A novel two-dimensional CdII

coordination polymer: poly[aqua[l4-2-(4-carboxylatobenzoyl)benzoato]-cadmium(II)]

Hui-Ru Chen* and Wen-Wen Zhang

Department of Pharmaceutical Technology and Biological Engineering, Changzhou

Institute of Engineering Technology, Changzhou 213164, People’s Republic of China

Correspondence e-mail: chrczie@gmail.com

Received 20 September 2014

Accepted 17 October 2014

The title CdII coordination framework, [Cd(C15H8O5)(H2O)]n

or [Cd(bpdc)(H2O)]n [H2bpdc is 2-(4-carboxybenzoyl)benzoic

acid], has been prepared and characterized using IR spectro-

scopy, elemental analysis, thermal analysis and single-crystal

X-ray diffraction. Each CdII centre is six-coordinated by

two O atoms from one 2-(4-carboxylatobenzoyl)benzoate

(bpdc2�) ligand in chelating mode, three O-donor atoms from

three other bpdc2� anions and one O atom from a coordinated

water molecule in an octahedral coordination environment.

Two crystallographically equivalent CdII cations are bridged

by one O atom of the 2-carboxylate group of one bpdc2�

ligand and by both O atoms of the 4-carboxylate group of a

second bpdc2� ligand to form a binuclear [(Cd)2(O)(OCO)]

secondary building unit. Adjacent secondary building units

are interlinked to form a one-dimensional [Cd(OCO)2]n chain.

The bpdc2� ligands link these rod-shaped chains to give rise to

a complex two-dimensional [Cd(bpdc)]n framework with a 4,4-

connected binodal net topology of point symbol {43.62.8}. The

compound exhibits a strong fluorescence emission and typical

ferroelectric behaviour in the solid state at room temperature.

Keywords: crystal structure; 2-(4-carboxybenzoyl)benzoic acid;{43.62.8} point symbol; photoluminescence properties;ferroelectric behaviour.

1. Introduction

During the past decade coordination polymers have attracted

great interest, not only owing to their intriguing variety of

topologies but also because of their potential applications in

many fields, such as ion-exchange media, heterogeneous

catalysts, optical devices, molecular magnets and gas-storage

devices (Du et al., 2013; Li et al., 2010; Luo et al., 2010; Ma et

al., 2009; Su et al., 2010). Generally, the assembly of coordi-

nation polymers is mainly affected by the combination of a few

factors, including temperature, the neutral ligands, the organic

anions and the metal atoms (Cook et al., 2013; Almeida Paz et

al., 2012). Among these factors, great effort has been devoted

to the design of suitable organic ligands to construct new

coordination polymers.

Organic ligands that contain carboxylic acid groups are

frequently used in coordination polymers since the carboxyl-

ate group has an excellent coordination capability and flexible

coordination patterns, which result in a wide diversity of

structures. 2-(4-Carboxybenzoyl)benzoic acid (H2bpdc), an

asymmetric V-shaped aromatic polycarboxylic acid derivative,

has been used as a bridging ligand in the synthesis of novel

coordination polymers (Chen et al., 2012; Hu et al., 2011, 2009;

Xu et al., 2012). Taking inspiration from the points mentioned

above, we explored the self-assembly of the CdII cation and

H2bpdc under hydrothermal conditions, and obtained a novel

two-dimensional coordination polymer, [Cd(bpdc)(H2O)]n,

(I), and we now report its synthesis, crystal structure and

physical properties.

2. Experimental

All chemicals used in the experiment were purchased from

commercial sources (Sigma–Aldrich) and were used without

further purification. The C and H elemental analyses were

performed on a Vario EL III elemental analyser (Elementar

Analysensysteme GmbH). The IR spectrum was recorded

from a KBr pellet in the range 4000–400 cm�1 on a VECTOR

22 spectrometer (Bruker). The fluorescence spectrum was

recorded on a Fluoro Max-P spectrophotometer (Perkin–

Elmer). Thermogravimetric analysis was performed on a

Perkin–Elmer Pyris 1 TGA analyser from 298 to 1123 K with a

heating rate of 20 K min�1 under nitrogen (TA Instruments).

The electric hysteresis loop was measured with a Premier II

ferroelectric tester at room temperature (Radiant Technology

Inc.).

2.1. Synthesis and crystallization

A mixture of Cd(NO3)2�6H2O (0.0346 g, 0.1 mmol), H2bpdc

(0.0271 g, 0.1 mmol) and KOH (0.0112 g, 0.2 mmol) in H2O

(10 ml) was sealed in a 16 ml Teflon-lined stainless steel

container and heated at 493 K for 72 h. After cooling to room

temperature, colourless block-shaped crystals of (I) were

research papers

Acta Cryst. (2014). C70, 1079–1082 doi:10.1107/S2053229614022852 # 2014 International Union of Crystallography 1079

Acta Crystallographica Section C

Structural Chemistry

ISSN 2053-2296

collected by filtration and washed in water and ethanol several

times (yield 22.9%, based on H2bpdc). Elemental analysis for

C15H10CdO6: C 45.19, H 2.53%; found: C 45.28, H 2.54%. IR

(KBr, �, cm�1): 3439 (m), 3057 (m), 1661 (s), 1578 (s), 1424

(vs), 1274 (s), 1234 (s), 841 (s), 771 (s), 722 (s).

2.2. Refinement

Crystal data, data collection and structure refinement

details are summarized in Table 1. C-bound H atoms were

placed in calculated positions and treated using a riding-model

approximation, with C—H = 0.93 A and Uiso(H) = 1.2Ueq(C).

Water H atoms were located in a difference Fourier map and

refined with Uiso(H) = 1.2Ueq(O) and with the O—H distances

restrained to 0.85 (2) A.

3. Results and discussion

X-ray crystallography reveals that the asymmetric unit of (I)

consists of a divalent CdII cation, one fully deprotonated 2-(4-

carboxylatobenzoyl)benzoate (bpdc2�) ligand and one aqua

ligand. As shown in Fig. 1, atom Cd1 is six-coordinated by two

O atoms from one bpdc2� ligand in a chelating mode, three

O-donor atoms from three individual bpdc2� anions and one

O atom from a coordinated water molecule in an octahedral

coordination environment (Table 2). The average of the

Cd—O distances [2.31 (4) A] is comparable with those for

other structures containing CdII (Wang et al., 2013; Wang,

2014).

In the bpdc2� ligand in (I), the dihedral angle between the

planes of the two benzene rings is 79.8 (2)� and the C5—C8—

C9 angle is 118.6 (3)�. The dihedral angles between the planes

of the carboxylate groups at C2 and C14 and those of their

adjacent benzene rings are 19.7 (3) and 17.5 (3)�, respectively.

Each bpdc2� anion in (I) acts in a �4-mode (�2-�1:�1 and

�2-�2:�1), with one carboxylate group bridging two CdII

cations in a bis-monodentate mode and the other carboxylate

group bridging two other CdII cations in a briding mode. Two

crystallographically equivalent CdII cations are bridged by

atom O1 of the 2-carboxylate group of one bpdc2� ligand and

by both O atoms of the 4-carboxylate group (O4—C15—O5)

of a second bpdc2� ligand to form a binuclear [(Cd1)2-

(O1)(O4–C15–O5)] secondary building unit (SBU) with a

Cd� � �Cd separation of 3.805 (2) A. As shown in Fig. 2, adja-

cent SBUs are interlinked to form a one-dimensional

[Cd(OCO)2]n chain extending along the c axis. The bpdc2�

ligands crosslink these rod-shaped SBUs to give rise to a

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1080 Chen and Zhang � [Cd(C15H8O5)(H2O)] Acta Cryst. (2014). C70, 1079–1082

Table 1Experimental details.

Crystal dataChemical formula [Cd(C15H8O5)(H2O)]Mr 398.63Crystal system, space group Orthorhombic, Aba2Temperature (K) 296a, b, c (A) 12.664 (6), 30.334 (15), 7.060 (4)V (A3) 2712 (2)Z 8Radiation type Mo K�� (mm�1) 1.64Crystal size (mm) 0.21 � 0.19 � 0.17

Data collectionDiffractometer Bruker SMART CCD area-detector

diffractometerAbsorption correction Multi-scan (SADABS; Bruker, 2000)Tmin, Tmax 0.725, 0.768No. of measured, independent and

observed [I > 2�(I)] reflections8238, 3061, 2511

Rint 0.034(sin �/�)max (A�1) 0.652

RefinementR[F 2 > 2�(F 2)], wR(F 2), S 0.028, 0.055, 0.99No. of reflections 3061No. of parameters 205No. of restraints 3H-atom treatment H atoms treated by a mixture of

independent and constrainedrefinement

�max, �min (e A�3) 0.36, �0.89Absolute structure Flack (1983), with 1218 Friedel pairsAbsolute structure parameter 0.02 (3)

Computer programs: SMART (Bruker 2000), SAINT (Bruker 2000), SHELXS97(Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999) andSHELXTL (Sheldrick, 2008).

Figure 1A view of the local coordination of the CdII cation in (I), showing theatom-numbering scheme. Displacement ellipsoids are drawn at the 30%probability level. [Symmetry codes: (i) �x + 1

2, y, z � 12; (ii) x + 1

2, �y + 1,z � 1

2; (iii) �x, �y + 1, z � 1.]

Figure 2A view of the infinite rod-shaped SBU in (I).

Table 2Selected geometric parameters (A, �).

Cd1—O1i 2.263 (3) Cd1—O6 2.307 (3)Cd1—O5ii 2.281 (3) Cd1—O1 2.358 (3)Cd1—O4iii 2.293 (3) Cd1—O2 2.360 (3)

O1i—Cd1—O5ii 80.26 (14) O4iii—Cd1—O1 147.99 (10)O1i—Cd1—O4iii 82.62 (10) O6—Cd1—O1 84.63 (11)O5ii—Cd1—O4iii 98.09 (17) O1i—Cd1—O2 91.61 (10)O1i—Cd1—O6 158.91 (11) O5ii—Cd1—O2 158.02 (13)O5ii—Cd1—O6 89.18 (13) O4iii—Cd1—O2 101.09 (10)O4iii—Cd1—O6 80.86 (11) O6—Cd1—O2 104.34 (12)O1i—Cd1—O1 116.10 (10) O1—Cd1—O2 55.37 (9)O5ii—Cd1—O1 110.11 (18)

Symmetry codes: (i) �xþ 12; y; z� 1

2; (ii) xþ 12;�yþ 1; z� 1

2; (iii) �x;�yþ 1; z� 1.

complex two-dimensional [Cd(bpdc)]n framework parallel to

the (010) crystal plane (Fig. 3).

The topology of this neutral [Cd(bpdc)]n two-dimensional

framework can be simplified by regarding both the CdII

cations and the bpdc2� ligands as 4-connected nodes. The

resulting network thus has a 4,4-connected binodal net

topology of point symbol {43.62.8} (Fig. 4). To the best of our

knowledge, this 4,4-connected binodal lattice has not yet been

reported in coordination polymer chemistry.

Interlayer interactions are fostered by weak O—H� � �O and

C—H� � �O hydrogen bonds (see Table 3), constructing a three-

dimensional supramolecular architecture.

To test the thermal stability of (I), thermogravimetric

analysis (TGA) was conducted. As shown in Fig. 5, the co-

ordinated water molecule was lost between 373 and 433 K

(observed 3.98%, calculated 4.52%). The anhydrous substance

was stable upon heating to 483 K. The decomposition of the

organic ligand was observed between 483 and 1063 K, and the

remaining weight corresponds to the formation of CdO

(observed 32.03%, calculated 32.21%).

Due to the excellent fluorescence properties of d10 metal

compounds, the solid-state photoluminescence properties of

(I) were investigated at room temperature. The H2bpdc ligand

exhibits a broad weak fluorescent emission centred at 394 nm

with an excitation maximum at 280 nm, which can probably be

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Acta Cryst. (2014). C70, 1079–1082 Chen and Zhang � [Cd(C15H8O5)(H2O)] 1081

Figure 3A view of the two-dimensional structure of (I), which extendsperpendicular to the b axis.

Figure 4A network perspective of the 4,4-connected binodal {43.62.8} pointsymbol in (I). The turquoise and black spheres represent the CdII atomsand bpdc2� ligands, respectively.

Table 3Hydrogen-bond geometry (A, �).

D—H� � �A D—H H� � �A D� � �A D—H� � �A

O6—H6A� � �O5iv 0.84 (2) 2.40 (3) 3.133 (8) 147 (4)O6—H6B� � �O3iii 0.85 (2) 2.13 (3) 2.828 (5) 139 (4)C3—H3� � �O3v 0.93 2.50 3.290 (6) 143C6—H6� � �O2vi 0.93 2.50 3.292 (5) 143

Symmetry codes: (iii) �x;�yþ 1; z � 1; (iv) �x;�yþ 1; z; (v) x; y; z� 1; (vi)x; y; zþ 1.

Figure 5The thermogravimetric plot for (I).

Figure 6The solid-state emission spectrum of (I), recorded at room temperature.

attributed to *–n or *– transitions, as reported previously

(Xu et al., 2012). Compound (I) exhibits a relatively strong

emission band centred on �410 nm upon excitation at 290 nm

(Fig. 6). Because the CdII cation is difficult to oxidize or

reduce, due to its d10 configuration, the emissive behaviour of

(I) can be attributed to ligand-centred electronic transitions

(Guo et al., 2011; Wen et al., 2007).

Since (I) crystallizes in the noncentrosymmetric space

group Aba2, which belongs to one of the ten polar point

groups, its ferroelectric features were investigated (Hang et al.,

2011; Zhang & Xiong, 2012). Fig. 7 clearly indicates that (I)

does indeed display ferroelectric behaviour, with a remnant

polarization (Pr) of ca 0.67 mC cm�2 and a coercive field (Ec)

of 475.35 V cm�1. The saturation value of the spontaneous

polarization (Ps) is �1.23 mC cm�2.

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2191–2194.Wen, L., Lu, Z., Lin, J., Tian, Z., Zhu, H. & Meng, Q. (2007). Cryst. Growth

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1082 Chen and Zhang � [Cd(C15H8O5)(H2O)] Acta Cryst. (2014). C70, 1079–1082

Figure 7The electric hysteresis loop for (I).

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sup-1Acta Cryst. (2014). C70, 1079-1082

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Acta Cryst. (2014). C70, 1079-1082 [doi:10.1107/S2053229614022852]

A novel two-dimensional CdII coordination polymer: poly[aqua[µ4-2-(4-

carboxylatobenzoyl)benzoato]cadmium(II)]

Hui-Ru Chen and Wen-Wen Zhang

Computing details

Data collection: SMART (Bruker 2000); cell refinement: SAINT (Bruker 2000); data reduction: SAINT (Bruker 2000);

program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97

(Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for

publication: SHELXTL (Sheldrick, 2008).

Poly[aqua[µ4-2-(4-carboxylatobenzoyl)benwq3074zoato]cadmium(II)]

Crystal data

[Cd(C15H8O5)(H2O)]Mr = 398.63Orthorhombic, Aba2Hall symbol: A 2 -2aca = 12.664 (6) Åb = 30.334 (15) Åc = 7.060 (4) ÅV = 2712 (2) Å3

Z = 8F(000) = 1568Dx = 1.953 Mg m−3

Mo Kα radiation, λ = 0.71073 ŵ = 1.64 mm−1

T = 296 KBlock, colourless0.21 × 0.19 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tubeGraphite monochromatorφ and ω scansAbsorption correction: multi-scan

SADABS (Bruker, 2000)Tmin = 0.725, Tmax = 0.768

8238 measured reflections3061 independent reflections2511 reflections with I > 2σ(I)Rint = 0.034θmax = 27.6°, θmin = 2.1°h = −8→16k = −39→25l = −9→9

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.028wR(F2) = 0.055S = 0.993061 reflections205 parameters3 restraintsPrimary atom site location: structure-invariant

direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2(Fo2) + (0.0207P)2]

where P = (Fo2 + 2Fc

2)/3(Δ/σ)max = 0.002Δρmax = 0.36 e Å−3

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sup-2Acta Cryst. (2014). C70, 1079-1082

Δρmin = −0.89 e Å−3 Absolute structure: Flack (1983), with 1218 Friedel pairs

Absolute structure parameter: 0.02 (3)

Special details

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)

x y z Uiso*/Ueq

C1 0.1456 (3) 0.46675 (13) 0.3340 (5) 0.0247 (9)C2 0.1314 (3) 0.50502 (15) 0.4667 (6) 0.0221 (10)C3 0.1242 (4) 0.54738 (15) 0.3946 (7) 0.0293 (12)H3 0.1260 0.5520 0.2644 0.035*C4 0.1143 (4) 0.58270 (17) 0.5164 (6) 0.0286 (12)H4 0.1118 0.6112 0.4675 0.034*C5 0.1080 (4) 0.57638 (16) 0.7112 (6) 0.0233 (10)C6 0.1151 (4) 0.53324 (15) 0.7841 (6) 0.0255 (11)H6 0.1117 0.5285 0.9141 0.031*C7 0.1269 (4) 0.49802 (16) 0.6622 (6) 0.0240 (11)H7 0.1318 0.4695 0.7103 0.029*C8 0.0973 (3) 0.61466 (13) 0.8439 (6) 0.0288 (9)C9 0.0826 (3) 0.65986 (13) 0.7619 (5) 0.0275 (9)C10 0.1692 (3) 0.68747 (16) 0.7589 (7) 0.0443 (12)H10 0.2327 0.6782 0.8118 0.053*C11 0.1619 (4) 0.72935 (16) 0.6764 (7) 0.0543 (14)H11 0.2207 0.7477 0.6751 0.065*C12 0.0700 (4) 0.74334 (12) 0.5987 (13) 0.0513 (11)H12 0.0661 0.7710 0.5424 0.062*C13 −0.0181 (3) 0.71616 (11) 0.6034 (9) 0.0367 (9)H13 −0.0812 0.7259 0.5509 0.044*C14 −0.0134 (3) 0.67491 (13) 0.6849 (5) 0.0262 (9)C15 −0.1114 (3) 0.64644 (13) 0.6943 (5) 0.0274 (9)Cd1 0.193946 (18) 0.400042 (7) 0.09130 (6) 0.02709 (7)O1 0.1826 (2) 0.43005 (9) 0.3988 (4) 0.0327 (6)O2 0.1235 (2) 0.47011 (9) 0.1631 (4) 0.0344 (7)O3 0.1084 (3) 0.61025 (9) 1.0158 (4) 0.0460 (8)O4 −0.1117 (2) 0.61486 (9) 0.8091 (4) 0.0369 (7)O5 −0.1862 (2) 0.65611 (8) 0.5860 (10) 0.0484 (7)O6 0.0677 (3) 0.35110 (12) 0.1977 (4) 0.0470 (8)H6A 0.074 (4) 0.3446 (15) 0.312 (3) 0.056*H6B 0.0031 (18) 0.3508 (16) 0.168 (6) 0.056*

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sup-3Acta Cryst. (2014). C70, 1079-1082

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

C1 0.020 (2) 0.025 (2) 0.028 (2) −0.0015 (16) 0.0025 (16) −0.0026 (16)C2 0.020 (2) 0.025 (3) 0.021 (2) 0.0005 (18) 0.0006 (17) 0.0037 (18)C3 0.040 (3) 0.024 (3) 0.023 (2) 0.006 (2) 0.0028 (19) 0.0031 (19)C4 0.039 (3) 0.019 (2) 0.027 (2) 0.000 (2) 0.0004 (18) 0.0010 (18)C5 0.024 (2) 0.024 (3) 0.022 (2) 0.004 (2) 0.0022 (17) −0.0033 (18)C6 0.027 (2) 0.027 (3) 0.022 (2) 0.003 (2) −0.0026 (18) 0.004 (2)C7 0.031 (2) 0.018 (2) 0.0229 (19) 0.0073 (19) −0.0050 (16) −0.0007 (16)C8 0.025 (2) 0.030 (2) 0.031 (2) 0.0004 (17) −0.0027 (17) 0.0001 (17)C9 0.033 (2) 0.025 (2) 0.0249 (19) −0.0001 (19) 0.0022 (17) −0.0073 (16)C10 0.034 (3) 0.041 (3) 0.057 (3) −0.006 (2) −0.005 (2) −0.010 (2)C11 0.057 (3) 0.038 (3) 0.068 (3) −0.020 (3) 0.016 (3) −0.013 (2)C12 0.079 (3) 0.027 (2) 0.048 (2) −0.008 (2) 0.008 (4) 0.010 (4)C13 0.054 (2) 0.0240 (19) 0.032 (2) 0.0026 (16) −0.001 (3) 0.001 (3)C14 0.036 (2) 0.023 (2) 0.0192 (18) −0.0026 (17) 0.0028 (16) −0.0013 (15)C15 0.031 (2) 0.022 (2) 0.029 (2) −0.0013 (18) 0.0039 (17) −0.0063 (17)Cd1 0.03306 (13) 0.02638 (13) 0.02184 (10) −0.00207 (11) −0.0006 (2) −0.0039 (2)O1 0.0399 (17) 0.0254 (16) 0.0328 (14) 0.0076 (13) −0.0088 (13) −0.0024 (12)O2 0.0449 (18) 0.0328 (17) 0.0254 (13) 0.0077 (13) 0.0012 (12) −0.0039 (11)O3 0.071 (2) 0.042 (2) 0.0247 (13) 0.0157 (16) −0.0099 (14) −0.0031 (12)O4 0.0443 (18) 0.0330 (17) 0.0334 (15) −0.0036 (14) 0.0100 (13) 0.0001 (13)O5 0.0400 (16) 0.0341 (15) 0.0711 (19) 0.0004 (12) −0.016 (3) −0.002 (3)O6 0.060 (2) 0.049 (2) 0.0322 (17) −0.0167 (18) −0.0028 (16) 0.0080 (15)

Geometric parameters (Å, º)

C1—O2 1.243 (4) C11—C12 1.354 (7)C1—O1 1.291 (4) C11—H11 0.9300C1—C2 1.503 (6) C12—C13 1.388 (5)C2—C3 1.385 (6) C12—H12 0.9300C2—C7 1.398 (6) C13—C14 1.378 (5)C3—C4 1.379 (6) C13—H13 0.9300C3—H3 0.9300 C14—C15 1.514 (5)C4—C5 1.391 (5) C15—O5 1.253 (6)C4—H4 0.9300 C15—O4 1.255 (5)C5—C6 1.409 (6) Cd1—O1i 2.263 (3)C5—C8 1.498 (6) Cd1—O5ii 2.281 (3)C6—C7 1.380 (6) Cd1—O4iii 2.293 (3)C6—H6 0.9300 Cd1—O6 2.307 (3)C7—H7 0.9300 Cd1—O1 2.358 (3)C8—O3 1.229 (5) Cd1—O2 2.360 (3)C8—C9 1.500 (5) O1—Cd1iv 2.263 (3)C9—C10 1.380 (6) O4—Cd1v 2.293 (3)C9—C14 1.409 (5) O5—Cd1vi 2.281 (3)C10—C11 1.401 (7) O6—H6A 0.836 (19)C10—H10 0.9300 O6—H6B 0.845 (19)

supporting information

sup-4Acta Cryst. (2014). C70, 1079-1082

O2—C1—O1 119.7 (3) C13—C12—H12 120.2O2—C1—C2 121.0 (4) C14—C13—C12 121.0 (5)O1—C1—C2 119.3 (3) C14—C13—H13 119.5C3—C2—C7 120.1 (5) C12—C13—H13 119.5C3—C2—C1 119.7 (4) C13—C14—C9 119.5 (4)C7—C2—C1 120.2 (4) C13—C14—C15 120.1 (4)C4—C3—C2 119.8 (5) C9—C14—C15 120.4 (3)C4—C3—H3 120.1 O5—C15—O4 124.8 (4)C2—C3—H3 120.1 O5—C15—C14 117.4 (4)C3—C4—C5 121.0 (5) O4—C15—C14 117.8 (4)C3—C4—H4 119.5 O1i—Cd1—O5ii 80.26 (14)C5—C4—H4 119.5 O1i—Cd1—O4iii 82.62 (10)C4—C5—C6 119.1 (5) O5ii—Cd1—O4iii 98.09 (17)C4—C5—C8 121.1 (5) O1i—Cd1—O6 158.91 (11)C6—C5—C8 119.8 (4) O5ii—Cd1—O6 89.18 (13)C7—C6—C5 119.9 (4) O4iii—Cd1—O6 80.86 (11)C7—C6—H6 120.1 O1i—Cd1—O1 116.10 (10)C5—C6—H6 120.1 O5ii—Cd1—O1 110.11 (18)C6—C7—C2 120.2 (5) O4iii—Cd1—O1 147.99 (10)C6—C7—H7 119.9 O6—Cd1—O1 84.63 (11)C2—C7—H7 119.9 O1i—Cd1—O2 91.61 (10)O3—C8—C9 119.7 (4) O5ii—Cd1—O2 158.02 (13)O3—C8—C5 121.5 (4) O4iii—Cd1—O2 101.09 (10)C9—C8—C5 118.6 (3) O6—Cd1—O2 104.34 (12)C10—C9—C14 118.9 (4) O1—Cd1—O2 55.37 (9)C10—C9—C8 117.5 (4) C1—O1—Cd1iv 144.1 (2)C14—C9—C8 123.5 (3) C1—O1—Cd1 91.7 (2)C9—C10—C11 120.3 (4) Cd1iv—O1—Cd1 110.81 (11)C9—C10—H10 119.9 C1—O2—Cd1 92.8 (2)C11—C10—H10 119.9 C15—O4—Cd1v 135.5 (3)C12—C11—C10 120.6 (4) C15—O5—Cd1vi 108.6 (3)C12—C11—H11 119.7 Cd1—O6—H6A 114 (3)C10—C11—H11 119.7 Cd1—O6—H6B 127 (3)C11—C12—C13 119.7 (5) H6A—O6—H6B 109 (4)C11—C12—H12 120.2

O2—C1—C2—C3 −19.3 (6) C10—C9—C14—C15 −177.0 (4)O1—C1—C2—C3 159.9 (4) C8—C9—C14—C15 4.6 (5)O2—C1—C2—C7 161.5 (5) C13—C14—C15—O5 18.1 (6)O1—C1—C2—C7 −19.3 (7) C9—C14—C15—O5 −163.0 (4)C7—C2—C3—C4 1.1 (8) C13—C14—C15—O4 −162.2 (4)C1—C2—C3—C4 −178.1 (4) C9—C14—C15—O4 16.7 (5)C2—C3—C4—C5 −2.1 (9) O2—C1—O1—Cd1iv 136.6 (3)C3—C4—C5—C6 1.9 (10) C2—C1—O1—Cd1iv −42.6 (6)C3—C4—C5—C8 −180.0 (4) O2—C1—O1—Cd1 6.4 (4)C4—C5—C6—C7 −0.7 (8) C2—C1—O1—Cd1 −172.8 (3)C8—C5—C6—C7 −178.8 (4) O1i—Cd1—O1—C1 68.99 (19)

supporting information

sup-5Acta Cryst. (2014). C70, 1079-1082

C5—C6—C7—C2 −0.3 (8) O5ii—Cd1—O1—C1 157.8 (2)C3—C2—C7—C6 0.1 (9) O4iii—Cd1—O1—C1 −51.9 (3)C1—C2—C7—C6 179.3 (4) O6—Cd1—O1—C1 −115.1 (2)C4—C5—C8—O3 −168.3 (5) O2—Cd1—O1—C1 −3.5 (2)C6—C5—C8—O3 9.8 (7) O1i—Cd1—O1—Cd1iv −82.36 (19)C4—C5—C8—C9 5.9 (7) O5ii—Cd1—O1—Cd1iv 6.42 (15)C6—C5—C8—C9 −175.9 (4) O4iii—Cd1—O1—Cd1iv 156.72 (14)O3—C8—C9—C10 72.0 (5) O6—Cd1—O1—Cd1iv 93.56 (14)C5—C8—C9—C10 −102.4 (5) O2—Cd1—O1—Cd1iv −154.89 (17)O3—C8—C9—C14 −109.6 (5) O1—C1—O2—Cd1 −6.4 (4)C5—C8—C9—C14 76.1 (5) C2—C1—O2—Cd1 172.8 (3)C14—C9—C10—C11 −1.4 (6) O1i—Cd1—O2—C1 −117.3 (2)C8—C9—C10—C11 177.1 (4) O5ii—Cd1—O2—C1 −49.8 (5)C9—C10—C11—C12 0.0 (8) O4iii—Cd1—O2—C1 159.9 (2)C10—C11—C12—C13 1.0 (10) O6—Cd1—O2—C1 76.6 (3)C11—C12—C13—C14 −0.5 (11) O1—Cd1—O2—C1 3.7 (2)C12—C13—C14—C9 −0.9 (8) O5—C15—O4—Cd1v −72.4 (6)C12—C13—C14—C15 177.9 (6) C14—C15—O4—Cd1v 107.9 (4)C10—C9—C14—C13 1.9 (6) O4—C15—O5—Cd1vi −10.9 (6)C8—C9—C14—C13 −176.6 (4) C14—C15—O5—Cd1vi 168.8 (3)

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) x+1/2, −y+1, z−1/2; (iii) −x, −y+1, z−1; (iv) −x+1/2, y, z+1/2; (v) −x, −y+1, z+1; (vi) x−1/2, −y+1, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O6—H6A···O5vii 0.84 (2) 2.40 (3) 3.133 (8) 147 (4)O6—H6B···O3iii 0.85 (2) 2.13 (3) 2.828 (5) 139 (4)C3—H3···O3viii 0.93 2.50 3.290 (6) 143C6—H6···O2ix 0.93 2.50 3.292 (5) 143

Symmetry codes: (iii) −x, −y+1, z−1; (vii) −x, −y+1, z; (viii) x, y, z−1; (ix) x, y, z+1.