.2 (4) | C55—C54—H54 | 120.00 |
C71—N72—C73 | 119.0 (4) | C54—C55—H55 | 120.00 |
N3—C2—N6 | 122.55 (19) | C56—C55—H55 | 120.00 |
N1—C2—N6 | 129.24 (17) | C55—C56—H56 | 120.00 |
N1—C2—N3 | 108.20 (16) | C51—C56—H56 | 120.00 |
N3—C4—C5 | 106.16 (17) | C61—C62—H62 | 119.00 |
O4—C4—N3 | 126.1 (2) | C63—C62—H62 | 119.00 |
O4—C4—C5 | 127.7 (2) | C64—C63—H63 | 120.00 |
C4—C5—C21 | 115.32 (19) | C62—C63—H63 | 120.00 |
C4—C5—C11 | 105.57 (17) | C63—C64—H64 | 120.00 |
C11—C5—C21 | 110.8 (2) | C65—C64—H64 | 120.00 |
N1—C5—C4 | 100.71 (17) | C64—C65—H65 | 120.00 |
N1—C5—C21 | 110.82 (16) | C66—C65—H65 | 120.00 |
N1—C5—C11 | 113.29 (18) | C65—C66—H66 | 119.00 |
N6—C7—C8 | 110.56 (17) | C61—C66—H66 | 119.00 |
O9—C8—C7 | 117.1 (2) | O31—C31A—N32 | 117.0 (7) |
O10—C8—C7 | 118.8 (2) | O31—C31B—N32 | 116.0 (10) |
O9—C8—O10 | 124.1 (2) | O31—C31A—H31A | 122.00 |
C12—C11—C16 | 119.4 (3) | N32—C31A—H31A | 121.00 |
C5—C11—C16 | 118.7 (2) | N32—C31B—H31B | 122.00 |
C5—C11—C12 | 121.8 (2) | O31—C31B—H31B | 122.00 |
C11—C12—C13 | 118.5 (3) | N32—C33A—H33C | 110.00 |
C12—C13—C14 | 119.0 (4) | H33A—C33A—H33B | 109.00 |
C13—C14—C15 | 122.0 (4) | N32—C33A—H33B | 109.00 |
C14—C15—C16 | 119.6 (4) | H33A—C33A—H33C | 109.00 |
C11—C16—C15 | 121.6 (3) | H33B—C33A—H33C | 109.00 |
C22—C21—C26 | 119.3 (2) | N32—C33A—H33A | 109.00 |
C5—C21—C26 | 122.4 (2) | N32—C33B—H33E | 110.00 |
C5—C21—C22 | 118.3 (2) | N32—C33B—H33F | 110.00 |
C21—C22—C23 | 119.7 (3) | H33D—C33B—H33E | 109.00 |
C22—C23—C24 | 121.5 (3) | N32—C33B—H33D | 109.00 |
C23—C24—C25 | 119.4 (3) | H33D—C33B—H33F | 109.00 |
C24—C25—C26 | 121.8 (4) | H33E—C33B—H33F | 110.00 |
C21—C26—C25 | 118.3 (3) | H34A—C34A—H34C | 109.00 |
N41—C42—N43 | 108.36 (18) | N32—C34A—H34C | 109.00 |
N41—C42—N46 | 129.01 (18) | H34A—C34A—H34B | 110.00 |
N43—C42—N46 | 122.63 (19) | N32—C34A—H34A | 110.00 |
N43—C44—C45 | 106.11 (16) | N32—C34A—H34B | 110.00 |
O44—C44—N43 | 125.98 (19) | H34B—C34A—H34C | 109.00 |
O44—C44—C45 | 127.9 (2) | N32—C34B—H34F | 109.00 |
C51—C45—C61 | 111.23 (19) | H34D—C34B—H34F | 109.00 |
C44—C45—C51 | 108.43 (16) | H34E—C34B—H34F | 110.00 |
N41—C45—C61 | 110.14 (16) | H34D—C34B—H34E | 110.00 |
C44—C45—C61 | 112.7 (2) | N32—C34B—H34D | 109.00 |
N41—C45—C44 | 100.79 (17) | N32—C34B—H34E | 109.00 |
N41—C45—C51 | 113.18 (19) | O71—C71—N72 | 118.3 (6) |
N46—C47—C48 | 110.89 (19) | O71—C71—H71 | 121.00 |
O49—C48—C47 | 115.89 (19) | N72—C71—H71 | 121.00 |
O49—C48—O50 | 123.9 (2) | N72—C73—H73A | 109.00 |
O50—C48—C47 | 120.2 (2) | N72—C73—H73B | 109.00 |
C52—C51—C56 | 119.1 (3) | N72—C73—H73C | 109.00 |
C45—C51—C56 | 119.3 (2) | H73A—C73—H73B | 109.00 |
C45—C51—C52 | 121.6 (2) | H73A—C73—H73C | 109.00 |
C51—C52—C53 | 119.8 (3) | H73B—C73—H73C | 109.00 |
C52—C53—C54 | 120.3 (3) | N72—C74—H74A | 109.00 |
C53—C54—C55 | 119.5 (3) | N72—C74—H74B | 109.00 |
C54—C55—C56 | 120.9 (3) | N72—C74—H74C | 110.00 |
C51—C56—C55 | 120.5 (3) | H74A—C74—H74B | 109.00 |
C62—C61—C66 | 118.1 (3) | H74A—C74—H74C | 109.00 |
C45—C61—C66 | 123.6 (2) | H74B—C74—H74C | 109.00 |
C45—C61—C62 | 118.4 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O50i | 0.86 | 1.99 | 2.828 (2) | 166 |
N41—H41···O10ii | 0.86 | 1.98 | 2.821 (2) | 167 |
O1—H1W···O31 | 0.84 (4) | 1.99 (4) | 2.828 (6) | 178 (4) |
O1—H2W···O71ii | 0.88 (5) | 1.90 (4) | 2.763 (5) | 168 (4) |
N3—H3···O49 | 0.86 | 1.93 | 2.676 (2) | 144 |
N43—H43···O9 | 0.86 | 1.96 | 2.698 (3) | 143 |
C24—H24···O44iii | 0.93 | 2.53 | 3.453 (4) | 170 |
Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1; (iii) −x, y+1/2, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Cu(C17H14N3O3)2]·2C3H7NO | [Cu(C20H21N4O4)2(H2O)]·2C3H7NO |
Mr | 826.37 | 844.38 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21 |
Temperature (K) | 291 | 293 |
a, b, c (Å) | 8.987 (4), 14.075 (6), 16.208 (7) | 8.7305 (3), 30.0213 (5), 9.0447 (2) |
β (°) | 95.913 (6) | 118.102 (4) |
V (Å3) | 2039.3 (15) | 2091.15 (12) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.60 | 0.59 |
Crystal size (mm) | 0.2 × 0.1 × 0.05 | 0.30 × 0.25 × 0.22 |
|
Data collection |
Diffractometer | Bruker SMART APEXII CCD diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.924, 0.979 | 0.825, 0.882 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28748, 3590, 2815 | 21287, 7171, 6447 |
Rint | 0.052 | 0.016 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.130, 1.14 | 0.026, 0.066, 1.00 |
No. of reflections | 3590 | 7171 |
No. of parameters | 269 | 545 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.67, −0.27 | 0.20, −0.17 |
Absolute structure | ? | Flack (1983), with 1462 Friedel pairs |
Absolute structure parameter | ? | 0.00 (1) |
Selected geometric parameters (Å, º) for (I) topCu1—O9 | 1.922 (2) | O9—C8 | 1.292 (3) |
Cu1—N6 | 1.951 (3) | O10—C8 | 1.218 (4) |
O4—C4 | 1.203 (4) | | |
| | | |
O9—Cu1—N6 | 84.32 (9) | O9—Cu1—N6i | 95.68 (9) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O10ii | 0.78 (4) | 2.02 (4) | 2.768 (4) | 160 (3) |
N3—H3···O9i | 0.83 (4) | 1.91 (3) | 2.663 (3) | 149 (3) |
C7—H71···O31iii | 0.97 | 2.35 | 3.268 (5) | 157 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) −x+1/2, y−1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topCu1—O1 | 2.341 (3) | Cu1—N46 | 1.971 (2) |
Cu1—O9 | 1.9523 (15) | O9—C8 | 1.273 (3) |
Cu1—O49 | 1.9606 (15) | O10—C8 | 1.234 (3) |
Cu1—N6 | 1.9751 (17) | | |
| | | |
O1—Cu1—O9 | 93.86 (10) | O9—Cu1—N6 | 83.46 (7) |
O1—Cu1—O49 | 92.32 (8) | O9—Cu1—N46 | 96.18 (8) |
O1—Cu1—N6 | 92.21 (8) | O49—Cu1—N6 | 95.96 (7) |
O1—Cu1—N46 | 100.81 (9) | O49—Cu1—N46 | 82.99 (7) |
O9—Cu1—O49 | 173.81 (9) | N6—Cu1—N46 | 166.97 (9) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O50i | 0.86 | 1.99 | 2.828 (2) | 166 |
N41—H41···O10ii | 0.86 | 1.98 | 2.821 (2) | 167 |
O1—H1W···O31 | 0.84 (4) | 1.99 (4) | 2.828 (6) | 178 (4) |
O1—H2W···O71ii | 0.88 (5) | 1.90 (4) | 2.763 (5) | 168 (4) |
N3—H3···O49 | 0.86 | 1.93 | 2.676 (2) | 144 |
N43—H43···O9 | 0.86 | 1.96 | 2.698 (3) | 143 |
C24—H24···O44iii | 0.93 | 2.53 | 3.453 (4) | 170 |
Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1; (iii) −x, y+1/2, −z+1. |
In our previous research, diphenyl- and arylidene-imidazoline-4-one amino acids have been studied from the viewpoint of their binding to ionotropic (iGluRs) (Kieć-Kononowicz et al., 1998) and/or metabotropic (iGluRs) receptors (Karolak-Wojciechowska & Kieć-Kononowicz, in preparation). From information based on the model of ligand-receptor interactions with iGluRs (Karolak-Wojciechowska et al., 2000), it was postulated that the presence of COO- ions in the amino acids studied was indispensable for binding (Karolak-Wojciechowska et al., 2001). For this reason, we are currently focusing our attention on interactions between such amino acids and metals. As a first example, we obtained an interesting six-coordinate potassium polymeric complex with o-Cl-benzylidene-imidazoline-4-one β-alanine and water molecules (Mrozek et al., 2003). Recently, we obtained the two title CuII complexes, (I) and (II), with 5,5-diphenyl-4-oxo-imidazolidinyl glycine, and present their crystal structures here.
The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively. In (I), the four-coordinate CuII ion lies on a crystallographic inversion centre and forms a square-planar CuN2O2 unit (Table 1). The O,N-bidentate unit, belonging to the 5,5-diphenyl-4-oxo-imidazolidinyl-glycine (hereinafter abbreviated as DPGly) ligand, forms a planar five-membered ring. Even though the coordination numbers in structures (I) and (II) are not the same, in both compounds the CuII atom is coordinated by two O,N-bidentate units, with atoms O9 and N6 [and O49 and N46 in (II)] in a trans geometry. An increase in the coordination number of CuII from four in (I) to five in (II) is caused by the presence of a water molecule. This results not only in bond-length elongation in the coordination environment (Tables 1 and 3), but also in a shift of the Cu atom from the basal plane towards the apical atom O1 (water molecule) in (II) [0.052 (5) Å for (I) and 0.1646 (11) Å for (II)]. Furthermore, the structure of (II) loses the centre of symmetry, with the space group changng from P21/n in (I) to P21 in (II). The distortion from ideal five-coordinate geometries can be best described by the degree of trigonality τ (Addison et al., 1984). For a regular square-pyramidal (SQP) geometry, the trigonality parameter is 0, and for a trigonal–bipyramidal (TBP) structure it increases to 1. In (II), τ = 0.114, indicating a slightly distorted SQP coordination geometry around CuII.
The bond valences around CuII atoms in both structures were computed according to Brown (1994) and O'Keeffe & Brese (1991) as νij = exp[(Rij- dij)/0.37], where Rij is the bond-valence parameter (in the formal sense, it is the single-bond length between the i and j atoms) and dij is the observed bond length. In the present structures, the application of this correlation allows one to compare the relative importance of Cu—L bonds of Cu polyhedra, and to check the valence-sum rule for the CuII atom (Brown, 2002). According to Shields et al. (2000), RCu—N and RCu—O were taken as 1.716 and 1.657 Å for (I), respectively, and 1.705 and 1.652 Å for (II), respectively. The estimated bond valences of the CuII atom show that, in both structures, the equatorial Cu—N bonds are distinctly stronger than the equatorial Cu—O ones [νCu—N = 0.530 and νCu—O = 0.489 v.u. in (I), and νCu—N(average) = 0.485 and νCu–O(average) = 0.439 v.u. in (II)]. The valence of the axial Cu–O1 bond in structure (II) amounts to 0.155 v.u. Finally, the valences of the four- and five-coordinate Cu atoms are consistent with the valence-sum rule (Vi = Σνij), which gives here VCu = 2.037 for (I) and 2.003 for (II).
The dihedral angles between the planes of the five-membered imidazole ring and the respective phenyl rings located on atoms C5 and C45 in (II) are not equal [76.76 (13)° for the C11–C16 ring, 57.34 (10)° for C21–C26, 67.04 (9)° for C51–C56 and 64.72 (11)° for C61–C66], while in (I) they are equal to within experimental error [68.78 (14) and 69.26 (14)° for the corresponding C11–C16 and C21–C26 rings, respectively].
In the structure of (I), intramolecular N3—H3···O9(-x, -y, -z) hydrogen bonds join two DPGly ligand molecules. This bond generates an S(6) graph-set motif (Etter et al., 1990) in the plane of the O,N-bidentate units. The complex molecules are connected together by N1—H1···O10(1 - x, -y, -z) hydrogen bonds, forming rings of graph-set R22(14). These rings construct ribbons running along the a axis which are slightly inclined with respect to the ac plane (Fig. 3 and Table 2). The distance between two parallel ribbons is equal to the b axis value [14.075 (6) Å], but at 0.5b another ribbon, oppositely inclined to the ac plane, is present. Between these two ribbons there is enough space for the location of all the phenyl rings from the DPGly molecules and the respective number of dimethylformamide (DMF) solvent molecules. The DMF molecules bridge successive ribbons through non-covalent interactions in the crystal of (I). Therefore, from one site, DMF atom O31 is involved in a weak C71—H71···O31(-x + 1/2, y - 1/2, -z + 1/2) interaction with the glycine atom C7 of one ribbon, while the other imidazolidinone carbonyl O atom from the second ribbon participates in a weak C34–H342···O4(-x, -y, 1 - z) interaction with a DMF C atom [3.514 (8) Å].
Analogous intra- and intermolecular N—H···O hydrogen bonds are also recognized in the structure of (II) (Fig. 4 and Table 4), with the final ribbons running along the c axis and with the distance between parallel ribbons amounting to the a axis value [8.7305 (3) Å]. The space between them contains not only the phenyl rings from the DPGly molecules and the respective number of DMF solvent molecules, but also a ligand water molecule. The solvent DMF molecules in (II) are differently anchored than in (I). Both DMF molecules are hydrogen-bonded to the coordinated water via relevant O1—H1W···O31 and O1—H2W···O41(x, y, z + 1) interactions. Additionally, weak hydrogen-bond C7—H7B···O71(x - 1, y, z) interactions involving one DMF molecule maintain the parallel ribbons. It is worth mentioning that one of the two imidazolidinone carbonyl O atoms in (II) (O44) is involved in an intermolecular interaction, creating a relatively strong C24—H24···O44(-x, 1/2 + y, 1 - z) hydrogen bond to a neighbouring ribbon at an angle of 170°. Due to this extended interaction, parallel ribbons form a helix down the b axis.