A new centrosymmetric tetranuclear complex, [Cu4(μ-Cl)6Cl2(C12H16N4O2)2], was obtained in varied yields by reaction of bis(3,5-dimethylpyrazol-1-yl)acetic acid (Hbdmpza) with CuCl2·2H2O in a highly concentrated acetonitrile solution. Two different types of coordination environment for the Cu atoms characterize the title compound, namely square-pyramidal CuCl2N2Cl and distorted square-planar CuCl4 donor sets. The tetranuclear molecule is located on a centre of inversion in the crystal structure and the molecules are connected via very strong bis-carboxylate hydrogen bonds, resulting in a polymeric chain.
Supporting information
CCDC reference: 636811
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.031
- wR factor = 0.071
- Data-to-parameter ratio = 18.4
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - Cl3 .. 7.58 su
Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
2 ALERT level G = General alerts; check
2 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
0 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
Hexakis-µ-chloro-dichloro-bis[(3,5-dimethylpyrazol-1-yl)acetic
acid-
κ2N,
N']tetracopper(II)
top
Crystal data top
[Cu4Cl8(C12H16N4O2)2] | Z = 1 |
Mr = 1034.34 | F(000) = 516 |
Triclinic, P1 | Dx = 1.871 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3869 (2) Å | Cell parameters from 2660 reflections |
b = 10.6666 (2) Å | θ = 2.6–27.5° |
c = 10.7902 (3) Å | µ = 2.91 mm−1 |
α = 117.6094 (10)° | T = 293 K |
β = 98.685 (1)° | Prism, green |
γ = 98.2172 (16)° | 0.15 × 0.13 × 0.10 mm |
V = 918.00 (4) Å3 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 4088 independent reflections |
Radiation source: fine-focus sealed tube | 3395 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 0.055 pixels mm-1 | θmax = 27.4°, θmin = 3.2° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | k = −11→13 |
Tmin = 0.669, Tmax = 0.760 | l = −13→13 |
5946 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0056P)2 + 0.8188P] where P = (Fo2 + 2Fc2)/3 |
4088 reflections | (Δ/σ)max = 0.001 |
222 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
Special details top
Experimental. 180 frames in 5 sets of ω scans. Rotation/frame = 2.0 °. Crystal-detector
distance = 35 mm. Measuring time = 150 s/°. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.30376 (3) | 0.21188 (3) | 0.34146 (3) | 0.03155 (9) | |
Cu2 | 0.59683 (3) | 0.42317 (3) | 0.63618 (3) | 0.03519 (10) | |
Cl1 | 0.35694 (8) | 0.30219 (8) | 0.58896 (8) | 0.04656 (18) | |
Cl2 | 0.55161 (7) | 0.32958 (7) | 0.38963 (7) | 0.03909 (16) | |
Cl3 | 0.20099 (7) | 0.40432 (7) | 0.31419 (8) | 0.04486 (18) | |
Cl4 | 0.66124 (10) | 0.41947 (8) | 0.83939 (9) | 0.0598 (2) | |
O1 | 0.3127 (2) | −0.0865 (2) | 0.4299 (2) | 0.0441 (5) | |
H1 | 0.3841 | −0.0507 | 0.4999 | 0.066* | |
O2 | 0.48045 (19) | −0.0269 (2) | 0.3271 (2) | 0.0400 (4) | |
N1 | 0.1142 (2) | 0.0802 (2) | 0.3197 (2) | 0.0333 (5) | |
N2 | 0.0980 (2) | −0.0677 (2) | 0.2447 (2) | 0.0324 (5) | |
N3 | 0.2629 (2) | −0.0797 (2) | 0.0963 (2) | 0.0312 (5) | |
N4 | 0.3046 (2) | 0.0662 (2) | 0.1394 (2) | 0.0312 (5) | |
C1 | −0.0357 (3) | 0.2467 (3) | 0.4520 (3) | 0.0479 (7) | |
H1A | 0.0548 | 0.3127 | 0.5207 | 0.072* | |
H1B | −0.1105 | 0.2408 | 0.5019 | 0.072* | |
H1C | −0.0686 | 0.2815 | 0.3877 | 0.072* | |
C2 | −0.0088 (3) | 0.0994 (3) | 0.3675 (3) | 0.0360 (6) | |
C3 | −0.1003 (3) | −0.0371 (3) | 0.3236 (3) | 0.0421 (7) | |
H3 | −0.1922 | −0.0537 | 0.3431 | 0.051* | |
C4 | −0.0311 (3) | −0.1409 (3) | 0.2475 (3) | 0.0362 (6) | |
C5 | −0.0745 (3) | −0.3031 (3) | 0.1754 (4) | 0.0501 (8) | |
H5A | −0.1665 | −0.3333 | 0.1940 | 0.075* | |
H5B | 0.0015 | −0.3370 | 0.2125 | 0.075* | |
H5C | −0.0867 | −0.3435 | 0.0732 | 0.075* | |
C6 | 0.2229 (3) | −0.1227 (3) | 0.1966 (3) | 0.0301 (5) | |
H6 | 0.1923 | −0.2294 | 0.1459 | 0.036* | |
C7 | 0.3521 (3) | −0.0732 (3) | 0.3281 (3) | 0.0307 (5) | |
C8 | 0.2125 (3) | −0.3271 (3) | −0.1219 (3) | 0.0446 (7) | |
H8A | 0.2672 | −0.3628 | −0.0677 | 0.067* | |
H8B | 0.2320 | −0.3657 | −0.2159 | 0.067* | |
H8C | 0.1082 | −0.3574 | −0.1317 | 0.067* | |
C9 | 0.2596 (3) | −0.1642 (3) | −0.0447 (3) | 0.0334 (6) | |
C10 | 0.3028 (3) | −0.0702 (3) | −0.0932 (3) | 0.0376 (6) | |
H10 | 0.3128 | −0.0955 | −0.1858 | 0.045* | |
C11 | 0.3291 (3) | 0.0716 (3) | 0.0235 (3) | 0.0329 (5) | |
C12 | 0.3764 (3) | 0.2118 (3) | 0.0247 (3) | 0.0418 (6) | |
H12A | 0.2947 | 0.2574 | 0.0299 | 0.063* | |
H12B | 0.4071 | 0.1930 | −0.0619 | 0.063* | |
H12C | 0.4578 | 0.2754 | 0.1071 | 0.063* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.03194 (17) | 0.02364 (17) | 0.02835 (18) | 0.00061 (12) | 0.00512 (13) | 0.00673 (14) |
Cu2 | 0.03733 (18) | 0.02595 (18) | 0.03091 (19) | 0.00189 (13) | −0.00043 (14) | 0.00922 (15) |
Cl1 | 0.0435 (4) | 0.0502 (4) | 0.0315 (4) | −0.0062 (3) | 0.0064 (3) | 0.0144 (3) |
Cl2 | 0.0345 (3) | 0.0351 (4) | 0.0310 (4) | −0.0012 (3) | 0.0071 (3) | 0.0060 (3) |
Cl3 | 0.0319 (3) | 0.0348 (4) | 0.0556 (5) | 0.0016 (3) | −0.0016 (3) | 0.0181 (3) |
Cl4 | 0.0919 (6) | 0.0342 (4) | 0.0388 (4) | 0.0086 (4) | −0.0109 (4) | 0.0164 (3) |
O1 | 0.0383 (10) | 0.0588 (13) | 0.0321 (11) | 0.0056 (9) | 0.0056 (8) | 0.0227 (11) |
O2 | 0.0326 (10) | 0.0461 (12) | 0.0436 (12) | 0.0040 (8) | 0.0072 (8) | 0.0262 (10) |
N1 | 0.0305 (11) | 0.0265 (11) | 0.0327 (12) | 0.0020 (8) | 0.0043 (9) | 0.0090 (10) |
N2 | 0.0306 (10) | 0.0246 (11) | 0.0324 (12) | 0.0012 (8) | 0.0032 (9) | 0.0093 (10) |
N3 | 0.0385 (11) | 0.0218 (11) | 0.0255 (11) | 0.0038 (8) | 0.0045 (9) | 0.0075 (9) |
N4 | 0.0366 (11) | 0.0219 (10) | 0.0281 (12) | 0.0027 (8) | 0.0029 (9) | 0.0095 (9) |
C1 | 0.0399 (15) | 0.0456 (18) | 0.0497 (19) | 0.0107 (13) | 0.0138 (14) | 0.0161 (15) |
C2 | 0.0304 (13) | 0.0392 (15) | 0.0313 (14) | 0.0056 (11) | 0.0048 (11) | 0.0134 (12) |
C3 | 0.0310 (13) | 0.0451 (17) | 0.0453 (18) | 0.0014 (12) | 0.0086 (12) | 0.0208 (14) |
C4 | 0.0308 (13) | 0.0362 (15) | 0.0339 (15) | −0.0030 (11) | −0.0008 (11) | 0.0170 (13) |
C5 | 0.0456 (16) | 0.0360 (16) | 0.055 (2) | −0.0066 (13) | 0.0056 (14) | 0.0179 (15) |
C6 | 0.0334 (12) | 0.0227 (12) | 0.0277 (13) | 0.0032 (10) | 0.0044 (10) | 0.0092 (11) |
C7 | 0.0376 (14) | 0.0207 (12) | 0.0294 (14) | 0.0059 (10) | 0.0065 (11) | 0.0098 (11) |
C8 | 0.0602 (18) | 0.0268 (14) | 0.0356 (16) | 0.0063 (13) | 0.0072 (13) | 0.0091 (13) |
C9 | 0.0369 (13) | 0.0261 (13) | 0.0267 (14) | 0.0057 (10) | 0.0013 (11) | 0.0072 (11) |
C10 | 0.0524 (16) | 0.0315 (14) | 0.0237 (14) | 0.0107 (12) | 0.0062 (12) | 0.0103 (12) |
C11 | 0.0357 (13) | 0.0320 (14) | 0.0281 (14) | 0.0068 (10) | 0.0028 (11) | 0.0145 (12) |
C12 | 0.0528 (17) | 0.0316 (15) | 0.0401 (17) | 0.0076 (12) | 0.0071 (13) | 0.0191 (13) |
Geometric parameters (Å, º) top
Cu1—N4 | 2.009 (2) | C1—H1B | 0.9600 |
Cu1—N1 | 2.012 (2) | C1—H1C | 0.9600 |
Cu1—Cl1 | 2.3205 (8) | C2—C3 | 1.401 (4) |
Cu1—Cl2 | 2.3354 (7) | C3—C4 | 1.359 (4) |
Cu1—Cl3 | 2.5042 (8) | C3—H3 | 0.9300 |
Cu2—Cl4 | 2.2050 (8) | C4—C5 | 1.489 (4) |
Cu2—Cl3i | 2.2485 (7) | C5—H5A | 0.9600 |
Cu2—Cl1 | 2.2823 (7) | C5—H5B | 0.9600 |
Cu2—Cl2 | 2.3087 (7) | C5—H5C | 0.9600 |
Cl3—Cu2i | 2.2485 (7) | C6—C7 | 1.539 (4) |
O1—C7 | 1.271 (3) | C6—H6 | 0.9800 |
O1—H1 | 0.8200 | C8—C9 | 1.495 (4) |
O2—C7 | 1.239 (3) | C8—H8A | 0.9600 |
N1—C2 | 1.337 (3) | C8—H8B | 0.9600 |
N1—N2 | 1.370 (3) | C8—H8C | 0.9600 |
N2—C4 | 1.358 (3) | C9—C10 | 1.370 (4) |
N2—C6 | 1.445 (3) | C10—C11 | 1.403 (4) |
N3—C9 | 1.355 (3) | C10—H10 | 0.9300 |
N3—N4 | 1.375 (3) | C11—C12 | 1.491 (4) |
N3—C6 | 1.434 (3) | C12—H12A | 0.9600 |
N4—C11 | 1.331 (3) | C12—H12B | 0.9600 |
C1—C2 | 1.490 (4) | C12—H12C | 0.9600 |
C1—H1A | 0.9600 | | |
| | | |
N4—Cu1—N1 | 88.39 (8) | C4—C3—H3 | 126.1 |
N4—Cu1—Cl1 | 152.83 (7) | C2—C3—H3 | 126.1 |
N1—Cu1—Cl1 | 89.33 (7) | N2—C4—C3 | 105.8 (2) |
N4—Cu1—Cl2 | 91.75 (6) | N2—C4—C5 | 122.3 (2) |
N1—Cu1—Cl2 | 165.17 (7) | C3—C4—C5 | 132.0 (2) |
Cl1—Cu1—Cl2 | 83.80 (2) | C4—C5—H5A | 109.5 |
N4—Cu1—Cl3 | 104.13 (6) | C4—C5—H5B | 109.5 |
N1—Cu1—Cl3 | 99.70 (6) | H5A—C5—H5B | 109.5 |
Cl1—Cu1—Cl3 | 102.94 (3) | C4—C5—H5C | 109.5 |
Cl2—Cu1—Cl3 | 94.65 (2) | H5A—C5—H5C | 109.5 |
Cl4—Cu2—Cl3i | 95.05 (3) | H5B—C5—H5C | 109.5 |
Cl4—Cu2—Cl1 | 92.67 (3) | N3—C6—N2 | 110.5 (2) |
Cl3i—Cu2—Cl1 | 162.56 (3) | N3—C6—C7 | 113.1 (2) |
Cl4—Cu2—Cl2 | 155.10 (3) | N2—C6—C7 | 109.6 (2) |
Cl3i—Cu2—Cl2 | 94.11 (3) | N3—C6—H6 | 107.8 |
Cl1—Cu2—Cl2 | 85.25 (2) | N2—C6—H6 | 107.8 |
Cu2—Cl1—Cu1 | 96.01 (3) | C7—C6—H6 | 107.8 |
Cu2—Cl2—Cu1 | 94.89 (3) | O2—C7—O1 | 126.2 (2) |
Cu2i—Cl3—Cu1 | 104.29 (3) | O2—C7—C6 | 119.9 (2) |
C7—O1—H1 | 109.5 | O1—C7—C6 | 113.8 (2) |
C2—N1—N2 | 105.68 (19) | C9—C8—H8A | 109.5 |
C2—N1—Cu1 | 135.58 (18) | C9—C8—H8B | 109.5 |
N2—N1—Cu1 | 118.67 (15) | H8A—C8—H8B | 109.5 |
C4—N2—N1 | 111.6 (2) | C9—C8—H8C | 109.5 |
C4—N2—C6 | 128.8 (2) | H8A—C8—H8C | 109.5 |
N1—N2—C6 | 118.70 (18) | H8B—C8—H8C | 109.5 |
C9—N3—N4 | 111.5 (2) | N3—C9—C10 | 106.1 (2) |
C9—N3—C6 | 129.1 (2) | N3—C9—C8 | 123.0 (2) |
N4—N3—C6 | 119.36 (19) | C10—C9—C8 | 130.8 (2) |
C11—N4—N3 | 105.6 (2) | C9—C10—C11 | 106.9 (2) |
C11—N4—Cu1 | 136.02 (17) | C9—C10—H10 | 126.5 |
N3—N4—Cu1 | 118.29 (15) | C11—C10—H10 | 126.5 |
C2—C1—H1A | 109.5 | N4—C11—C10 | 109.9 (2) |
C2—C1—H1B | 109.5 | N4—C11—C12 | 122.6 (2) |
H1A—C1—H1B | 109.5 | C10—C11—C12 | 127.5 (2) |
C2—C1—H1C | 109.5 | C11—C12—H12A | 109.5 |
H1A—C1—H1C | 109.5 | C11—C12—H12B | 109.5 |
H1B—C1—H1C | 109.5 | H12A—C12—H12B | 109.5 |
N1—C2—C3 | 109.1 (2) | C11—C12—H12C | 109.5 |
N1—C2—C1 | 122.3 (2) | H12A—C12—H12C | 109.5 |
C3—C2—C1 | 128.6 (2) | H12B—C12—H12C | 109.5 |
C4—C3—C2 | 107.9 (2) | | |
| | | |
Cl4—Cu2—Cl1—Cu1 | −156.89 (3) | Cl1—Cu1—N4—N3 | 45.5 (2) |
Cl3i—Cu2—Cl1—Cu1 | 86.83 (10) | Cl2—Cu1—N4—N3 | 125.28 (16) |
Cl2—Cu2—Cl1—Cu1 | −1.76 (3) | Cl3—Cu1—N4—N3 | −139.48 (15) |
N4—Cu1—Cl1—Cu2 | 83.43 (13) | N2—N1—C2—C3 | 0.9 (3) |
N1—Cu1—Cl1—Cu2 | 168.58 (7) | Cu1—N1—C2—C3 | −175.9 (2) |
Cl2—Cu1—Cl1—Cu2 | 1.75 (3) | N2—N1—C2—C1 | −178.5 (3) |
Cl3—Cu1—Cl1—Cu2 | −91.62 (3) | Cu1—N1—C2—C1 | 4.7 (4) |
Cl4—Cu2—Cl2—Cu1 | 87.86 (8) | N1—C2—C3—C4 | −0.1 (3) |
Cl3i—Cu2—Cl2—Cu1 | −160.77 (3) | C1—C2—C3—C4 | 179.3 (3) |
Cl1—Cu2—Cl2—Cu1 | 1.75 (3) | N1—N2—C4—C3 | 1.4 (3) |
N4—Cu1—Cl2—Cu2 | −154.84 (6) | C6—N2—C4—C3 | 170.1 (3) |
N1—Cu1—Cl2—Cu2 | −64.5 (3) | N1—N2—C4—C5 | −179.3 (2) |
Cl1—Cu1—Cl2—Cu2 | −1.72 (3) | C6—N2—C4—C5 | −10.6 (4) |
Cl3—Cu1—Cl2—Cu2 | 100.82 (3) | C2—C3—C4—N2 | −0.8 (3) |
N4—Cu1—Cl3—Cu2i | −96.11 (6) | C2—C3—C4—C5 | 179.9 (3) |
N1—Cu1—Cl3—Cu2i | 173.11 (7) | C9—N3—C6—N2 | −116.5 (3) |
Cl1—Cu1—Cl3—Cu2i | 81.55 (3) | N4—N3—C6—N2 | 59.9 (3) |
Cl2—Cu1—Cl3—Cu2i | −3.13 (3) | C9—N3—C6—C7 | 120.2 (3) |
N4—Cu1—N1—C2 | −146.3 (3) | N4—N3—C6—C7 | −63.4 (3) |
Cl1—Cu1—N1—C2 | 60.8 (3) | C4—N2—C6—N3 | 129.1 (3) |
Cl2—Cu1—N1—C2 | 123.0 (3) | N1—N2—C6—N3 | −62.8 (3) |
Cl3—Cu1—N1—C2 | −42.2 (3) | C4—N2—C6—C7 | −105.5 (3) |
N4—Cu1—N1—N2 | 37.31 (18) | N1—N2—C6—C7 | 62.5 (3) |
Cl1—Cu1—N1—N2 | −115.61 (18) | N3—C6—C7—O2 | −12.7 (3) |
Cl2—Cu1—N1—N2 | −53.4 (4) | N2—C6—C7—O2 | −136.5 (2) |
Cl3—Cu1—N1—N2 | 141.37 (17) | N3—C6—C7—O1 | 167.9 (2) |
C2—N1—N2—C4 | −1.4 (3) | N2—C6—C7—O1 | 44.1 (3) |
Cu1—N1—N2—C4 | 176.00 (17) | N4—N3—C9—C10 | 1.0 (3) |
C2—N1—N2—C6 | −171.4 (2) | C6—N3—C9—C10 | 177.6 (2) |
Cu1—N1—N2—C6 | 6.0 (3) | N4—N3—C9—C8 | −177.7 (2) |
C9—N3—N4—C11 | −0.7 (3) | C6—N3—C9—C8 | −1.0 (4) |
C6—N3—N4—C11 | −177.7 (2) | N3—C9—C10—C11 | −0.9 (3) |
C9—N3—N4—Cu1 | 175.98 (16) | C8—C9—C10—C11 | 177.7 (3) |
C6—N3—N4—Cu1 | −1.0 (3) | N3—N4—C11—C10 | 0.1 (3) |
N1—Cu1—N4—C11 | 135.5 (3) | Cu1—N4—C11—C10 | −175.66 (19) |
Cl1—Cu1—N4—C11 | −139.1 (2) | N3—N4—C11—C12 | 179.7 (2) |
Cl2—Cu1—N4—C11 | −59.3 (2) | Cu1—N4—C11—C12 | 3.9 (4) |
Cl3—Cu1—N4—C11 | 35.9 (3) | C9—C10—C11—N4 | 0.5 (3) |
N1—Cu1—N4—N3 | −39.88 (17) | C9—C10—C11—C12 | −179.1 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2ii | 0.82 | 1.83 | 2.638 (3) | 170 |
Symmetry code: (ii) −x+1, −y, −z+1. |