In the title dimeric complex, [Cu
2(C
4H
4O
4)
2(C
7H
6N
2S)
4], which possesses a centre of symmetry, the Cu atoms are enclosed in a 14-membered ring. They adopt a distorted square-bipyramidal (4+2) coordination. The four closest donor atoms are two N atoms of 2-aminobenzothiazole ligands and two O atoms of the succinate carboxylate groups. They form a square-planar
cis arrangement, with an average Cu—N distance of 2.003 (3) Å and Cu—O distances of 1.949 (3) and 1.965 (3) Å. Two longer Cu—O bonds of 2.709 (3) and 2.613 (3) Å involving the remaining O atoms of the carboxylate groups complete the sixfold coordination of the Cu atoms. The H atoms of each amino group of the 2-aminobenzothiazole molecules form intra- and intermolecular N—H
O hydrogen bonds. A nearly perpendicular intermolecular C—H
Cg interaction (
Cg is the centroid of the imidazole ring) is observed. The intramolecular Cu
Cu distance is 6.384 (2) Å.
Supporting information
CCDC reference: 140922
The title complex was prepared by dissolving equimolar quantities (1 mmol) of 2-aminobenzothiazole, succinic acid and copper(II) chloride dihydrate (CuCl2.2H2O) in water (80 ml). After heating to boiling, the solution was filtered and allowed to cool. After several hours, green crystals of (I) were obtained.
Refined C—H distances are in the range 0.82 (6)–0.98 (4) Å.
Data collection: P3 software; cell refinement: P3 software; data reduction: XDISK in SHELXTL/PC (Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: XP in SHELXTL/PC; software used to prepare material for publication: SHELXL97.
Bis[bis(2-amino-1,3-benzothiazole-N
3)(µ-succinato-O,
O',
O'',
O''')copper(II)]
top
Crystal data top
[Cu2(C4H4O4)2(C7H6N2S)4] | F(000) = 980 |
Mr = 960.08 | Dx = 1.630 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 32 reflections |
a = 9.239 (2) Å | θ = 4.2–14.3° |
b = 15.643 (3) Å | µ = 1.36 mm−1 |
c = 13.859 (3) Å | T = 293 K |
β = 102.37 (2)° | Prism, green |
V = 1956.5 (7) Å3 | 0.23 × 0.13 × 0.13 mm |
Z = 2 | |
Data collection top
Siemens P3 diffractometer | 2516 reflections with I > 2σ(I) |
Radiation source: FK60-10 Siemens Mo tube | Rint = 0.035 |
Graphite monochromator | θmax = 25°, θmin = 2.0° |
ω–2θ scans | h = −10→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→18 |
Tmin = 0.740, Tmax = 0.848 | l = 0→16 |
3561 measured reflections | 2 standard reflections every 100 reflections |
3414 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.029P)2 + 2.511P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.090 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.33 e Å−3 |
3414 reflections | Δρmin = −0.28 e Å−3 |
326 parameters | |
Crystal data top
[Cu2(C4H4O4)2(C7H6N2S)4] | V = 1956.5 (7) Å3 |
Mr = 960.08 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.239 (2) Å | µ = 1.36 mm−1 |
b = 15.643 (3) Å | T = 293 K |
c = 13.859 (3) Å | 0.23 × 0.13 × 0.13 mm |
β = 102.37 (2)° | |
Data collection top
Siemens P3 diffractometer | 2516 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.035 |
Tmin = 0.740, Tmax = 0.848 | 2 standard reflections every 100 reflections |
3561 measured reflections | intensity decay: none |
3414 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.090 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.33 e Å−3 |
3414 reflections | Δρmin = −0.28 e Å−3 |
326 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'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. The title structure was solved by direct methods and refined by full-matrix least-squares calculations. All non-H atoms were refined anisotropically. All H atoms were located from a difference synthesis and refined isotropically. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.21597 (5) | 0.14174 (3) | 0.44318 (3) | 0.02887 (14) | |
S1 | 0.02645 (13) | 0.40288 (7) | 0.34243 (9) | 0.0489 (3) | |
O1 | 0.2069 (3) | 0.02104 (17) | 0.4075 (2) | 0.0399 (7) | |
O2 | −0.0109 (3) | 0.06109 (18) | 0.3208 (2) | 0.0461 (7) | |
N1 | 0.1651 (3) | 0.26506 (19) | 0.4161 (2) | 0.0318 (7) | |
N2 | −0.0472 (4) | 0.2410 (3) | 0.2925 (3) | 0.0454 (10) | |
C1 | 0.0489 (4) | 0.2918 (2) | 0.3505 (3) | 0.0333 (9) | |
C2 | 0.1844 (5) | 0.4141 (3) | 0.4372 (3) | 0.0405 (10) | |
C3 | 0.2447 (6) | 0.4886 (3) | 0.4831 (4) | 0.0529 (13) | |
C4 | 0.3697 (6) | 0.4822 (3) | 0.5565 (4) | 0.0518 (12) | |
C5 | 0.4345 (5) | 0.4032 (3) | 0.5834 (3) | 0.0450 (11) | |
C6 | 0.3734 (5) | 0.3291 (3) | 0.5383 (3) | 0.0378 (10) | |
C7 | 0.2453 (4) | 0.3341 (2) | 0.4656 (3) | 0.0324 (9) | |
C8 | 0.0815 (4) | 0.0057 (2) | 0.3494 (3) | 0.0330 (9) | |
C9 | 0.0591 (4) | −0.0856 (3) | 0.3135 (3) | 0.0355 (9) | |
S11 | 0.67702 (13) | 0.09556 (8) | 0.39673 (10) | 0.0548 (3) | |
O11 | 0.0856 (3) | 0.12443 (17) | 0.53640 (18) | 0.0365 (6) | |
O12 | 0.3021 (3) | 0.14884 (18) | 0.6353 (2) | 0.0403 (7) | |
N11 | 0.4114 (3) | 0.1470 (2) | 0.4028 (2) | 0.0332 (7) | |
N12 | 0.5517 (5) | 0.0973 (3) | 0.5535 (3) | 0.0492 (10) | |
C11 | 0.5323 (4) | 0.1145 (2) | 0.4575 (3) | 0.0377 (10) | |
C12 | 0.5644 (5) | 0.1335 (3) | 0.2882 (3) | 0.0453 (11) | |
C13 | 0.5944 (6) | 0.1410 (3) | 0.1945 (4) | 0.0558 (13) | |
C14 | 0.4876 (7) | 0.1733 (3) | 0.1196 (4) | 0.0596 (15) | |
C15 | 0.3510 (6) | 0.1987 (3) | 0.1360 (4) | 0.0519 (13) | |
C16 | 0.3191 (5) | 0.1913 (3) | 0.2280 (3) | 0.0408 (10) | |
C17 | 0.4249 (5) | 0.1591 (2) | 0.3050 (3) | 0.0389 (10) | |
C18 | 0.1670 (4) | 0.1302 (2) | 0.6214 (3) | 0.0307 (8) | |
C19 | 0.1000 (5) | 0.1146 (3) | 0.7098 (3) | 0.0360 (9) | |
H3 | 0.201 (6) | 0.534 (4) | 0.469 (4) | 0.09 (2)* | |
H4 | 0.408 (4) | 0.528 (3) | 0.586 (3) | 0.043 (12)* | |
H5 | 0.516 (5) | 0.402 (3) | 0.632 (3) | 0.053 (14)* | |
H6 | 0.416 (4) | 0.278 (2) | 0.553 (3) | 0.030 (10)* | |
H13 | 0.689 (6) | 0.121 (3) | 0.188 (4) | 0.071 (16)* | |
H14 | 0.508 (5) | 0.179 (3) | 0.059 (4) | 0.067 (15)* | |
H15 | 0.284 (5) | 0.218 (3) | 0.090 (4) | 0.057 (16)* | |
H16 | 0.229 (4) | 0.207 (2) | 0.238 (3) | 0.025 (10)* | |
H21 | −0.041 (5) | 0.188 (3) | 0.301 (4) | 0.057 (15)* | |
H22 | −0.108 (5) | 0.264 (3) | 0.250 (3) | 0.040 (13)* | |
H81 | 0.120 (4) | −0.123 (2) | 0.364 (3) | 0.033 (10)* | |
H82 | 0.096 (4) | −0.084 (2) | 0.253 (3) | 0.037 (11)* | |
H121 | 0.477 (6) | 0.100 (3) | 0.579 (3) | 0.056 (15)* | |
H122 | 0.620 (6) | 0.067 (3) | 0.581 (4) | 0.061 (16)* | |
H191 | 0.163 (4) | 0.079 (2) | 0.746 (3) | 0.019 (9)* | |
H192 | 0.115 (5) | 0.166 (3) | 0.745 (3) | 0.049 (13)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.0257 (2) | 0.0294 (2) | 0.0318 (2) | 0.0018 (2) | 0.00677 (17) | 0.0019 (2) |
S1 | 0.0522 (7) | 0.0339 (6) | 0.0553 (7) | 0.0111 (5) | −0.0003 (6) | 0.0072 (5) |
O1 | 0.0253 (14) | 0.0327 (15) | 0.0606 (19) | −0.0008 (12) | 0.0069 (13) | −0.0077 (13) |
O2 | 0.0544 (19) | 0.0363 (16) | 0.0424 (17) | 0.0082 (14) | −0.0011 (14) | 0.0051 (13) |
N1 | 0.0306 (18) | 0.0306 (17) | 0.0347 (18) | 0.0026 (14) | 0.0083 (14) | 0.0033 (14) |
N2 | 0.042 (2) | 0.041 (2) | 0.046 (2) | 0.0055 (19) | −0.0083 (18) | 0.0049 (19) |
C1 | 0.033 (2) | 0.031 (2) | 0.036 (2) | 0.0044 (17) | 0.0086 (18) | 0.0011 (17) |
C2 | 0.044 (3) | 0.035 (2) | 0.042 (2) | 0.0038 (19) | 0.010 (2) | −0.0003 (19) |
C3 | 0.069 (4) | 0.032 (3) | 0.058 (3) | −0.002 (2) | 0.013 (3) | −0.001 (2) |
C4 | 0.067 (3) | 0.043 (3) | 0.047 (3) | −0.009 (3) | 0.014 (2) | −0.013 (2) |
C5 | 0.049 (3) | 0.049 (3) | 0.038 (2) | −0.012 (2) | 0.009 (2) | −0.005 (2) |
C6 | 0.041 (2) | 0.037 (2) | 0.036 (2) | 0.0031 (19) | 0.0095 (19) | 0.0007 (18) |
C7 | 0.036 (2) | 0.033 (2) | 0.031 (2) | −0.0002 (17) | 0.0129 (17) | 0.0024 (16) |
C8 | 0.037 (2) | 0.030 (2) | 0.035 (2) | −0.0038 (18) | 0.0152 (19) | 0.0026 (17) |
C9 | 0.034 (2) | 0.039 (2) | 0.036 (2) | −0.0010 (18) | 0.0139 (19) | −0.0002 (19) |
S11 | 0.0350 (6) | 0.0591 (8) | 0.0765 (9) | 0.0064 (5) | 0.0255 (6) | −0.0020 (6) |
O11 | 0.0353 (15) | 0.0439 (17) | 0.0301 (14) | −0.0045 (12) | 0.0063 (12) | 0.0000 (12) |
O12 | 0.0338 (15) | 0.0427 (16) | 0.0447 (16) | −0.0085 (13) | 0.0092 (12) | −0.0041 (14) |
N11 | 0.0246 (16) | 0.0314 (17) | 0.0474 (19) | 0.0001 (14) | 0.0162 (14) | −0.0049 (15) |
N12 | 0.033 (2) | 0.056 (3) | 0.059 (3) | 0.010 (2) | 0.011 (2) | 0.009 (2) |
C11 | 0.025 (2) | 0.033 (2) | 0.058 (3) | 0.0009 (17) | 0.0162 (19) | −0.0025 (19) |
C12 | 0.044 (2) | 0.039 (2) | 0.061 (3) | −0.009 (2) | 0.029 (2) | −0.012 (2) |
C13 | 0.055 (3) | 0.052 (3) | 0.071 (3) | −0.011 (3) | 0.037 (3) | −0.011 (3) |
C14 | 0.081 (4) | 0.053 (3) | 0.058 (3) | −0.025 (3) | 0.047 (3) | −0.018 (3) |
C15 | 0.066 (4) | 0.049 (3) | 0.044 (3) | −0.016 (3) | 0.017 (3) | −0.008 (2) |
C16 | 0.037 (2) | 0.041 (2) | 0.048 (3) | −0.002 (2) | 0.018 (2) | −0.005 (2) |
C17 | 0.042 (2) | 0.031 (2) | 0.048 (2) | −0.0073 (18) | 0.019 (2) | −0.0063 (18) |
C18 | 0.030 (2) | 0.0248 (19) | 0.037 (2) | −0.0012 (16) | 0.0063 (16) | −0.0020 (16) |
C19 | 0.035 (2) | 0.040 (2) | 0.033 (2) | −0.0070 (19) | 0.0048 (18) | 0.0003 (19) |
Geometric parameters (Å, º) top
Cu—O1 | 1.949 (3) | C9—C19i | 1.506 (5) |
Cu—O2 | 2.709 (3) | C9—H81 | 0.98 (4) |
Cu—O11 | 1.965 (3) | C9—H82 | 0.98 (4) |
Cu—O12 | 2.613 (3) | O11—C18 | 1.258 (4) |
Cu—N1 | 2.002 (3) | O12—C18 | 1.255 (4) |
Cu—N11 | 2.004 (3) | S11—C11 | 1.751 (4) |
O1—C8 | 1.284 (5) | S11—C12 | 1.740 (5) |
O2—C8 | 1.221 (4) | N11—C11 | 1.310 (5) |
S1—C1 | 1.751 (4) | N11—C17 | 1.400 (5) |
S1—C2 | 1.750 (4) | N12—C11 | 1.331 (6) |
N1—C1 | 1.317 (5) | N12—H121 | 0.84 (5) |
N1—C7 | 1.403 (5) | N12—H122 | 0.82 (5) |
N2—C1 | 1.327 (5) | C12—C13 | 1.390 (6) |
N2—H21 | 0.84 (5) | C12—C17 | 1.416 (6) |
N2—H22 | 0.81 (4) | C13—C14 | 1.366 (8) |
C2—C3 | 1.385 (6) | C13—H13 | 0.95 (5) |
C2—C7 | 1.394 (5) | C14—C15 | 1.388 (7) |
C3—C4 | 1.370 (7) | C14—H14 | 0.91 (5) |
C3—H3 | 0.82 (6) | C15—C16 | 1.374 (6) |
C4—C5 | 1.389 (7) | C15—H15 | 0.85 (5) |
C4—H4 | 0.86 (4) | C16—C17 | 1.378 (6) |
C5—C6 | 1.379 (6) | C16—H16 | 0.90 (4) |
C5—H5 | 0.89 (4) | C18—C19 | 1.506 (5) |
C6—C7 | 1.383 (5) | C19—C9i | 1.506 (5) |
C6—H6 | 0.90 (4) | C19—H191 | 0.88 (3) |
C8—C9 | 1.512 (5) | C19—H192 | 0.94 (4) |
| | | |
O1—Cu—O2 | 53.45 (10) | O1—C8—C9 | 115.1 (3) |
O1—Cu—O11 | 91.98 (11) | C19i—C9—C8 | 114.4 (3) |
O1—Cu—O12 | 106.69 (11) | C19i—C9—H81 | 111 (2) |
O1—Cu—N1 | 152.89 (12) | C8—C9—H81 | 108 (2) |
O1—Cu—N11 | 87.75 (12) | C19i—C9—H82 | 109 (2) |
O2—Cu—O11 | 81.17 (10) | C8—C9—H82 | 102 (2) |
O2—Cu—O12 | 133.15 (9) | H81—C9—H82 | 112 (3) |
O2—Cu—N1 | 102.25 (11) | C11—S11—C12 | 88.9 (2) |
O2—Cu—N11 | 117.82 (11) | C18—O11—Cu | 106.1 (2) |
O11—Cu—O12 | 55.36 (9) | C18—O12—Cu | 76.0 (2) |
O11—Cu—N1 | 95.97 (12) | C11—N11—C17 | 111.8 (3) |
O11—Cu—N11 | 154.90 (12) | C11—N11—Cu | 122.0 (3) |
O12—Cu—N1 | 99.11 (11) | C17—N11—Cu | 123.2 (3) |
O12—Cu—N11 | 100.77 (11) | C11—N12—H121 | 118 (3) |
N1—Cu—N11 | 95.60 (13) | C11—N12—H122 | 121 (4) |
C1—S1—C2 | 89.04 (19) | H121—N12—H122 | 117 (5) |
C8—O1—Cu | 108.9 (2) | N11—C11—N12 | 124.9 (4) |
C8—O2—Cu | 74.6 (2) | N11—C11—S11 | 115.5 (3) |
C1—N1—C7 | 111.1 (3) | N12—C11—S11 | 119.6 (3) |
C1—N1—Cu | 124.0 (3) | C13—C12—C17 | 120.1 (5) |
C7—N1—Cu | 124.9 (2) | C13—C12—S11 | 129.4 (4) |
C1—N2—H21 | 119 (3) | C17—C12—S11 | 110.6 (3) |
C1—N2—H22 | 117 (3) | C14—C13—C12 | 119.0 (5) |
H21—N2—H22 | 124 (5) | C14—C13—H13 | 125 (3) |
N1—C1—N2 | 124.7 (4) | C12—C13—H13 | 116 (3) |
N1—C1—S1 | 115.3 (3) | C13—C14—C15 | 121.1 (5) |
N2—C1—S1 | 120.0 (3) | C13—C14—H14 | 119 (3) |
C3—C2—C7 | 121.8 (4) | C15—C14—H14 | 120 (3) |
C3—C2—S1 | 128.2 (4) | C16—C15—C14 | 120.7 (5) |
C7—C2—S1 | 110.1 (3) | C16—C15—H15 | 118 (3) |
C4—C3—C2 | 118.2 (5) | C14—C15—H15 | 122 (3) |
C4—C3—H3 | 122 (4) | C15—C16—C17 | 119.5 (4) |
C2—C3—H3 | 120 (4) | C15—C16—H16 | 120 (2) |
C3—C4—C5 | 120.7 (5) | C17—C16—H16 | 120 (2) |
C3—C4—H4 | 119 (3) | C16—C17—N11 | 127.2 (4) |
C5—C4—H4 | 120 (3) | C16—C17—C12 | 119.7 (4) |
C6—C5—C4 | 121.0 (4) | N11—C17—C12 | 113.2 (4) |
C6—C5—H5 | 121 (3) | O11—C18—O12 | 122.4 (3) |
C4—C5—H5 | 117 (3) | O12—C18—C19 | 118.8 (3) |
C5—C6—C7 | 119.1 (4) | O11—C18—C19 | 118.8 (3) |
C5—C6—H6 | 122 (2) | C9i—C19—C18 | 115.3 (3) |
C7—C6—H6 | 119 (2) | C9i—C19—H191 | 115 (2) |
C6—C7—C2 | 119.2 (4) | C18—C19—H191 | 103 (2) |
C6—C7—N1 | 126.3 (4) | C9i—C19—H192 | 113 (3) |
C2—C7—N1 | 114.5 (3) | C18—C19—H192 | 104 (3) |
O1—C8—O2 | 123.0 (4) | H191—C19—H192 | 105 (3) |
O2—C8—C9 | 121.8 (4) | | |
Symmetry code: (i) −x, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O2 | 0.84 (5) | 2.01 (5) | 2.852 (5) | 176 (5) |
N2—H22···O12ii | 0.81 (4) | 2.12 (4) | 2.890 (5) | 159 (5) |
N12—H121···O12 | 0.84 (5) | 2.09 (5) | 2.894 (5) | 161 (5) |
N12—H122···O1iii | 0.82 (5) | 2.09 (5) | 2.859 (5) | 157 (5) |
C14—H14···Cgiv | 0.91 (5) | 2.69 | 3.563 | 162 |
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z+1; (iv) x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | [Cu2(C4H4O4)2(C7H6N2S)4] |
Mr | 960.08 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.239 (2), 15.643 (3), 13.859 (3) |
β (°) | 102.37 (2) |
V (Å3) | 1956.5 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.36 |
Crystal size (mm) | 0.23 × 0.13 × 0.13 |
|
Data collection |
Diffractometer | Siemens P3 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.740, 0.848 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3561, 3414, 2516 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.090, 1.03 |
No. of reflections | 3414 |
No. of parameters | 326 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.33, −0.28 |
Selected geometric parameters (Å, º) topCu—O1 | 1.949 (3) | N1—C1 | 1.317 (5) |
Cu—O2 | 2.709 (3) | N1—C7 | 1.403 (5) |
Cu—O11 | 1.965 (3) | N2—C1 | 1.327 (5) |
Cu—O12 | 2.613 (3) | O11—C18 | 1.258 (4) |
Cu—N1 | 2.002 (3) | O12—C18 | 1.255 (4) |
Cu—N11 | 2.004 (3) | S11—C11 | 1.751 (4) |
O1—C8 | 1.284 (5) | S11—C12 | 1.740 (5) |
O2—C8 | 1.221 (4) | N11—C11 | 1.310 (5) |
S1—C1 | 1.751 (4) | N11—C17 | 1.400 (5) |
S1—C2 | 1.750 (4) | N12—C11 | 1.331 (6) |
| | | |
O1—Cu—O2 | 53.45 (10) | N1—C1—N2 | 124.7 (4) |
O1—Cu—O11 | 91.98 (11) | N1—C1—S1 | 115.3 (3) |
O1—Cu—O12 | 106.69 (11) | N2—C1—S1 | 120.0 (3) |
O1—Cu—N1 | 152.89 (12) | C3—C2—S1 | 128.2 (4) |
O1—Cu—N11 | 87.75 (12) | C7—C2—S1 | 110.1 (3) |
O2—Cu—O11 | 81.17 (10) | C6—C7—N1 | 126.3 (4) |
O2—Cu—O12 | 133.15 (9) | C2—C7—N1 | 114.5 (3) |
O2—Cu—N1 | 102.25 (11) | O1—C8—O2 | 123.0 (4) |
O2—Cu—N11 | 117.82 (11) | C11—S11—C12 | 88.9 (2) |
O11—Cu—O12 | 55.36 (9) | C11—N11—C17 | 111.8 (3) |
O11—Cu—N1 | 95.97 (12) | N11—C11—N12 | 124.9 (4) |
O11—Cu—N11 | 154.90 (12) | N11—C11—S11 | 115.5 (3) |
O12—Cu—N1 | 99.11 (11) | N12—C11—S11 | 119.6 (3) |
O12—Cu—N11 | 100.77 (11) | C13—C12—S11 | 129.4 (4) |
N1—Cu—N11 | 95.60 (13) | C17—C12—S11 | 110.6 (3) |
C1—S1—C2 | 89.04 (19) | N11—C17—C12 | 113.2 (4) |
C1—N1—C7 | 111.1 (3) | O11—C18—O12 | 122.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O2 | 0.84 (5) | 2.01 (5) | 2.852 (5) | 176 (5) |
N2—H22···O12i | 0.81 (4) | 2.12 (4) | 2.890 (5) | 159 (5) |
N12—H121···O12 | 0.84 (5) | 2.09 (5) | 2.894 (5) | 161 (5) |
N12—H122···O1ii | 0.82 (5) | 2.09 (5) | 2.859 (5) | 157 (5) |
C14—H14···Cgiii | 0.91 (5) | 2.69 | 3.563 | 162 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1, −y, −z+1; (iii) x+1/2, −y+1/2, z−1/2. |
This work forms part of a continuing study of CuII complexes with benzimidazole and dicarboxylic acids (Tosik & Bukowska-Strzyżewska, 1992; Tosik et al., 1995a,b; Sieroń & Bukowska-Strzyżewska, 1998, 1999a), and with carboxylate anions and 2-aminobenzothiazole (Sieroń & Bukowska-Strzyżewska, 1999b), giving a second example of Cu–(2-aminobenzothiazole) coordination. In the molecule of the title compound, (I) (Fig. 1), both succinate ions adopt the rare synclinal conformation with respect to the central C—C bonds [C8–C9–C19i–C18i = −73.2 (5)°; symmetry code: (i) −x, −y, 1 − z] and take the bridge position between the two Cu atoms, forming a dinuclear centrosymmetrical complex with a Cu···Cu distance of 6.384 (2) Å. A 14-membered ring is formed around a centre of symmetry. The Cu atoms adopt very distorted square-bipyramidal coordinations. The four basal bonds are formed by two cis-N atoms of 2-aminobenzothiazole, with an average Cu—N distance of 2.003 (3) Å, and two cis-O atoms of two carboxylate groups, with Cu—O distances of 1.949 (3) and 1.965 (3) Å. The square-planar coordination is visible deformed in the direction of the tetrahedral coordination. The deviations from the N1/N11/O1/O11 least-square plane are −0.404 (1) and −0.472 (2) Å for the trans-situated N1 and O1 atoms, and O.444 (2) and 0.433 (2) Å for the N11 and O11 atoms, respectively. The deviation of Cu atom from this plane is only 0.022 (2) Å. Two distinctly longer Cu—O2 and Cu—O12 bonds of 2.709 (3) and 2.613 (3) Å complete the sixfold coordination. The observed O2—Cu—O12 angle is only 133.2 (1)°. The dihedral angle between the planes of the two cis-carboxylate groups is 89.9 (5)° and between the average planes of the two 2-aminobenzothiazole ligands is 82.2 (1)°. The five and six-membered rings of the 2-aminobenzothiazole molecules are ideally planar and in one molecule ideally coplanar. In the second molecule (containing S1 and N1 atoms), the five and six-membered rings form a dihedral angle of 2.7 (2)°.
The geometry of intra- and intermolecular hydrogen bonds and of the intermolecular C—H···Cg(π-ring) interaction, where Cg is the centroid of the imidazole ring (containing S1 and N1), are given in Table 2. The observed H···Cg distance is 2.69 Å. The molecular packing is illustrated in Fig. 2. The trans-situated carboxylate ions and 2-aminobenzothiazole molecules are connected by N—H···O intramolecular hydrogen bonds, forming six-membered rings. The individual carboxylate ions are differently involved in the intermolecular N—H···O hydrogen-bond system. The C8/O1/O2 group forms an intramolecular hydrogen bond through the O2 atom and an intermolecular hydrogen bond through the O1 atom. In the C18/O11/O12 group, only O12 is involved in hydrogen bonding, forming both inter- and intramolecular N2(12)—H···O12 hydrogen bonds. This causes distinctly different delocalization of π bonds in both carboxylic groups. The bonds C8–O1 [1.284 (5) Å] and C8–O2 [1.221 (4) Å] are differentiated, while C18–O11 [1.258 (4) Å] and C18–O12 [1.255 (4) Å] are practically identical. The different structure of both Cu-coordinated carboxylic groups causes the differentiation of both short and long Cu—O bonds; Cu–O1 [1.949 (3) Å] is distinctly shorter than Cu—O11 [1.965 (3) Å], and Cu–O2 [2.709 (3) Å] is longer than Cu–O12 [2.613 (3) Å]. The observed regularity is consistent with the valence bond sum rule (Brown, 1994). The application of the bond valence–bond length correlation allows comparison of the relative importance of Cu—N and different Cu—O bonds of the CuII polyhedron and also allows a check of the valence sum rule. According to Brown (1994), the bond length to bond valence correlation represents a measure of the strength of a bond that is independent of the atomic size. The valence sum rule states that the sum of the valences of the bond formed by an atom is equal to the valence (formal oxidation state) of the atom (Vi = Σνij). The bond valences were computed according to Brown (1992, 1997) 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. RCu—O and RCu—N were taken as 1.679 and 1.713 Å (see Sieroń & Bukowska-Strzyżewska, 1999a). The computed bond valences of the CuII atom are: νCu—O1 = 0.482, νCu—O2 = 0.062, νCu—O11 = 0.462, νCu—O12 = 0.080, νCu—N1 = 0.458, νCu—N2 = 0.455 v.u. (valence unit), thus, the computed valence of the CuII atoms (VCu) is 2.00 v.u.
The conformations on the two terminal C—C bonds of the succinate ion are different. On the C18—C19 bond, the conformations are synperiplanar and antiperiplanar [torsion angles O11—C18—C19—C9i = 5.0 (6)° and O12—C18—C19—C9i = −175.2 (4)°], and on the C8—C9 bond, the conformations are antiperiplanar and synclinal [torsion angles O1–C8–C9–C19i = 151.4 (4) and O2–C8–C9–C19i = −32.0 (6)°]. The structure illustrates the influence of weak hydrogen bonds on the conformation of the aliphatic chain and the differentiation of Cu—O bond lengths.
Compound (I) is a second example of bis(µ-dicarboxylate) coordination in a CuII complex with formation of a dimeric molecular structure. A similar coordination was observed in the complex bis[(µ2-adipato-O,O':O'',O''')(N,N-diethylenediamine)copper(II)] (Pajunen & Nasakkala, 1977).