Synthesis, structure and properties of a new three-dimensional inter­penetrated metal-organic framework with 3,3'-azodi­benzoic acid (H₂azdc) and 1,4-bis­(1H-imidazol-1-yl)butane (bimb): {[Cd(azdc)(bimb)₂]·H₂O}_n

A new three-dimensional inter­penetrated Cd^II-organic framework based on 3,3'-azodi­benzoic acid [3,3'-(diazenedi­yl)di­benzoic acid, H₂azdc] and the aux­iliary flexible ligand 1,4-bis­(1H-imidazol-1-yl)butane (bimb), namely poly[[bis­[[mu]₂-1,4-bis­(1H-imidazol-1-yl)butane-[kappa]²N³:N^3'][[mu]₂-3,3'-(diazenedi­yl)di­ben­zoato-[kappa]²O:O']cadmium(II)] monohydrate], {[Cd(C₁₄H₈N₂O₄)(C₁₀H₁₄N₂)₂]·H₂O}_n, (1), was obtained by a typical solution reaction in mixed solvents (water and N,N'-di­methyl­formamide). Each Cd^II centre is six-coordinated by two O atoms of bis-monodentate bridging carboxyl­ate groups from two azdc^2- ligands and by four N atoms from four bimb ligands, forming an octa­hedral coordination environment. The Cd^II ions are connected by the bimb ligands, resulting in two-dimensional (4,4) layers, which are further pillared by the azdc^2- ligands, affording a threefold inter­penetrated three-dimensional [alpha]-Po topological framework with the Schläfli symbol 4¹²6³. The thermal stability and solid-state fluorescence properties of (1) have been investigated.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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: publCIF (Westrip, 2010).

Poly[[bis[µ₂-1,4-bis(1H-imidazol-1-yl)butane-κ²N³:N^3'][µ₂-3,3'-(diazenediyl)dibenzoato-κ²O:O']cadmium(II)] monohydrate]

Crystal data

[Cd(C14H8N2O4)(C10H14N4)2]·H2O	F(000) = 1600
Mr = 779.14	Dx = 1.490 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.3202 (13) Å	Cell parameters from 9906 reflections
b = 14.3929 (13) Å	θ = 2.5–27.5°
c = 23.679 (3) Å	µ = 0.69 mm^−1
β = 99.157 (4)°	T = 296 K
V = 3472.4 (7) Å^3	Block, yellow
Z = 4	0.28 × 0.20 × 0.14 mm

Data collection

Bruker APEXII area-detector diffractometer	3998 independent reflections
Radiation source: fine-focus sealed tube	3396 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −13→13
Tmin = 0.848, Tmax = 0.908	k = −18→18
34516 measured reflections	l = −30→30

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.156	H-atom parameters constrained
S = 1.29	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 26.4708P] where P = (Fo^2 + 2Fc^2)/3
3998 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 2.32 e Å^−3
2 restraints	Δρmin = −0.72 e Å^−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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.1939 (5)	1.0154 (3)	0.3952 (2)	0.0328 (11)
C2	0.3347 (5)	1.0336 (3)	0.3865 (2)	0.0296 (10)
C3	0.3665 (5)	1.0334 (4)	0.3320 (2)	0.0319 (10)
H3	0.3016	1.0256	0.3003	0.038*
C4	0.4974 (5)	1.0450 (4)	0.3252 (2)	0.0403 (12)
C5	0.5952 (6)	1.0565 (5)	0.3718 (3)	0.0559 (17)
H5	0.6824	1.0614	0.3667	0.067*
C6	0.5626 (6)	1.0605 (6)	0.4256 (3)	0.0623 (19)
H6	0.6272	1.0713	0.4570	0.075*
C7	0.4331 (5)	1.0484 (5)	0.4331 (2)	0.0449 (13)
H7	0.4117	1.0502	0.4698	0.054*
C8	−0.1158 (6)	0.8827 (4)	0.3836 (2)	0.0446 (13)
H8	−0.0579	0.9129	0.3634	0.054*
C9	−0.2662 (7)	0.7895 (5)	0.4035 (3)	0.0587 (17)
H9	−0.3306	0.7438	0.4011	0.070*
C10	−0.2243 (6)	0.8438 (5)	0.4487 (3)	0.0499 (14)
H10	−0.2560	0.8419	0.4833	0.060*
C11	−0.2070 (11)	0.7727 (5)	0.3035 (3)	0.090 (3)
H11A	−0.1351	0.7294	0.3034	0.108*
H11B	−0.2882	0.7377	0.2954	0.108*
C12	−0.2041 (11)	0.8373 (7)	0.2596 (3)	0.095 (3)
H12A	−0.1205	0.8696	0.2659	0.114*
H12B	−0.2728	0.8830	0.2607	0.114*
C13	0.0838 (5)	0.8493 (4)	0.6034 (2)	0.0364 (11)
H13	0.0661	0.8936	0.6298	0.044*
C14	0.1075 (8)	0.7833 (5)	0.5256 (3)	0.069 (2)
H14	0.1096	0.7733	0.4870	0.083*
C15	0.1359 (10)	0.7186 (5)	0.5670 (3)	0.078 (3)
H15	0.1604	0.6573	0.5624	0.093*
C16	0.1391 (8)	0.7213 (5)	0.6751 (3)	0.0641 (19)
H16A	0.0978	0.7612	0.7000	0.077*
H16B	0.0957	0.6614	0.6734	0.077*
C17	0.2766 (9)	0.7093 (8)	0.6992 (3)	0.093 (3)
H17A	0.3193	0.7696	0.7023	0.112*
H17B	0.3187	0.6714	0.6736	0.112*
Cd1	0.0000	1.0000	0.5000	0.02904 (16)
N1	0.5437 (5)	1.0453 (4)	0.2710 (2)	0.0491 (12)
N2	−0.1285 (4)	0.9020 (3)	0.43653 (17)	0.0368 (10)
N3	−0.1972 (6)	0.8139 (4)	0.3622 (2)	0.0513 (13)
N4	0.0753 (4)	0.8650 (3)	0.54834 (18)	0.0364 (9)
N5	0.1211 (6)	0.7622 (3)	0.6171 (2)	0.0483 (12)
O1	0.1763 (4)	1.0003 (3)	0.44551 (16)	0.0489 (10)
O2	0.1087 (4)	1.0132 (3)	0.35170 (17)	0.0533 (11)
O1W	0.0000	0.8945 (6)	0.7500	0.106 (3)
H1WA	0.0363	0.9262	0.7785	0.127*	0.50
H1WB	−0.0282	0.9307	0.7224	0.127*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.031 (2)	0.034 (3)	0.037 (2)	0.0030 (19)	0.016 (2)	0.006 (2)
C2	0.028 (2)	0.035 (2)	0.029 (2)	0.0035 (19)	0.0135 (18)	0.0032 (19)
C3	0.030 (2)	0.037 (2)	0.031 (2)	0.002 (2)	0.0120 (19)	0.004 (2)
C4	0.037 (3)	0.048 (3)	0.041 (3)	0.002 (2)	0.024 (2)	0.008 (2)
C5	0.029 (3)	0.085 (5)	0.056 (4)	−0.007 (3)	0.012 (3)	0.011 (3)
C6	0.039 (3)	0.100 (6)	0.046 (3)	−0.012 (3)	0.001 (3)	0.003 (4)
C7	0.035 (3)	0.068 (4)	0.032 (3)	0.001 (3)	0.009 (2)	0.004 (3)
C8	0.056 (3)	0.047 (3)	0.031 (3)	−0.007 (3)	0.007 (2)	0.002 (2)
C9	0.054 (4)	0.062 (4)	0.056 (4)	−0.025 (3)	−0.005 (3)	0.001 (3)
C10	0.053 (3)	0.059 (4)	0.039 (3)	−0.014 (3)	0.011 (3)	0.005 (3)
C11	0.168 (10)	0.046 (4)	0.046 (4)	−0.018 (5)	−0.008 (5)	−0.008 (3)
C12	0.143 (9)	0.087 (6)	0.047 (4)	−0.007 (6)	−0.008 (5)	−0.023 (4)
C13	0.037 (3)	0.033 (3)	0.039 (3)	−0.001 (2)	0.005 (2)	0.001 (2)
C14	0.103 (6)	0.062 (4)	0.041 (3)	0.039 (4)	0.008 (4)	−0.003 (3)
C15	0.139 (8)	0.047 (4)	0.045 (4)	0.043 (5)	0.009 (4)	0.000 (3)
C16	0.096 (6)	0.048 (4)	0.051 (4)	0.011 (4)	0.019 (4)	0.019 (3)
C17	0.096 (7)	0.139 (9)	0.042 (4)	0.012 (6)	0.001 (4)	0.032 (5)
Cd1	0.0271 (2)	0.0374 (3)	0.0222 (2)	0.0021 (2)	0.00255 (16)	0.0035 (2)
N1	0.042 (3)	0.068 (3)	0.044 (3)	0.007 (2)	0.026 (2)	0.006 (2)
N2	0.037 (2)	0.044 (2)	0.028 (2)	−0.005 (2)	0.0013 (17)	−0.0002 (18)
N3	0.069 (3)	0.047 (3)	0.034 (2)	−0.011 (3)	−0.005 (2)	−0.005 (2)
N4	0.035 (2)	0.040 (2)	0.033 (2)	0.0051 (19)	0.0008 (17)	0.0038 (18)
N5	0.068 (3)	0.036 (2)	0.040 (3)	0.009 (2)	0.007 (2)	0.009 (2)
O1	0.042 (2)	0.073 (3)	0.0368 (19)	0.014 (2)	0.0207 (16)	0.013 (2)
O2	0.0335 (19)	0.086 (3)	0.041 (2)	0.000 (2)	0.0082 (16)	0.008 (2)
O1W	0.166 (10)	0.080 (6)	0.061 (5)	0.000	−0.010 (6)	0.000

Geometric parameters (Å, º)

C1—O2	1.244 (6)	C12—H12A	0.9700
C1—O1	1.252 (6)	C12—H12B	0.9700
C1—C2	1.523 (6)	C13—N4	1.312 (7)
C2—C3	1.381 (6)	C13—N5	1.337 (7)
C2—C7	1.391 (7)	C13—H13	0.9300
C3—C4	1.395 (7)	C14—C15	1.348 (9)
C3—H3	0.9300	C14—N4	1.357 (8)
C4—C5	1.382 (8)	C14—H14	0.9300
C4—N1	1.440 (6)	C15—N5	1.373 (8)
C5—C6	1.368 (9)	C15—H15	0.9300
C5—H5	0.9300	C16—C17	1.453 (11)
C6—C7	1.388 (8)	C16—N5	1.477 (7)
C6—H6	0.9300	C16—H16A	0.9700
C7—H7	0.9300	C16—H16B	0.9700
C8—N2	1.311 (7)	C17—C12^ii	1.563 (10)
C8—N3	1.345 (7)	C17—H17A	0.9700
C8—H8	0.9300	C17—H17B	0.9700
C9—C10	1.340 (9)	Cd1—N2	2.318 (4)
C9—N3	1.346 (9)	Cd1—N2^iii	2.318 (4)
C9—H9	0.9300	Cd1—N4^iii	2.325 (4)
C10—N2	1.361 (7)	Cd1—N4	2.325 (4)
C10—H10	0.9300	Cd1—O1^iii	2.392 (3)
C11—C12	1.399 (11)	Cd1—O1	2.392 (3)
C11—N3	1.498 (8)	N1—N1^iv	1.231 (10)
C11—H11A	0.9700	O1W—H1WA	0.8500
C11—H11B	0.9700	O1W—H1WB	0.8500
C12—C17^i	1.563 (10)
O2—C1—O1	126.4 (5)	N4—C14—H14	124.8
O2—C1—C2	117.1 (4)	C14—C15—N5	105.8 (6)
O1—C1—C2	116.4 (5)	C14—C15—H15	127.1
C3—C2—C7	119.3 (4)	N5—C15—H15	127.1
C3—C2—C1	120.0 (4)	C17—C16—N5	112.6 (6)
C7—C2—C1	120.7 (4)	C17—C16—H16A	109.1
C2—C3—C4	119.1 (5)	N5—C16—H16A	109.1
C2—C3—H3	120.5	C17—C16—H16B	109.1
C4—C3—H3	120.5	N5—C16—H16B	109.1
C5—C4—C3	121.3 (5)	H16A—C16—H16B	107.8
C5—C4—N1	114.1 (5)	C16—C17—C12^ii	112.7 (8)
C3—C4—N1	124.7 (5)	C16—C17—H17A	109.1
C6—C5—C4	119.4 (5)	C12^ii—C17—H17A	109.1
C6—C5—H5	120.3	C16—C17—H17B	109.1
C4—C5—H5	120.3	C12^ii—C17—H17B	109.1
C5—C6—C7	119.9 (6)	H17A—C17—H17B	107.8
C5—C6—H6	120.0	N2—Cd1—N2^iii	180.00 (18)
C7—C6—H6	120.0	N2—Cd1—N4^iii	94.45 (16)
C6—C7—C2	120.9 (5)	N2^iii—Cd1—N4^iii	85.55 (16)
C6—C7—H7	119.5	N2—Cd1—N4	85.55 (16)
C2—C7—H7	119.5	N2^iii—Cd1—N4	94.45 (16)
N2—C8—N3	111.4 (5)	N4^iii—Cd1—N4	180.00 (19)
N2—C8—H8	124.3	N2—Cd1—O1^iii	86.73 (16)
N3—C8—H8	124.3	N2^iii—Cd1—O1^iii	93.27 (15)
C10—C9—N3	106.7 (5)	N4^iii—Cd1—O1^iii	92.50 (15)
C10—C9—H9	126.6	N4—Cd1—O1^iii	87.50 (15)
N3—C9—H9	126.6	N2—Cd1—O1	93.27 (15)
C9—C10—N2	110.0 (5)	N2^iii—Cd1—O1	86.73 (16)
C9—C10—H10	125.0	N4^iii—Cd1—O1	87.50 (15)
N2—C10—H10	125.0	N4—Cd1—O1	92.50 (15)
C12—C11—N3	114.8 (6)	O1^iii—Cd1—O1	180.000 (1)
C12—C11—H11A	108.6	N1^iv—N1—C4	114.5 (6)
N3—C11—H11A	108.6	C8—N2—C10	105.0 (5)
C12—C11—H11B	108.6	C8—N2—Cd1	127.9 (4)
N3—C11—H11B	108.6	C10—N2—Cd1	126.7 (4)
H11A—C11—H11B	107.5	C8—N3—C9	106.8 (5)
C11—C12—C17^i	112.3 (8)	C8—N3—C11	125.9 (6)
C11—C12—H12A	109.1	C9—N3—C11	127.2 (6)
C17^i—C12—H12A	109.1	C13—N4—C14	105.2 (5)
C11—C12—H12B	109.1	C13—N4—Cd1	126.7 (4)
C17^i—C12—H12B	109.1	C14—N4—Cd1	127.8 (4)
H12A—C12—H12B	107.9	C13—N5—C15	106.6 (5)
N4—C13—N5	112.0 (5)	C13—N5—C16	126.1 (5)
N4—C13—H13	124.0	C15—N5—C16	127.4 (5)
N5—C13—H13	124.0	C1—O1—Cd1	138.7 (3)
C15—C14—N4	110.5 (6)	H1WA—O1W—H1WB	109.5
C15—C14—H14	124.8
O2—C1—C2—C3	−9.4 (7)	O1—Cd1—N2—C10	154.3 (5)
O1—C1—C2—C3	167.7 (5)	N2—C8—N3—C9	1.0 (8)
O2—C1—C2—C7	172.1 (5)	N2—C8—N3—C11	−178.6 (7)
O1—C1—C2—C7	−10.8 (8)	C10—C9—N3—C8	−0.3 (8)
C7—C2—C3—C4	2.1 (8)	C10—C9—N3—C11	179.2 (7)
C1—C2—C3—C4	−176.5 (5)	C12—C11—N3—C8	−42.5 (13)
C2—C3—C4—C5	0.2 (9)	C12—C11—N3—C9	138.0 (10)
C2—C3—C4—N1	179.4 (5)	N5—C13—N4—C14	0.6 (7)
C3—C4—C5—C6	−2.9 (11)	N5—C13—N4—Cd1	175.0 (4)
N1—C4—C5—C6	177.8 (7)	C15—C14—N4—C13	−0.3 (9)
C4—C5—C6—C7	3.2 (12)	C15—C14—N4—Cd1	−174.5 (6)
C5—C6—C7—C2	−1.0 (12)	N2—Cd1—N4—C13	−131.2 (5)
C3—C2—C7—C6	−1.7 (9)	N2^iii—Cd1—N4—C13	48.8 (5)
C1—C2—C7—C6	176.8 (6)	O1^iii—Cd1—N4—C13	−44.3 (4)
N3—C9—C10—N2	−0.4 (8)	O1—Cd1—N4—C13	135.7 (4)
N3—C11—C12—C17^i	−176.4 (8)	N2—Cd1—N4—C14	41.9 (6)
N4—C14—C15—N5	−0.2 (11)	N2^iii—Cd1—N4—C14	−138.1 (6)
N5—C16—C17—C12^ii	−177.9 (7)	O1^iii—Cd1—N4—C14	128.8 (6)
C5—C4—N1—N1^iv	−172.5 (4)	O1—Cd1—N4—C14	−51.2 (6)
C3—C4—N1—N1^iv	8.2 (7)	N4—C13—N5—C15	−0.8 (8)
N3—C8—N2—C10	−1.2 (7)	N4—C13—N5—C16	−179.4 (6)
N3—C8—N2—Cd1	172.0 (4)	C14—C15—N5—C13	0.6 (10)
C9—C10—N2—C8	1.0 (7)	C14—C15—N5—C16	179.2 (8)
C9—C10—N2—Cd1	−172.3 (4)	C17—C16—N5—C13	−106.0 (9)
N4^iii—Cd1—N2—C8	70.2 (5)	C17—C16—N5—C15	75.6 (11)
N4—Cd1—N2—C8	−109.8 (5)	O2—C1—O1—Cd1	−20.9 (10)
O1^iii—Cd1—N2—C8	162.5 (5)	C2—C1—O1—Cd1	162.4 (4)
O1—Cd1—N2—C8	−17.5 (5)	N2—Cd1—O1—C1	52.8 (6)
N4^iii—Cd1—N2—C10	−118.0 (5)	N2^iii—Cd1—O1—C1	−127.2 (6)
N4—Cd1—N2—C10	62.0 (5)	N4^iii—Cd1—O1—C1	−41.5 (6)
O1^iii—Cd1—N2—C10	−25.7 (5)	N4—Cd1—O1—C1	138.5 (6)

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x, −y+2, −z+1; (iv) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2^v	0.85	1.98	2.822 (6)	172
O1W—H1WB···O2^iii	0.85	1.99	2.822 (6)	166

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