Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034538/tk2179sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034538/tk2179Isup2.hkl |
CCDC reference: 657615
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.008 Å
- R factor = 0.084
- wR factor = 0.142
- Data-to-parameter ratio = 20.8
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT731_ALERT_1_B Bond Calc 0.90(9), Rep 0.90(2) ...... 4.50 su-Ra O3 -H31 1.555 1.555 PLAT735_ALERT_1_B D-H Calc 0.90(9), Rep 0.90(2) ...... 4.50 su-Ra O3 -H31 1.555 1.555
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.80 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.50 Ratio PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT731_ALERT_1_C Bond Calc 0.90(8), Rep 0.90(2) ...... 4.00 su-Ra O3 -H32 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.89(5), Rep 0.89(2) ...... 2.50 su-Ra N3 -H3 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.89(5), Rep 0.89(2) ...... 2.50 su-Ra N3 -H3 1.555 1.555 PLAT736_ALERT_1_C H...A Calc 2.37(10), Rep 2.37(3) ...... 3.33 su-Ra H31 -CL1 1.555 1.555 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 H2 O
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of N1 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of N2 = ... R PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.17 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu2 (2) 1.97 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
The title complex was synthesized using a modification of the published procedure (Zhang et al., 1995). 1-Acetato-4-undecyl-1,4,7-triazacyclononane trihydrochloride (0.1 g, 0.22 mmol) was dissolved in MeOH (5 ml) and mixed with 1 equivalent of CuCl2.6H2O (0.038 g, 0.22 mmol) dissolved in MeOH (1 ml). Addition of 1.1 equivalent NaOAc (0.0076 g, 0.2 4 mmol) dissolved in MeOH resulted in a dark-green solution. Slow evaporation of the solution resulted in the deposition of blue-green crystals suitable for X-ray diffraction analysis. The solid was collected by filtration and air-dried (0.04 g, 18%). IR (KBr): 3199, 2920, 1578 (νC—O), 1491, 1466, 1445, 1403, 1313 (νC—O) cm-1. UV/vis (MeCN): λmax(ε) 265 (934), 461 (114) nm (L.mol-1.cm).
The amine-H3 atom and the water-H31 and H32 atoms and were located and refined with the latter having O—H distances restrained to approximately 0.90 Å. Otherwise, all H atoms were included in the riding model approximation with C—H = 0.95–0.99 Å, and with Uiso(H) = 1.2Ueq(C). The maximum and minimum electron density peaks were located 1.23 and 1.81 Å from the H3A and H6A atoms, respectively.
The title complex, (I), crystallizes in the monoclinic space group (P21/c), with the asymmetric unit comprising one half of the molecule [Cu(AcC11tacn)Cl.H2O]2.CuCl2, Fig. 1; the Cu2 atom is located on a crystallographic inversion centre. The three N atoms from the macrocycle coordinate facially to Cu1, which is also bound to a terminal Cl with the fifth coordination site completed by the O atom derived from the N-acetyl group. Two of these units are further connected via the keto-O atoms to a four coordinate copper dichloride entity. The Cu1—Cl1 bond distance (2.2645 (14) Å) is slightly longer than the Cu2—Cl2 distance of 2.2512 (14) Å, but this may also reflect the interaction of Cl1 with the water molecule via a O3—H31···Cl1 (2.37 (3) Å) hydrogen bond. The Cu—N distances are inequivalent with the C11 substituted N atom having the longest bond (Cu1—N2 2.289 (4) Å) whilst the secondary amine has the shortest (Cu1—N3 1.985 (4) Å).
The cell contents, when viewed along the b axis, Fig. 2, show the straight chain C11 units form interdigitated layers which separate the hydrophilic {Cu(Actacn)Cl}.CuCl2 moieties, the latter associated via intermolecular N3—H3···Cl2i hydrogen bonds (Table 1).
There are several reports of carboxylate functionalized 1,4,7-triazacyclononane (tacn) (Mondal et al., 2003; Neves et al., 1988; Graham et al., 1997; Studer et al., 1989; Schulz et al., 1996). In contrast, the arrangement of long hydrophobic carbon tails has been underrepresented (Fallis et al., 1998; Battle & Martin, 2006). The title complex combines both groups and results in a trinuclear copper complex. For synthesis, see: Zhang et al. (1995).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97.
Fig. 1. A view of (I) showing atomic labelling and displacement ellipsoids at the 50% probability level. | |
Fig. 2. Cell contents as viewed down the b axis. H atoms have been omitted for clarity. |
[Cu3Cl4(C17H38N3O2)2]·2H2O | F(000) = 1106 |
Mr = 1049.50 | Dx = 1.422 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25491 reflections |
a = 22.1182 (11) Å | θ = 2.8–27.5° |
b = 7.8330 (4) Å | µ = 1.56 mm−1 |
c = 14.6177 (7) Å | T = 123 K |
β = 104.570 (2)° | Plate, blue-green |
V = 2451.1 (2) Å3 | 0.20 × 0.10 × 0.05 mm |
Z = 2 |
Bruker X8 APEX CCD diffractometer | 5625 independent reflections |
Radiation source: fine-focus sealed tube | 4994 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
φ scans | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −28→28 |
Tmin = 0.746, Tmax = 0.926 | k = −10→10 |
25491 measured reflections | l = −18→18 |
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)] = 0.084 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.32 | w = 1/[σ2(Fo2) + 12.2399P] where P = (Fo2 + 2Fc2)/3 |
5625 reflections | (Δ/σ)max = 0.001 |
271 parameters | Δρmax = 0.62 e Å−3 |
3 restraints | Δρmin = −1.02 e Å−3 |
[Cu3Cl4(C17H38N3O2)2]·2H2O | V = 2451.1 (2) Å3 |
Mr = 1049.50 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 22.1182 (11) Å | µ = 1.56 mm−1 |
b = 7.8330 (4) Å | T = 123 K |
c = 14.6177 (7) Å | 0.20 × 0.10 × 0.05 mm |
β = 104.570 (2)° |
Bruker X8 APEX CCD diffractometer | 5625 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 4994 reflections with I > 2σ(I) |
Tmin = 0.746, Tmax = 0.926 | Rint = 0.071 |
25491 measured reflections |
R[F2 > 2σ(F2)] = 0.084 | 3 restraints |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.32 | w = 1/[σ2(Fo2) + 12.2399P] where P = (Fo2 + 2Fc2)/3 |
5625 reflections | Δρmax = 0.62 e Å−3 |
271 parameters | Δρmin = −1.02 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.61289 (3) | 0.74292 (8) | −0.20823 (4) | 0.01211 (15) | |
Cu2 | 0.5000 | 0.5000 | 0.0000 | 0.0165 (2) | |
Cl1 | 0.61753 (6) | 1.00100 (16) | −0.13697 (9) | 0.0193 (3) | |
Cl2 | 0.41046 (7) | 0.64527 (17) | −0.05565 (10) | 0.0252 (3) | |
O1 | 0.56465 (17) | 0.6326 (5) | −0.1290 (2) | 0.0154 (8) | |
O2 | 0.49883 (18) | 0.4205 (5) | −0.1271 (3) | 0.0189 (8) | |
O3 | 0.7218 (3) | 1.1587 (10) | 0.0423 (4) | 0.0563 (16) | |
N1 | 0.5975 (2) | 0.5189 (5) | −0.2818 (3) | 0.0145 (9) | |
N2 | 0.7136 (2) | 0.6474 (6) | −0.1574 (3) | 0.0147 (9) | |
N3 | 0.6437 (2) | 0.8278 (6) | −0.3163 (3) | 0.0167 (9) | |
C1 | 0.6565 (2) | 0.4132 (6) | −0.2570 (4) | 0.0150 (10) | |
H1A | 0.6788 | 0.4268 | −0.3073 | 0.018* | |
H1B | 0.6451 | 0.2913 | −0.2549 | 0.018* | |
C2 | 0.6998 (3) | 0.4626 (6) | −0.1629 (4) | 0.0176 (11) | |
H2A | 0.6804 | 0.4307 | −0.1113 | 0.021* | |
H2B | 0.7394 | 0.3982 | −0.1537 | 0.021* | |
C3 | 0.7453 (3) | 0.7104 (7) | −0.2280 (4) | 0.0191 (11) | |
H3A | 0.7463 | 0.6189 | −0.2744 | 0.023* | |
H3B | 0.7889 | 0.7416 | −0.1964 | 0.023* | |
C4 | 0.7115 (3) | 0.8647 (7) | −0.2790 (4) | 0.0212 (12) | |
H4A | 0.7169 | 0.9627 | −0.2349 | 0.025* | |
H4B | 0.7298 | 0.8961 | −0.3319 | 0.025* | |
C5 | 0.6297 (3) | 0.7046 (7) | −0.3966 (4) | 0.0182 (11) | |
H5A | 0.6685 | 0.6444 | −0.4000 | 0.022* | |
H5B | 0.6137 | 0.7668 | −0.4568 | 0.022* | |
C6 | 0.5813 (3) | 0.5755 (7) | −0.3828 (3) | 0.0166 (11) | |
H6A | 0.5392 | 0.6282 | −0.3992 | 0.020* | |
H6B | 0.5807 | 0.4759 | −0.4247 | 0.020* | |
C7 | 0.5455 (2) | 0.4318 (7) | −0.2560 (4) | 0.0167 (11) | |
H7A | 0.5541 | 0.3077 | −0.2505 | 0.020* | |
H7B | 0.5068 | 0.4494 | −0.3066 | 0.020* | |
C8 | 0.5361 (2) | 0.4972 (7) | −0.1645 (4) | 0.0164 (11) | |
C9 | 0.7438 (2) | 0.7052 (7) | −0.0614 (4) | 0.0195 (12) | |
H9A | 0.7154 | 0.6792 | −0.0205 | 0.023* | |
H9B | 0.7481 | 0.8309 | −0.0628 | 0.023* | |
C10 | 0.8079 (3) | 0.6299 (8) | −0.0148 (4) | 0.0269 (14) | |
H10A | 0.8035 | 0.5073 | −0.0014 | 0.032* | |
H10B | 0.8354 | 0.6397 | −0.0585 | 0.032* | |
C11 | 0.8375 (2) | 0.7237 (8) | 0.0771 (4) | 0.0214 (12) | |
H11A | 0.8443 | 0.8442 | 0.0618 | 0.026* | |
H11B | 0.8075 | 0.7230 | 0.1172 | 0.026* | |
C12 | 0.8988 (3) | 0.6509 (8) | 0.1337 (4) | 0.0258 (13) | |
H12A | 0.9311 | 0.6706 | 0.0987 | 0.031* | |
H12B | 0.8942 | 0.5260 | 0.1398 | 0.031* | |
C13 | 0.9208 (3) | 0.7283 (8) | 0.2317 (4) | 0.0274 (14) | |
H13A | 0.9258 | 0.8529 | 0.2251 | 0.033* | |
H13B | 0.8879 | 0.7107 | 0.2658 | 0.033* | |
C14 | 0.9817 (3) | 0.6562 (8) | 0.2914 (4) | 0.0265 (13) | |
H14A | 1.0155 | 0.6814 | 0.2600 | 0.032* | |
H14B | 0.9779 | 0.5306 | 0.2947 | 0.032* | |
C15 | 0.9999 (3) | 0.7275 (9) | 0.3913 (4) | 0.0276 (14) | |
H15A | 1.0033 | 0.8532 | 0.3877 | 0.033* | |
H15B | 0.9661 | 0.7018 | 0.4225 | 0.033* | |
C16 | 1.0606 (3) | 0.6581 (9) | 0.4518 (4) | 0.0278 (14) | |
H16A | 1.0946 | 0.6851 | 0.4211 | 0.033* | |
H16B | 1.0575 | 0.5323 | 0.4549 | 0.033* | |
C17 | 1.0781 (3) | 0.7283 (8) | 0.5517 (4) | 0.0289 (14) | |
H17A | 1.0442 | 0.7010 | 0.5825 | 0.035* | |
H17B | 1.0810 | 0.8542 | 0.5486 | 0.035* | |
C18 | 1.1396 (3) | 0.6591 (9) | 0.6132 (4) | 0.0301 (15) | |
H18A | 1.1369 | 0.5333 | 0.6172 | 0.036* | |
H18B | 1.1738 | 0.6866 | 0.5831 | 0.036* | |
C19 | 1.1551 (3) | 0.7339 (11) | 0.7131 (5) | 0.0417 (18) | |
H19A | 1.1947 | 0.6861 | 0.7499 | 0.063* | |
H19B | 1.1217 | 0.7051 | 0.7436 | 0.063* | |
H19C | 1.1588 | 0.8582 | 0.7096 | 0.063* | |
H3 | 0.622 (3) | 0.919 (6) | −0.343 (5) | 0.05 (2)* | |
H31 | 0.695 (5) | 1.105 (16) | −0.006 (6) | 0.16 (6)* | |
H32 | 0.714 (8) | 1.266 (8) | 0.059 (11) | 0.22 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0141 (3) | 0.0100 (3) | 0.0124 (3) | −0.0002 (2) | 0.0038 (2) | −0.0010 (2) |
Cu2 | 0.0238 (5) | 0.0127 (4) | 0.0126 (4) | −0.0055 (4) | 0.0041 (4) | 0.0013 (3) |
Cl1 | 0.0247 (7) | 0.0129 (6) | 0.0199 (6) | −0.0012 (5) | 0.0051 (5) | −0.0045 (5) |
Cl2 | 0.0362 (8) | 0.0131 (6) | 0.0223 (7) | 0.0035 (6) | 0.0000 (6) | −0.0011 (5) |
O1 | 0.021 (2) | 0.0137 (18) | 0.0123 (18) | −0.0014 (15) | 0.0064 (15) | −0.0017 (14) |
O2 | 0.021 (2) | 0.023 (2) | 0.0146 (19) | −0.0062 (16) | 0.0069 (16) | −0.0001 (15) |
O3 | 0.051 (4) | 0.075 (5) | 0.042 (3) | −0.008 (3) | 0.008 (3) | −0.007 (3) |
N1 | 0.016 (2) | 0.012 (2) | 0.014 (2) | 0.0021 (17) | 0.0015 (17) | −0.0001 (17) |
N2 | 0.013 (2) | 0.017 (2) | 0.015 (2) | −0.0003 (17) | 0.0032 (17) | 0.0002 (18) |
N3 | 0.020 (2) | 0.017 (2) | 0.013 (2) | 0.0017 (19) | 0.0038 (18) | −0.0005 (18) |
C1 | 0.021 (3) | 0.006 (2) | 0.017 (3) | 0.001 (2) | 0.003 (2) | 0.0011 (19) |
C2 | 0.020 (3) | 0.011 (2) | 0.020 (3) | 0.005 (2) | 0.003 (2) | 0.005 (2) |
C3 | 0.017 (3) | 0.022 (3) | 0.021 (3) | −0.001 (2) | 0.009 (2) | 0.001 (2) |
C4 | 0.021 (3) | 0.018 (3) | 0.027 (3) | −0.005 (2) | 0.010 (2) | 0.001 (2) |
C5 | 0.027 (3) | 0.014 (3) | 0.016 (3) | 0.001 (2) | 0.010 (2) | 0.001 (2) |
C6 | 0.023 (3) | 0.016 (3) | 0.009 (2) | 0.002 (2) | 0.000 (2) | −0.001 (2) |
C7 | 0.018 (3) | 0.015 (3) | 0.019 (3) | −0.002 (2) | 0.007 (2) | −0.008 (2) |
C8 | 0.018 (3) | 0.018 (3) | 0.014 (3) | 0.001 (2) | 0.005 (2) | −0.001 (2) |
C9 | 0.015 (3) | 0.025 (3) | 0.016 (3) | 0.000 (2) | 0.000 (2) | 0.001 (2) |
C10 | 0.021 (3) | 0.034 (3) | 0.023 (3) | 0.007 (3) | −0.001 (2) | −0.008 (3) |
C11 | 0.018 (3) | 0.028 (3) | 0.017 (3) | 0.000 (2) | 0.001 (2) | −0.002 (2) |
C12 | 0.019 (3) | 0.030 (3) | 0.026 (3) | 0.000 (3) | 0.001 (2) | 0.002 (3) |
C13 | 0.022 (3) | 0.034 (3) | 0.022 (3) | −0.004 (3) | −0.002 (2) | 0.006 (3) |
C14 | 0.021 (3) | 0.030 (3) | 0.025 (3) | −0.002 (3) | 0.001 (2) | 0.004 (3) |
C15 | 0.018 (3) | 0.035 (4) | 0.026 (3) | −0.002 (3) | −0.001 (2) | 0.001 (3) |
C16 | 0.019 (3) | 0.035 (4) | 0.026 (3) | −0.001 (3) | 0.000 (2) | 0.002 (3) |
C17 | 0.025 (3) | 0.034 (4) | 0.024 (3) | −0.005 (3) | 0.000 (2) | 0.009 (3) |
C18 | 0.021 (3) | 0.034 (4) | 0.030 (3) | −0.001 (3) | −0.002 (3) | 0.007 (3) |
C19 | 0.026 (3) | 0.063 (5) | 0.032 (4) | −0.004 (4) | 0.000 (3) | −0.002 (4) |
Cu1—O1 | 1.962 (4) | C7—C8 | 1.495 (7) |
Cu1—N3 | 1.986 (5) | C7—H7A | 0.9900 |
Cu1—N1 | 2.041 (4) | C7—H7B | 0.9900 |
Cu1—Cl1 | 2.2645 (14) | C9—C10 | 1.529 (7) |
Cu1—N2 | 2.289 (4) | C9—H9A | 0.9900 |
Cu2—O2 | 1.954 (4) | C9—H9B | 0.9900 |
Cu2—O2i | 1.954 (4) | C10—C11 | 1.526 (7) |
Cu2—Cl2 | 2.2512 (14) | C10—H10A | 0.9900 |
Cu2—Cl2i | 2.2512 (15) | C10—H10B | 0.9900 |
O1—C8 | 1.276 (6) | C11—C12 | 1.512 (7) |
O2—C8 | 1.251 (6) | C11—H11A | 0.9900 |
O3—H31 | 0.90 (2) | C11—H11B | 0.9900 |
O3—H32 | 0.90 (2) | C12—C13 | 1.519 (8) |
N1—C7 | 1.466 (7) | C12—H12A | 0.9900 |
N1—C6 | 1.496 (6) | C12—H12B | 0.9900 |
N1—C1 | 1.510 (6) | C13—C14 | 1.518 (8) |
N2—C9 | 1.466 (6) | C13—H13A | 0.9900 |
N2—C3 | 1.470 (7) | C13—H13B | 0.9900 |
N2—C2 | 1.477 (6) | C14—C15 | 1.520 (8) |
N3—C4 | 1.490 (7) | C14—H14A | 0.9900 |
N3—C5 | 1.491 (7) | C14—H14B | 0.9900 |
N3—H3 | 0.89 (2) | C15—C16 | 1.511 (8) |
C1—C2 | 1.516 (7) | C15—H15A | 0.9900 |
C1—H1A | 0.9900 | C15—H15B | 0.9900 |
C1—H1B | 0.9900 | C16—C17 | 1.516 (8) |
C2—H2A | 0.9900 | C16—H16A | 0.9900 |
C2—H2B | 0.9900 | C16—H16B | 0.9900 |
C3—C4 | 1.515 (8) | C17—C18 | 1.529 (8) |
C3—H3A | 0.9900 | C17—H17A | 0.9900 |
C3—H3B | 0.9900 | C17—H17B | 0.9900 |
C4—H4A | 0.9900 | C18—C19 | 1.529 (9) |
C4—H4B | 0.9900 | C18—H18A | 0.9900 |
C5—C6 | 1.523 (7) | C18—H18B | 0.9900 |
C5—H5A | 0.9900 | C19—H19A | 0.9800 |
C5—H5B | 0.9900 | C19—H19B | 0.9800 |
C6—H6A | 0.9900 | C19—H19C | 0.9800 |
C6—H6B | 0.9900 | ||
O1—Cu1—N3 | 164.51 (17) | N1—C7—H7A | 109.3 |
O1—Cu1—N1 | 83.65 (16) | C8—C7—H7A | 109.3 |
N3—Cu1—N1 | 85.07 (18) | N1—C7—H7B | 109.3 |
O1—Cu1—Cl1 | 95.16 (11) | C8—C7—H7B | 109.3 |
N3—Cu1—Cl1 | 94.70 (14) | H7A—C7—H7B | 108.0 |
N1—Cu1—Cl1 | 172.72 (13) | O2—C8—O1 | 122.3 (5) |
O1—Cu1—N2 | 107.10 (15) | O2—C8—C7 | 118.8 (5) |
N3—Cu1—N2 | 82.35 (17) | O1—C8—C7 | 118.9 (5) |
N1—Cu1—N2 | 84.80 (16) | N2—C9—C10 | 117.1 (5) |
Cl1—Cu1—N2 | 102.39 (12) | N2—C9—H9A | 108.0 |
O2—Cu2—O2i | 180 | C10—C9—H9A | 108.0 |
O2—Cu2—Cl2 | 91.00 (12) | N2—C9—H9B | 108.0 |
O2i—Cu2—Cl2 | 89.00 (12) | C10—C9—H9B | 108.0 |
O2—Cu2—Cl2i | 89.00 (12) | H9A—C9—H9B | 107.3 |
O2i—Cu2—Cl2i | 91.00 (12) | C11—C10—C9 | 110.5 (5) |
Cl2—Cu2—Cl2i | 180 | C11—C10—H10A | 109.5 |
C8—O1—Cu1 | 114.3 (3) | C9—C10—H10A | 109.5 |
C8—O2—Cu2 | 114.2 (3) | C11—C10—H10B | 109.5 |
H31—O3—H32 | 120 (10) | C9—C10—H10B | 109.5 |
C7—N1—C6 | 112.5 (4) | H10A—C10—H10B | 108.1 |
C7—N1—C1 | 111.7 (4) | C12—C11—C10 | 115.3 (5) |
C6—N1—C1 | 112.2 (4) | C12—C11—H11A | 108.5 |
C7—N1—Cu1 | 107.6 (3) | C10—C11—H11A | 108.5 |
C6—N1—Cu1 | 103.4 (3) | C12—C11—H11B | 108.5 |
C1—N1—Cu1 | 109.0 (3) | C10—C11—H11B | 108.5 |
C9—N2—C3 | 112.7 (4) | H11A—C11—H11B | 107.5 |
C9—N2—C2 | 113.1 (4) | C11—C12—C13 | 113.4 (5) |
C3—N2—C2 | 114.7 (4) | C11—C12—H12A | 108.9 |
C9—N2—Cu1 | 112.4 (3) | C13—C12—H12A | 108.9 |
C3—N2—Cu1 | 105.0 (3) | C11—C12—H12B | 108.9 |
C2—N2—Cu1 | 97.6 (3) | C13—C12—H12B | 108.9 |
C4—N3—C5 | 113.8 (4) | H12A—C12—H12B | 107.7 |
C4—N3—Cu1 | 106.8 (3) | C14—C13—C12 | 114.9 (5) |
C5—N3—Cu1 | 111.4 (3) | C14—C13—H13A | 108.5 |
C4—N3—H3 | 113 (5) | C12—C13—H13A | 108.5 |
C5—N3—H3 | 101 (5) | C14—C13—H13B | 108.5 |
Cu1—N3—H3 | 111 (5) | C12—C13—H13B | 108.5 |
N1—C1—C2 | 112.9 (4) | H13A—C13—H13B | 107.5 |
N1—C1—H1A | 109.0 | C13—C14—C15 | 113.4 (5) |
C2—C1—H1A | 109.0 | C13—C14—H14A | 108.9 |
N1—C1—H1B | 109.0 | C15—C14—H14A | 108.9 |
C2—C1—H1B | 109.0 | C13—C14—H14B | 108.9 |
H1A—C1—H1B | 107.8 | C15—C14—H14B | 108.9 |
N2—C2—C1 | 112.0 (4) | H14A—C14—H14B | 107.7 |
N2—C2—H2A | 109.2 | C16—C15—C14 | 114.3 (5) |
C1—C2—H2A | 109.2 | C16—C15—H15A | 108.7 |
N2—C2—H2B | 109.2 | C14—C15—H15A | 108.7 |
C1—C2—H2B | 109.2 | C16—C15—H15B | 108.7 |
H2A—C2—H2B | 107.9 | C14—C15—H15B | 108.7 |
N2—C3—C4 | 110.5 (4) | H15A—C15—H15B | 107.6 |
N2—C3—H3A | 109.6 | C15—C16—C17 | 114.0 (5) |
C4—C3—H3A | 109.6 | C15—C16—H16A | 108.8 |
N2—C3—H3B | 109.6 | C17—C16—H16A | 108.8 |
C4—C3—H3B | 109.6 | C15—C16—H16B | 108.8 |
H3A—C3—H3B | 108.1 | C17—C16—H16B | 108.8 |
N3—C4—C3 | 110.6 (4) | H16A—C16—H16B | 107.6 |
N3—C4—H4A | 109.5 | C16—C17—C18 | 114.2 (6) |
C3—C4—H4A | 109.5 | C16—C17—H17A | 108.7 |
N3—C4—H4B | 109.5 | C18—C17—H17A | 108.7 |
C3—C4—H4B | 109.5 | C16—C17—H17B | 108.7 |
H4A—C4—H4B | 108.1 | C18—C17—H17B | 108.7 |
N3—C5—C6 | 109.8 (4) | H17A—C17—H17B | 107.6 |
N3—C5—H5A | 109.7 | C19—C18—C17 | 112.2 (6) |
C6—C5—H5A | 109.7 | C19—C18—H18A | 109.2 |
N3—C5—H5B | 109.7 | C17—C18—H18A | 109.2 |
C6—C5—H5B | 109.7 | C19—C18—H18B | 109.2 |
H5A—C5—H5B | 108.2 | C17—C18—H18B | 109.2 |
N1—C6—C5 | 109.0 (4) | H18A—C18—H18B | 107.9 |
N1—C6—H6A | 109.9 | C18—C19—H19A | 109.5 |
C5—C6—H6A | 109.9 | C18—C19—H19B | 109.5 |
N1—C6—H6B | 109.9 | H19A—C19—H19B | 109.5 |
C5—C6—H6B | 109.9 | C18—C19—H19C | 109.5 |
H6A—C6—H6B | 108.3 | H19A—C19—H19C | 109.5 |
N1—C7—C8 | 111.4 (4) | H19B—C19—H19C | 109.5 |
Symmetry code: (i) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H31···Cl1 | 0.90 (2) | 2.37 (3) | 3.267 (7) | 172 (12) |
N3—H3···Cl2ii | 0.89 (2) | 2.31 (3) | 3.161 (5) | 160 (7) |
Symmetry code: (ii) −x+1, y+1/2, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu3Cl4(C17H38N3O2)2]·2H2O |
Mr | 1049.50 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 22.1182 (11), 7.8330 (4), 14.6177 (7) |
β (°) | 104.570 (2) |
V (Å3) | 2451.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.56 |
Crystal size (mm) | 0.20 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Bruker X8 APEX CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.746, 0.926 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25491, 5625, 4994 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.084, 0.142, 1.32 |
No. of reflections | 5625 |
No. of parameters | 271 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + 12.2399P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.62, −1.02 |
Computer programs: APEX2 (Bruker, 2005), APEX2, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H31···Cl1 | 0.90 (2) | 2.37 (3) | 3.267 (7) | 172 (12) |
N3—H3···Cl2i | 0.89 (2) | 2.31 (3) | 3.161 (5) | 160 (7) |
Symmetry code: (i) −x+1, y+1/2, −z−1/2. |
The title complex, (I), crystallizes in the monoclinic space group (P21/c), with the asymmetric unit comprising one half of the molecule [Cu(AcC11tacn)Cl.H2O]2.CuCl2, Fig. 1; the Cu2 atom is located on a crystallographic inversion centre. The three N atoms from the macrocycle coordinate facially to Cu1, which is also bound to a terminal Cl with the fifth coordination site completed by the O atom derived from the N-acetyl group. Two of these units are further connected via the keto-O atoms to a four coordinate copper dichloride entity. The Cu1—Cl1 bond distance (2.2645 (14) Å) is slightly longer than the Cu2—Cl2 distance of 2.2512 (14) Å, but this may also reflect the interaction of Cl1 with the water molecule via a O3—H31···Cl1 (2.37 (3) Å) hydrogen bond. The Cu—N distances are inequivalent with the C11 substituted N atom having the longest bond (Cu1—N2 2.289 (4) Å) whilst the secondary amine has the shortest (Cu1—N3 1.985 (4) Å).
The cell contents, when viewed along the b axis, Fig. 2, show the straight chain C11 units form interdigitated layers which separate the hydrophilic {Cu(Actacn)Cl}.CuCl2 moieties, the latter associated via intermolecular N3—H3···Cl2i hydrogen bonds (Table 1).