metal-organic compounds
Bis(n-dodecylammonium) bis(chloranilato)diethanolcuprate(II)
aDepartment of Chemistry, Faculty of Science, Fukuoka University, Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
*Correspondence e-mail: kawata@fukuoka-u.ac.jp
In the title compound, (C12H25NH3)2[Cu(C6Cl2O4)2(C2H5OH)2], the CuII atom lies on a crystallographic inversion center and is coordinated in a distorted octahedral geometry by four O atoms of two chloranilate ligands and two O atoms of two ethanol molecules which are trans to each other in the axial positions. In the crystal, the CuII mononuclear dianions are linked by O—H⋯O hydrogen bonds into a tape along the a-axis direction. The tapes are linked through N—H⋯O hydrogen bonds between the dianion and the n-dodecylammonium cation, forming a two-dimensional network parallel to the ab plane.
CCDC reference: 981983
Related literature
For metal complexes of chloranilic acid, see: Kawata & Kitagawa (2002); Kawata et al. (2000); Luo et al. (2004); Abrahams et al. (2011); Nagayoshi et al. (2003); Nishimura et al. (2013).
Experimental
Crystal data
|
|
Data collection: CrystalClear (Rigaku, 2010); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: Il Milione (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure.
Supporting information
CCDC reference: 981983
10.1107/S1600536814001202/is5334sup1.cif
contains datablocks General, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814001202/is5334Isup2.hkl
An aqueous solution of copper sulfate pentahydrate (1 ml, 20 mmol L-1) was transferred to a glass tube, and then a mixture of n-dodecylamine (1 ml, 40 mmol L-1) in ethanol-water (1:1) solution and H2CA (1 ml, 60 mmol L-1) in ethanol solution was poured into the tube without mixing the two solutions. Violet crystals began to form at ambient temperature within two weeks. One of these crystals was used for X-ray crystallography.
The C-bound H atoms in the alkyl chain of Hda+ ion and the ethyl group of the ethanol molecule were placed at calculated positions with C—H = 0.99 (CH2) and C—H = 0.98 (CH3) Å, and were treated as riding on their parent atoms with Uiso(H) set to 1.2Ueq(C). The O-bound and N-bound H atoms were located in a difference Fourier map and refined freely.
Chloranilic acid (H2CA = 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) and its homologues, which contain two chelating coordination sites, are capable of bridging metal centers to form monomeric molecules, chains, sheets, or three-dimensional structures (Kawata & Kitagawa, 2002; Luo et al., 2004; Abrahams et al., 2011). In line with our study of metal-chloranilate complexes, we have been trying to develop metal-chloranilate hybrid materials and have found host–guest compounds (Kawata et al., 2000; Nagayoshi et al., 2003; Nishimura et al., 2013). We report here, a novel inorganic-organic hybrid system by using metal-chloranirate complexes as host layers and alkylamines as guests.
The title compound, (C12H25NH3)2[Cu(C6Cl2O4)2(C2H5OH)2], consists of the mononuclear [Cu(CA)2(EtOH)2]2- dianion and the protonated n-dodecylamine (Hda+). The CuII atom lies on a crystallographic inversion center. The geometry around the CuII atom is a distorted octahedron involving four O atoms of two CA2- anions and two O atoms from two ethanol molecules which are trans to each other. The axial bond distances are much longer than the equatorial ones (Table 1). The [Cu(CA)2(EtOH)2]2- anions make a tape structure running along the a axis (Fig. 2) via an intermolecular O—H···O hydrogen bond (Table 2) between the coordinated ethanol molecule and the terminal oxygen atom of CA2-. The tapes are linked through N—H···O hydrogen bonds (Table 2) between the dianion and the Hda+ cation, forming a two-dimensional network expanding parallel to the ab plane (Fig. 3).
For metal complexes of chloranilic acid, see: Kawata & Kitagawa (2002); Kawata et al. (2000); Luo et al. (2004); Abrahams et al. (2011); Nagayoshi et al. (2003); Nishimura et al. (2013).
Data collection: CrystalClear (Rigaku, 2010); cell
CrystalClear (Rigaku, 2010); data reduction: CrystalClear (Rigaku, 2010); program(s) used to solve structure: Il Milione (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).Fig. 1. An ORTEP drawing of the title complex compound, showing 50% probability displacement elipsoids. | |
Fig. 2. A packing diagram showing tape structures of [Cu(CA)2(EtOH)2]2- ions. The dashed lines denote the O—H···O hydrogen bonds. | |
Fig. 3. A packing diagram of the title compound, viewed along the b axis. |
(C12H28N)2[Cu(C6Cl2O4)2(C2H6O)2] | Z = 1 |
Mr = 942.34 | F(000) = 499.00 |
Triclinic, P1 | Dx = 1.366 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
a = 9.2192 (15) Å | Cell parameters from 3320 reflections |
b = 9.4791 (13) Å | θ = 3.1–27.5° |
c = 15.162 (3) Å | µ = 0.76 mm−1 |
α = 76.894 (9)° | T = 100 K |
β = 89.133 (10)° | Platelet, violet |
γ = 63.110 (6)° | 0.40 × 0.30 × 0.05 mm |
V = 1145.1 (4) Å3 |
Rigaku Saturn724 diffractometer | 4796 reflections with F2 > 2.0σ(F2) |
Detector resolution: 7.111 pixels mm-1 | Rint = 0.025 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | h = −11→11 |
Tmin = 0.868, Tmax = 0.962 | k = −12→12 |
17151 measured reflections | l = −19→19 |
5207 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.037P)2 + 0.6543P] where P = (Fo2 + 2Fc2)/3 |
5207 reflections | (Δ/σ)max = 0.001 |
275 parameters | Δρmax = 0.92 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Primary atom site location: structure-invariant direct methods |
(C12H28N)2[Cu(C6Cl2O4)2(C2H6O)2] | γ = 63.110 (6)° |
Mr = 942.34 | V = 1145.1 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.2192 (15) Å | Mo Kα radiation |
b = 9.4791 (13) Å | µ = 0.76 mm−1 |
c = 15.162 (3) Å | T = 100 K |
α = 76.894 (9)° | 0.40 × 0.30 × 0.05 mm |
β = 89.133 (10)° |
Rigaku Saturn724 diffractometer | 5207 independent reflections |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | 4796 reflections with F2 > 2.0σ(F2) |
Tmin = 0.868, Tmax = 0.962 | Rint = 0.025 |
17151 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.92 e Å−3 |
5207 reflections | Δρmin = −0.34 e Å−3 |
275 parameters |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 0.5000 | 1.0000 | 0.01636 (8) | |
Cl1 | 0.53483 (4) | −0.04086 (4) | 1.14542 (2) | 0.01736 (8) | |
Cl2 | −0.00556 (4) | 0.55604 (4) | 0.85100 (2) | 0.01622 (8) | |
O1 | 0.52991 (12) | 0.28029 (12) | 1.05403 (7) | 0.0178 (2) | |
O2 | 0.29500 (12) | 0.53156 (12) | 0.94162 (7) | 0.0165 (2) | |
O3 | −0.00228 (12) | 0.23827 (12) | 0.94210 (7) | 0.0169 (2) | |
O4 | 0.22249 (13) | −0.00706 (13) | 1.06624 (7) | 0.0198 (2) | |
O5 | 0.66424 (15) | 0.42290 (16) | 0.87749 (8) | 0.0302 (3) | |
N1 | 0.12545 (15) | −0.08274 (16) | 0.90253 (9) | 0.0157 (2) | |
C1 | 0.40568 (16) | 0.26123 (17) | 1.03371 (9) | 0.0135 (3) | |
C2 | 0.27283 (16) | 0.40582 (16) | 0.96559 (9) | 0.0135 (3) | |
C3 | 0.13943 (16) | 0.39417 (17) | 0.93232 (9) | 0.0139 (3) | |
C4 | 0.11687 (16) | 0.25682 (16) | 0.96583 (9) | 0.0135 (3) | |
C5 | 0.24721 (16) | 0.11209 (16) | 1.03867 (9) | 0.0139 (3) | |
C6 | 0.38592 (17) | 0.12498 (17) | 1.06779 (9) | 0.0141 (3) | |
C7 | 0.6455 (2) | 0.3845 (2) | 0.79473 (12) | 0.0291 (4) | |
H7A | 0.6655 | 0.2697 | 0.8072 | 0.035* | |
H7B | 0.7267 | 0.3966 | 0.7543 | 0.035* | |
C8 | 0.4764 (2) | 0.4956 (3) | 0.74834 (13) | 0.0372 (4) | |
H8A | 0.4575 | 0.6090 | 0.7352 | 0.045* | |
H8B | 0.3963 | 0.4826 | 0.7882 | 0.045* | |
H8C | 0.4648 | 0.4678 | 0.6913 | 0.045* | |
C9 | 0.08326 (18) | −0.09264 (18) | 0.80967 (10) | 0.0191 (3) | |
H9A | −0.0364 | −0.0289 | 0.7937 | 0.023* | |
H9B | 0.1153 | −0.2077 | 0.8105 | 0.023* | |
C10 | 0.16933 (18) | −0.02718 (18) | 0.73788 (10) | 0.0190 (3) | |
H10A | 0.1583 | −0.0583 | 0.6812 | 0.023* | |
H10B | 0.2873 | −0.0805 | 0.7590 | 0.023* | |
C11 | 0.10505 (18) | 0.15795 (18) | 0.71583 (10) | 0.0192 (3) | |
H11A | −0.0115 | 0.2123 | 0.6917 | 0.023* | |
H11B | 0.1121 | 0.1906 | 0.7726 | 0.023* | |
C12 | 0.20052 (18) | 0.21605 (19) | 0.64636 (10) | 0.0198 (3) | |
H12A | 0.3173 | 0.1602 | 0.6704 | 0.024* | |
H12B | 0.1925 | 0.1840 | 0.5896 | 0.024* | |
C13 | 0.13993 (19) | 0.40005 (19) | 0.62405 (11) | 0.0220 (3) | |
H13A | 0.1439 | 0.4327 | 0.6812 | 0.026* | |
H13B | 0.0244 | 0.4558 | 0.5979 | 0.026* | |
C14 | 0.23900 (19) | 0.45781 (19) | 0.55735 (11) | 0.0212 (3) | |
H14A | 0.3548 | 0.4015 | 0.5832 | 0.025* | |
H14B | 0.2340 | 0.4264 | 0.4999 | 0.025* | |
C15 | 0.17839 (19) | 0.64171 (19) | 0.53626 (11) | 0.0222 (3) | |
H15A | 0.1724 | 0.6741 | 0.5944 | 0.027* | |
H15B | 0.0662 | 0.6972 | 0.5051 | 0.027* | |
C16 | 0.28427 (19) | 0.70182 (19) | 0.47717 (11) | 0.0236 (3) | |
H16A | 0.2956 | 0.6647 | 0.4203 | 0.028* | |
H16B | 0.3948 | 0.6522 | 0.5098 | 0.028* | |
C17 | 0.2144 (2) | 0.88713 (19) | 0.45306 (11) | 0.0243 (3) | |
H17A | 0.1068 | 0.9357 | 0.4173 | 0.029* | |
H17B | 0.1959 | 0.9241 | 0.5102 | 0.029* | |
C18 | 0.3209 (2) | 0.9526 (2) | 0.39921 (12) | 0.0273 (4) | |
H18A | 0.3426 | 0.9137 | 0.3427 | 0.033* | |
H18B | 0.4272 | 0.9083 | 0.4356 | 0.033* | |
C19 | 0.2427 (2) | 1.1383 (2) | 0.37427 (13) | 0.0307 (4) | |
H19A | 0.1422 | 1.1817 | 0.3327 | 0.037* | |
H19B | 0.2100 | 1.1772 | 0.4302 | 0.037* | |
C20 | 0.3529 (3) | 1.2073 (2) | 0.32906 (15) | 0.0389 (5) | |
H20A | 0.3835 | 1.1722 | 0.2726 | 0.047* | |
H20B | 0.4516 | 1.1675 | 0.3703 | 0.047* | |
H20C | 0.2946 | 1.3268 | 0.3151 | 0.047* | |
H1 | 0.769 (3) | 0.374 (3) | 0.8970 (16) | 0.044 (6)* | |
H2 | 0.235 (3) | −0.131 (2) | 0.9169 (13) | 0.021 (5)* | |
H3 | 0.088 (2) | 0.020 (2) | 0.9063 (12) | 0.020 (4)* | |
H4 | 0.082 (2) | −0.129 (2) | 0.9432 (14) | 0.025 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01280 (12) | 0.01202 (12) | 0.02484 (14) | −0.00770 (10) | −0.00397 (9) | −0.00092 (10) |
Cl1 | 0.01591 (16) | 0.01415 (16) | 0.01890 (16) | −0.00615 (13) | −0.00402 (12) | 0.00037 (12) |
Cl2 | 0.01428 (15) | 0.01421 (16) | 0.01823 (16) | −0.00668 (12) | −0.00354 (12) | 0.00018 (12) |
O1 | 0.0131 (5) | 0.0140 (5) | 0.0256 (6) | −0.0073 (4) | −0.0046 (4) | −0.0007 (4) |
O2 | 0.0147 (5) | 0.0131 (5) | 0.0222 (5) | −0.0083 (4) | −0.0027 (4) | −0.0008 (4) |
O3 | 0.0140 (5) | 0.0160 (5) | 0.0223 (5) | −0.0092 (4) | −0.0012 (4) | −0.0024 (4) |
O4 | 0.0184 (5) | 0.0163 (5) | 0.0257 (6) | −0.0116 (5) | −0.0023 (4) | 0.0013 (5) |
O5 | 0.0188 (6) | 0.0397 (7) | 0.0288 (7) | −0.0085 (6) | −0.0005 (5) | −0.0129 (6) |
N1 | 0.0147 (6) | 0.0150 (6) | 0.0187 (6) | −0.0089 (5) | 0.0003 (5) | −0.0017 (5) |
C1 | 0.0107 (6) | 0.0137 (7) | 0.0164 (7) | −0.0055 (5) | 0.0006 (5) | −0.0045 (5) |
C2 | 0.0121 (6) | 0.0126 (7) | 0.0164 (7) | −0.0059 (5) | 0.0020 (5) | −0.0041 (5) |
C3 | 0.0112 (6) | 0.0131 (7) | 0.0157 (7) | −0.0046 (5) | −0.0007 (5) | −0.0024 (5) |
C4 | 0.0115 (6) | 0.0136 (7) | 0.0159 (7) | −0.0058 (5) | 0.0019 (5) | −0.0046 (5) |
C5 | 0.0131 (7) | 0.0134 (7) | 0.0153 (7) | −0.0065 (6) | 0.0021 (5) | −0.0032 (5) |
C6 | 0.0128 (6) | 0.0126 (6) | 0.0146 (6) | −0.0046 (5) | −0.0019 (5) | −0.0015 (5) |
C7 | 0.0311 (9) | 0.0265 (9) | 0.0253 (8) | −0.0106 (8) | −0.0011 (7) | −0.0038 (7) |
C8 | 0.0294 (10) | 0.0532 (12) | 0.0259 (9) | −0.0172 (9) | −0.0008 (7) | −0.0082 (9) |
C9 | 0.0191 (7) | 0.0196 (7) | 0.0211 (7) | −0.0118 (6) | −0.0029 (6) | −0.0032 (6) |
C10 | 0.0194 (7) | 0.0191 (7) | 0.0184 (7) | −0.0091 (6) | 0.0018 (6) | −0.0040 (6) |
C11 | 0.0185 (7) | 0.0187 (7) | 0.0190 (7) | −0.0090 (6) | 0.0017 (6) | −0.0009 (6) |
C12 | 0.0192 (7) | 0.0216 (8) | 0.0168 (7) | −0.0093 (6) | 0.0010 (6) | −0.0014 (6) |
C13 | 0.0196 (7) | 0.0219 (8) | 0.0231 (8) | −0.0100 (6) | 0.0042 (6) | −0.0020 (6) |
C14 | 0.0209 (8) | 0.0220 (8) | 0.0197 (7) | −0.0104 (6) | 0.0026 (6) | −0.0022 (6) |
C15 | 0.0180 (7) | 0.0215 (8) | 0.0241 (8) | −0.0084 (6) | 0.0030 (6) | −0.0017 (6) |
C16 | 0.0211 (8) | 0.0207 (8) | 0.0253 (8) | −0.0085 (6) | 0.0053 (6) | −0.0012 (6) |
C17 | 0.0221 (8) | 0.0215 (8) | 0.0249 (8) | −0.0083 (7) | 0.0062 (6) | −0.0016 (6) |
C18 | 0.0256 (8) | 0.0215 (8) | 0.0305 (9) | −0.0092 (7) | 0.0098 (7) | −0.0027 (7) |
C19 | 0.0348 (10) | 0.0216 (9) | 0.0308 (9) | −0.0105 (8) | 0.0100 (8) | −0.0033 (7) |
C20 | 0.0473 (12) | 0.0270 (10) | 0.0437 (11) | −0.0195 (9) | 0.0166 (9) | −0.0067 (8) |
Cu1—O1i | 1.9489 (11) | C10—C11 | 1.530 (2) |
Cu1—O1 | 1.9489 (10) | C10—H10A | 0.9900 |
Cu1—O2i | 1.9657 (10) | C10—H10B | 0.9900 |
Cu1—O2 | 1.9657 (10) | C11—C12 | 1.528 (2) |
Cu1—O5i | 2.4097 (13) | C11—H11A | 0.9900 |
Cu1—O5 | 2.4097 (13) | C11—H11B | 0.9900 |
Cl1—C6 | 1.7317 (14) | C12—C13 | 1.525 (2) |
Cl2—C3 | 1.7315 (14) | C12—H12A | 0.9900 |
O1—C1 | 1.2893 (17) | C12—H12B | 0.9900 |
O2—C2 | 1.2713 (17) | C13—C14 | 1.526 (2) |
O3—C4 | 1.2579 (17) | C13—H13A | 0.9900 |
O4—C5 | 1.2322 (17) | C13—H13B | 0.9900 |
O5—C7 | 1.417 (2) | C14—C15 | 1.525 (2) |
O5—H1 | 0.88 (3) | C14—H14A | 0.9900 |
N1—C9 | 1.5005 (19) | C14—H14B | 0.9900 |
N1—H2 | 0.90 (2) | C15—C16 | 1.525 (2) |
N1—H3 | 0.89 (2) | C15—H15A | 0.9900 |
N1—H4 | 0.87 (2) | C15—H15B | 0.9900 |
C1—C6 | 1.370 (2) | C16—C17 | 1.525 (2) |
C1—C2 | 1.5242 (19) | C16—H16A | 0.9900 |
C2—C3 | 1.3950 (19) | C16—H16B | 0.9900 |
C3—C4 | 1.3922 (19) | C17—C18 | 1.521 (2) |
C4—C5 | 1.5517 (19) | C17—H17A | 0.9900 |
C5—C6 | 1.4241 (19) | C17—H17B | 0.9900 |
C7—C8 | 1.499 (2) | C18—C19 | 1.524 (2) |
C7—H7A | 0.9900 | C18—H18A | 0.9900 |
C7—H7B | 0.9900 | C18—H18B | 0.9900 |
C8—H8A | 0.9800 | C19—C20 | 1.518 (3) |
C8—H8B | 0.9800 | C19—H19A | 0.9900 |
C8—H8C | 0.9800 | C19—H19B | 0.9900 |
C9—C10 | 1.521 (2) | C20—H20A | 0.9800 |
C9—H9A | 0.9900 | C20—H20B | 0.9800 |
C9—H9B | 0.9900 | C20—H20C | 0.9800 |
O1i—Cu1—O1 | 180.00 (6) | C11—C10—H10A | 108.6 |
O1i—Cu1—O2i | 84.09 (4) | C9—C10—H10B | 108.6 |
O1—Cu1—O2i | 95.91 (4) | C11—C10—H10B | 108.6 |
O1i—Cu1—O2 | 95.91 (4) | H10A—C10—H10B | 107.6 |
O1—Cu1—O2 | 84.09 (4) | C12—C11—C10 | 112.43 (12) |
O2i—Cu1—O2 | 179.999 (1) | C12—C11—H11A | 109.1 |
O1i—Cu1—O5i | 94.24 (5) | C10—C11—H11A | 109.1 |
O1—Cu1—O5i | 85.76 (5) | C12—C11—H11B | 109.1 |
O2i—Cu1—O5i | 96.70 (4) | C10—C11—H11B | 109.1 |
O2—Cu1—O5i | 83.30 (4) | H11A—C11—H11B | 107.9 |
O1i—Cu1—O5 | 85.76 (5) | C13—C12—C11 | 113.42 (12) |
O1—Cu1—O5 | 94.24 (5) | C13—C12—H12A | 108.9 |
O2i—Cu1—O5 | 83.30 (4) | C11—C12—H12A | 108.9 |
O2—Cu1—O5 | 96.70 (4) | C13—C12—H12B | 108.9 |
O5i—Cu1—O5 | 179.999 (1) | C11—C12—H12B | 108.9 |
C1—O1—Cu1 | 112.48 (9) | H12A—C12—H12B | 107.7 |
C2—O2—Cu1 | 112.47 (9) | C12—C13—C14 | 113.58 (13) |
C7—O5—Cu1 | 136.61 (11) | C12—C13—H13A | 108.9 |
C7—O5—H1 | 108.8 (16) | C14—C13—H13A | 108.9 |
Cu1—O5—H1 | 110.5 (15) | C12—C13—H13B | 108.9 |
C9—N1—H2 | 111.6 (12) | C14—C13—H13B | 108.9 |
C9—N1—H3 | 111.9 (12) | H13A—C13—H13B | 107.7 |
H2—N1—H3 | 106.3 (17) | C15—C14—C13 | 113.12 (13) |
C9—N1—H4 | 110.2 (13) | C15—C14—H14A | 109.0 |
H2—N1—H4 | 109.3 (17) | C13—C14—H14A | 109.0 |
H3—N1—H4 | 107.4 (17) | C15—C14—H14B | 109.0 |
O1—C1—C6 | 125.59 (13) | C13—C14—H14B | 109.0 |
O1—C1—C2 | 115.10 (12) | H14A—C14—H14B | 107.8 |
C6—C1—C2 | 119.31 (12) | C14—C15—C16 | 114.58 (13) |
O2—C2—C3 | 124.12 (13) | C14—C15—H15A | 108.6 |
O2—C2—C1 | 115.58 (12) | C16—C15—H15A | 108.6 |
C3—C2—C1 | 120.29 (12) | C14—C15—H15B | 108.6 |
C4—C3—C2 | 121.21 (13) | C16—C15—H15B | 108.6 |
C4—C3—Cl2 | 119.01 (10) | H15A—C15—H15B | 107.6 |
C2—C3—Cl2 | 119.74 (11) | C15—C16—C17 | 113.00 (13) |
O3—C4—C3 | 125.49 (13) | C15—C16—H16A | 109.0 |
O3—C4—C5 | 115.72 (12) | C17—C16—H16A | 109.0 |
C3—C4—C5 | 118.79 (12) | C15—C16—H16B | 109.0 |
O4—C5—C6 | 124.97 (13) | C17—C16—H16B | 109.0 |
O4—C5—C4 | 116.59 (12) | H16A—C16—H16B | 107.8 |
C6—C5—C4 | 118.43 (12) | C18—C17—C16 | 115.02 (13) |
C1—C6—C5 | 121.74 (12) | C18—C17—H17A | 108.5 |
C1—C6—Cl1 | 120.25 (11) | C16—C17—H17A | 108.5 |
C5—C6—Cl1 | 117.98 (10) | C18—C17—H17B | 108.5 |
O5—C7—C8 | 110.19 (15) | C16—C17—H17B | 108.5 |
O5—C7—H7A | 109.6 | H17A—C17—H17B | 107.5 |
C8—C7—H7A | 109.6 | C17—C18—C19 | 112.76 (14) |
O5—C7—H7B | 109.6 | C17—C18—H18A | 109.0 |
C8—C7—H7B | 109.6 | C19—C18—H18A | 109.0 |
H7A—C7—H7B | 108.1 | C17—C18—H18B | 109.0 |
C7—C8—H8A | 109.5 | C19—C18—H18B | 109.0 |
C7—C8—H8B | 109.5 | H18A—C18—H18B | 107.8 |
H8A—C8—H8B | 109.5 | C20—C19—C18 | 114.12 (15) |
C7—C8—H8C | 109.5 | C20—C19—H19A | 108.7 |
H8A—C8—H8C | 109.5 | C18—C19—H19A | 108.7 |
H8B—C8—H8C | 109.5 | C20—C19—H19B | 108.7 |
N1—C9—C10 | 111.53 (12) | C18—C19—H19B | 108.7 |
N1—C9—H9A | 109.3 | H19A—C19—H19B | 107.6 |
C10—C9—H9A | 109.3 | C19—C20—H20A | 109.5 |
N1—C9—H9B | 109.3 | C19—C20—H20B | 109.5 |
C10—C9—H9B | 109.3 | H20A—C20—H20B | 109.5 |
H9A—C9—H9B | 108.0 | C19—C20—H20C | 109.5 |
C9—C10—C11 | 114.68 (12) | H20A—C20—H20C | 109.5 |
C9—C10—H10A | 108.6 | H20B—C20—H20C | 109.5 |
O2i—Cu1—O1—C1 | 175.55 (10) | C2—C3—C4—C5 | −2.5 (2) |
O2—Cu1—O1—C1 | −4.45 (10) | Cl2—C3—C4—C5 | 179.98 (9) |
O5i—Cu1—O1—C1 | 79.23 (10) | O3—C4—C5—O4 | 0.18 (18) |
O5—Cu1—O1—C1 | −100.77 (10) | C3—C4—C5—O4 | −179.84 (13) |
O1i—Cu1—O2—C2 | −178.08 (10) | O3—C4—C5—C6 | 179.43 (12) |
O1—Cu1—O2—C2 | 1.92 (10) | C3—C4—C5—C6 | −0.59 (19) |
O5i—Cu1—O2—C2 | −84.49 (10) | O1—C1—C6—C5 | −177.45 (13) |
O5—Cu1—O2—C2 | 95.51 (10) | C2—C1—C6—C5 | 2.4 (2) |
O1i—Cu1—O5—C7 | −104.22 (16) | O1—C1—C6—Cl1 | 0.2 (2) |
O1—Cu1—O5—C7 | 75.77 (16) | C2—C1—C6—Cl1 | −179.89 (10) |
O2i—Cu1—O5—C7 | 171.24 (16) | O4—C5—C6—C1 | 179.66 (14) |
O2—Cu1—O5—C7 | −8.76 (16) | C4—C5—C6—C1 | 0.5 (2) |
Cu1—O1—C1—C6 | −174.25 (12) | O4—C5—C6—Cl1 | 1.9 (2) |
Cu1—O1—C1—C2 | 5.85 (15) | C4—C5—C6—Cl1 | −177.24 (9) |
Cu1—O2—C2—C3 | −178.16 (11) | Cu1—O5—C7—C8 | 39.7 (2) |
Cu1—O2—C2—C1 | 0.64 (15) | N1—C9—C10—C11 | −70.83 (16) |
O1—C1—C2—O2 | −4.48 (18) | C9—C10—C11—C12 | 177.58 (12) |
C6—C1—C2—O2 | 175.61 (13) | C10—C11—C12—C13 | −179.36 (12) |
O1—C1—C2—C3 | 174.36 (13) | C11—C12—C13—C14 | 177.86 (13) |
C6—C1—C2—C3 | −5.5 (2) | C12—C13—C14—C15 | −179.44 (13) |
O2—C2—C3—C4 | −175.74 (13) | C13—C14—C15—C16 | 174.36 (14) |
C1—C2—C3—C4 | 5.5 (2) | C14—C15—C16—C17 | 176.68 (14) |
O2—C2—C3—Cl2 | 1.7 (2) | C15—C16—C17—C18 | 176.30 (14) |
C1—C2—C3—Cl2 | −176.99 (10) | C16—C17—C18—C19 | 178.04 (15) |
C2—C3—C4—O3 | 177.46 (13) | C17—C18—C19—C20 | 174.00 (16) |
Cl2—C3—C4—O3 | 0.0 (2) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H1···O3ii | 0.88 (3) | 1.94 (3) | 2.8145 (16) | 172 (3) |
N1—H2···O1iii | 0.91 (3) | 1.97 (2) | 2.8562 (16) | 167 (3) |
N1—H3···O3 | 0.89 (3) | 2.05 (3) | 2.928 (2) | 168.3 (17) |
N1—H4···O3iv | 0.87 (3) | 2.12 (3) | 2.9784 (19) | 171 (3) |
N1—H4···O4iv | 0.87 (3) | 2.50 (3) | 2.9842 (19) | 116.2 (13) |
Symmetry codes: (ii) x+1, y, z; (iii) −x+1, −y, −z+2; (iv) −x, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H1···O3i | 0.88 (3) | 1.94 (3) | 2.8145 (16) | 172 (3) |
N1—H2···O1ii | 0.91 (3) | 1.97 (2) | 2.8562 (16) | 167 (3) |
N1—H3···O3 | 0.89 (3) | 2.05 (3) | 2.928 (2) | 168.3 (17) |
N1—H4···O3iii | 0.87 (3) | 2.12 (3) | 2.9784 (19) | 171 (3) |
N1—H4···O4iii | 0.87 (3) | 2.50 (3) | 2.9842 (19) | 116.2 (13) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+2; (iii) −x, −y, −z+2. |
Acknowledgements
This work was supported by the fund Grant-in-Aids for Science Research (No. 25410078) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
References
Abrahams, B. F., Grannas, M. J., Hudson, T. A., Hughes, S. A., Pranoto, N. H. & Robson, R. (2011). Dalton Trans. 40, 12242–12247. Web of Science CSD CrossRef CAS PubMed Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G., Siliqi, D. & Spagna, R. (2007). J. Appl. Cryst. 40, 609–613. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kawata, S. & Kitagawa, S. (2002). Coord. Chem. Rev. 224, 11–34. Google Scholar
Kawata, S., Kumagai, H., Adachi, K. & Kitagawa, S. (2000). Dalton Trans. pp. 2409–2417. Web of Science CSD CrossRef Google Scholar
Luo, T., Liu, Y., Tsai, H., Su, C., Ueng, C. & Lu, K. (2004). Eur. J. Inorg. Chem. pp. 4253–4258. Web of Science CSD CrossRef Google Scholar
Nagayoshi, K., Kabir, M. K., Tobita, H., Honda, K., Kawahara, M., Katada, M., Adachi, K., Nishikawa, H., Ikemoto, I., Kumagai, H., Hosokoshi, Y., Inoue, K., Kitagawa, S. & Kawata, S. (2003). J. Am. Chem. Soc. 125, 221–232. Web of Science CSD CrossRef PubMed CAS Google Scholar
Nishimura, Y., Himegi, A., Fuyuhiro, A., Hayami, S. & Kawata, S. (2013). Acta Cryst. E69, m119–m120. CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Chloranilic acid (H2CA = 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) and its homologues, which contain two chelating coordination sites, are capable of bridging metal centers to form monomeric molecules, chains, sheets, or three-dimensional structures (Kawata & Kitagawa, 2002; Luo et al., 2004; Abrahams et al., 2011). In line with our study of metal-chloranilate complexes, we have been trying to develop metal-chloranilate hybrid materials and have found host–guest compounds (Kawata et al., 2000; Nagayoshi et al., 2003; Nishimura et al., 2013). We report here, a novel inorganic-organic hybrid system by using metal-chloranirate complexes as host layers and alkylamines as guests.
The title compound, (C12H25NH3)2[Cu(C6Cl2O4)2(C2H5OH)2], consists of the mononuclear [Cu(CA)2(EtOH)2]2- dianion and the protonated n-dodecylamine (Hda+). The CuII atom lies on a crystallographic inversion center. The geometry around the CuII atom is a distorted octahedron involving four O atoms of two CA2- anions and two O atoms from two ethanol molecules which are trans to each other. The axial bond distances are much longer than the equatorial ones (Table 1). The [Cu(CA)2(EtOH)2]2- anions make a tape structure running along the a axis (Fig. 2) via an intermolecular O—H···O hydrogen bond (Table 2) between the coordinated ethanol molecule and the terminal oxygen atom of CA2-. The tapes are linked through N—H···O hydrogen bonds (Table 2) between the dianion and the Hda+ cation, forming a two-dimensional network expanding parallel to the ab plane (Fig. 3).