Synthesis, structure and luminescence properties of two new acyl­amide metal-organic frameworks showing 4-connected CdSO₄ and a threefold inter­penetrating dia net

Two new acyl­amide metal-organic frameworks (MOFs), based on mixed N- and O-donor ligands, with 4-connected topologies have been obtained, namely poly[[[mu]₂-N¹,N⁴-bis­(pyridin-3-yl)terephthalamide]­bis­([mu]₃-4,4'-oxy­di­benzo­ato)di­zinc(II)], [Zn₂(C₁₄H₈O₅)₂(C₁₈H₁₄N₄O₂)]_n, (1), and poly[[([mu]₂-benzene-1,4-di­carboxyl­ato)[[mu]₂-N⁴,N^4'-bis­(pyridin-3-yl)-[1,1'-biphen­yl]-4,4'-dicarboxamide]­di­cadmium(II)] dihydrate], {[Cd(C₈H₄O₄)(C₂₄H₁₈N₄O₂)]·2H₂O}_n, (2). Complex (1) is a 4-connected CdSO₄ net with no inter­penetration, where the Zn^II cation is regarded as a 4-connecting node with square geometry. Complex (2) is a 4-connected dia net with threefold inter­penetration, where the Cd^II cation acts as a 4-connecting node with tetra­hedral geometry. The results of thermogravimetric and luminescence analyses are described in detail.

Computing details

For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(1) Poly[[µ₂-N¹,N⁴-bis(pyridin-3-yl)terephthalamide]bis(µ₃-4,4'-oxydibenzoato)dizinc(II)]

Crystal data

[Zn2(C14H8O5)2(C18H14N4O2)]	F(000) = 1960
Mr = 961.48	Dx = 1.602 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.1681 (11) Å	Cell parameters from 7515 reflections
b = 13.0753 (6) Å	θ = 2.3–27.5°
c = 13.2643 (6) Å	µ = 1.28 mm^−1
β = 97.251 (3)°	T = 296 K
V = 3986.0 (3) Å^3	Block, colourless
Z = 4	0.15 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3508 independent reflections
Radiation source: fine-focus sealed tube	3156 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −27→27
Tmin = 0.831, Tmax = 0.883	k = −15→15
15307 measured reflections	l = −15→15

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 2.4443P] where P = (Fo^2 + 2Fc^2)/3
3508 reflections	(Δ/σ)max = 0.002
289 parameters	Δρmax = 0.25 e Å^−3
1 restraint	Δρmin = −0.26 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.13312 (8)	0.96525 (15)	1.15367 (13)	0.0352 (4)
H1	0.1187	0.9025	1.1721	0.042*
C2	0.12116 (7)	1.05220 (14)	1.20735 (13)	0.0320 (4)
C3	0.14191 (9)	1.14547 (15)	1.17736 (15)	0.0383 (4)
H3	0.1346	1.2052	1.2117	0.046*
C4	0.17353 (9)	1.14860 (16)	1.09607 (15)	0.0414 (5)
H4	0.1871	1.2107	1.0743	0.050*
C5	0.18488 (8)	1.05974 (16)	1.04761 (14)	0.0408 (5)
H5	0.2069	1.0622	0.9937	0.049*
C6	0.06887 (8)	0.96708 (15)	1.33522 (14)	0.0361 (4)
C7	0.03264 (7)	0.98706 (14)	1.41927 (13)	0.0310 (4)
C8	0.02800 (8)	0.90811 (14)	1.48834 (13)	0.0330 (4)
H8	0.0464	0.8460	1.4803	0.040*
C9	0.00384 (7)	1.07839 (14)	1.43136 (13)	0.0328 (4)
H9	0.0060	1.1311	1.3849	0.039*
C10	0.25456 (8)	0.82624 (16)	0.86084 (14)	0.0359 (4)
C11	0.28819 (8)	0.86307 (15)	0.77983 (14)	0.0344 (4)
C12	0.31670 (8)	0.79310 (16)	0.72473 (15)	0.0408 (4)
H12	0.3148	0.7237	0.7394	0.049*
C13	0.34773 (9)	0.82510 (16)	0.64876 (16)	0.0456 (5)
H13	0.3668	0.7778	0.6123	0.055*
C14	0.35036 (8)	0.92828 (16)	0.62706 (15)	0.0403 (5)
C15	0.32203 (8)	0.99941 (16)	0.68021 (16)	0.0426 (5)
H15	0.3238	1.0687	0.6650	0.051*
C16	0.29105 (8)	0.96621 (15)	0.75614 (15)	0.0404 (4)
H16	0.2718	1.0136	0.7920	0.048*
C17	0.42896 (8)	0.91441 (15)	0.52767 (15)	0.0404 (5)
C18	0.43484 (9)	0.89724 (18)	0.42763 (16)	0.0488 (5)
H18	0.4050	0.9142	0.3768	0.059*
C19	0.48600 (10)	0.85417 (17)	0.40348 (16)	0.0475 (5)
H19	0.4903	0.8423	0.3357	0.057*
C20	0.53052 (8)	0.82857 (14)	0.47810 (15)	0.0360 (4)
C21	0.52321 (9)	0.84584 (17)	0.57858 (16)	0.0467 (5)
H21	0.5527	0.8284	0.6299	0.056*
C22	0.47228 (9)	0.88894 (19)	0.60301 (16)	0.0511 (6)
H22	0.4675	0.9006	0.6706	0.061*
C23	0.58444 (8)	0.77777 (14)	0.45101 (16)	0.0396 (4)
N1	0.16496 (6)	0.96917 (12)	1.07590 (11)	0.0357 (4)
N2	0.08781 (7)	1.05112 (12)	1.28870 (11)	0.0346 (3)
H2A	0.0784	1.1096	1.3114	0.042*
O1	0.08082 (8)	0.88033 (11)	1.31228 (12)	0.0635 (5)
O2	0.22474 (6)	0.89074 (11)	0.90261 (10)	0.0460 (3)
O3	0.25498 (6)	0.73245 (11)	0.88436 (10)	0.0414 (3)
O4	0.37867 (6)	0.96457 (12)	0.54858 (12)	0.0552 (4)
O5	0.62231 (6)	0.75485 (12)	0.52573 (12)	0.0528 (4)
O6	0.58908 (6)	0.75736 (11)	0.36117 (12)	0.0513 (4)
Zn1	0.186378 (9)	0.834058 (17)	1.012802 (16)	0.03536 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0364 (9)	0.0397 (10)	0.0322 (10)	0.0026 (8)	0.0148 (8)	0.0017 (8)
C2	0.0316 (9)	0.0388 (10)	0.0274 (9)	0.0033 (7)	0.0104 (7)	0.0007 (7)
C3	0.0428 (10)	0.0391 (11)	0.0350 (10)	0.0022 (8)	0.0120 (8)	−0.0024 (8)
C4	0.0450 (11)	0.0419 (11)	0.0400 (11)	−0.0037 (9)	0.0168 (9)	0.0046 (9)
C5	0.0408 (10)	0.0503 (12)	0.0348 (10)	−0.0002 (9)	0.0188 (8)	0.0026 (9)
C6	0.0407 (10)	0.0381 (11)	0.0324 (10)	0.0039 (8)	0.0162 (8)	−0.0005 (8)
C7	0.0286 (8)	0.0372 (10)	0.0290 (9)	−0.0016 (7)	0.0102 (7)	−0.0046 (7)
C8	0.0335 (9)	0.0315 (9)	0.0363 (10)	0.0021 (7)	0.0132 (8)	−0.0017 (8)
C9	0.0342 (9)	0.0323 (10)	0.0335 (9)	−0.0013 (8)	0.0110 (7)	0.0013 (8)
C10	0.0280 (9)	0.0501 (12)	0.0305 (9)	−0.0012 (8)	0.0076 (7)	−0.0005 (8)
C11	0.0295 (9)	0.0428 (11)	0.0327 (10)	0.0014 (8)	0.0108 (7)	0.0018 (8)
C12	0.0438 (11)	0.0404 (11)	0.0413 (11)	0.0077 (9)	0.0175 (9)	0.0059 (9)
C13	0.0502 (12)	0.0464 (12)	0.0451 (12)	0.0155 (9)	0.0256 (10)	0.0040 (9)
C14	0.0353 (10)	0.0496 (12)	0.0396 (10)	0.0109 (9)	0.0189 (8)	0.0112 (9)
C15	0.0414 (10)	0.0389 (11)	0.0511 (12)	0.0057 (9)	0.0195 (9)	0.0064 (9)
C16	0.0386 (10)	0.0433 (11)	0.0431 (11)	0.0059 (8)	0.0199 (8)	−0.0019 (9)
C17	0.0402 (10)	0.0400 (11)	0.0461 (11)	0.0067 (9)	0.0253 (9)	0.0075 (9)
C18	0.0476 (11)	0.0615 (14)	0.0397 (11)	0.0151 (10)	0.0149 (9)	0.0128 (10)
C19	0.0557 (13)	0.0567 (13)	0.0345 (11)	0.0109 (10)	0.0225 (10)	0.0044 (9)
C20	0.0379 (10)	0.0302 (10)	0.0437 (11)	−0.0010 (8)	0.0202 (9)	−0.0034 (8)
C21	0.0399 (11)	0.0609 (14)	0.0404 (11)	0.0066 (9)	0.0089 (9)	−0.0079 (10)
C22	0.0501 (12)	0.0704 (16)	0.0360 (11)	0.0118 (11)	0.0178 (9)	−0.0088 (10)
C23	0.0393 (10)	0.0306 (10)	0.0531 (10)	−0.0040 (8)	0.0225 (9)	−0.0049 (9)
N1	0.0358 (8)	0.0431 (9)	0.0312 (8)	0.0038 (7)	0.0156 (6)	−0.0018 (7)
N2	0.0411 (8)	0.0342 (8)	0.0322 (8)	0.0033 (7)	0.0186 (7)	−0.0035 (6)
O1	0.0995 (13)	0.0377 (9)	0.0654 (10)	0.0116 (8)	0.0573 (10)	0.0020 (7)
O2	0.0488 (8)	0.0527 (9)	0.0419 (8)	0.0032 (7)	0.0266 (6)	0.0010 (7)
O3	0.0398 (7)	0.0459 (9)	0.0397 (7)	−0.0056 (6)	0.0092 (6)	0.0061 (6)
O4	0.0532 (9)	0.0604 (10)	0.0600 (9)	0.0244 (7)	0.0384 (7)	0.0262 (8)
O5	0.0398 (8)	0.0611 (10)	0.0603 (10)	0.0121 (7)	0.0168 (7)	−0.0031 (8)
O6	0.0545 (8)	0.0502 (9)	0.0559 (8)	0.0022 (7)	0.0326 (7)	−0.0108 (7)
Zn1	0.03386 (14)	0.04101 (15)	0.03455 (14)	0.00082 (9)	0.01733 (9)	−0.00154 (9)

Geometric parameters (Å, º)

C1—N1	1.343 (2)	C13—C14	1.382 (3)
C1—C2	1.388 (3)	C14—C15	1.382 (3)
C2—C3	1.387 (3)	C14—O4	1.383 (2)
C2—N2	1.404 (2)	C15—C16	1.379 (3)
C3—C4	1.379 (3)	C17—C22	1.365 (3)
C4—C5	1.369 (3)	C17—C18	1.369 (3)
C5—N1	1.342 (3)	C17—O4	1.395 (2)
C6—O1	1.215 (2)	C18—C19	1.386 (3)
C6—N2	1.360 (2)	C19—C20	1.378 (3)
C6—C7	1.501 (2)	C20—C21	1.383 (3)
C7—C9	1.387 (3)	C20—C23	1.498 (3)
C7—C8	1.393 (3)	C21—C22	1.383 (3)
C8—C9^i	1.381 (2)	C23—O6	1.239 (2)
C9—C8^i	1.381 (2)	C23—O5	1.274 (3)
C10—O2	1.262 (2)	N1—Zn1	2.0427 (16)
C10—O3	1.265 (2)	O2—Zn1	1.9503 (13)
C10—C11	1.485 (3)	O3—Zn1^ii	1.9987 (13)
C11—C16	1.388 (3)	O5—Zn1^iii	1.9101 (14)
C11—C12	1.389 (3)	Zn1—O5^iv	1.9102 (14)
C12—C13	1.375 (3)	Zn1—O3^ii	1.9987 (13)
N1—C1—C2	121.84 (17)	C22—C17—C18	121.02 (18)
C3—C2—C1	118.30 (16)	C22—C17—O4	121.64 (18)
C3—C2—N2	118.25 (16)	C18—C17—O4	117.22 (18)
C1—C2—N2	123.43 (16)	C17—C18—C19	118.9 (2)
C4—C3—C2	119.20 (18)	C20—C19—C18	121.16 (19)
C5—C4—C3	119.63 (18)	C19—C20—C21	118.74 (18)
N1—C5—C4	121.63 (16)	C19—C20—C23	120.46 (18)
O1—C6—N2	122.95 (16)	C21—C20—C23	120.72 (19)
O1—C6—C7	120.99 (17)	C22—C21—C20	120.3 (2)
N2—C6—C7	116.06 (16)	C17—C22—C21	119.89 (19)
C9—C7—C8	118.93 (15)	O6—C23—O5	124.25 (18)
C9—C7—C6	123.92 (16)	O6—C23—C20	120.16 (19)
C8—C7—C6	117.15 (16)	O5—C23—C20	115.54 (17)
C9^i—C8—C7	120.36 (17)	C5—N1—C1	119.36 (16)
C8^i—C9—C7	120.70 (17)	C5—N1—Zn1	122.61 (12)
O2—C10—O3	121.81 (17)	C1—N1—Zn1	117.85 (13)
O2—C10—C11	117.86 (18)	C6—N2—C2	126.67 (16)
O3—C10—C11	120.29 (17)	C10—O2—Zn1	113.68 (13)
C16—C11—C12	118.77 (17)	C10—O3—Zn1^ii	124.99 (12)
C16—C11—C10	121.55 (17)	C14—O4—C17	118.42 (15)
C12—C11—C10	119.67 (18)	C23—O5—Zn1^iii	122.69 (13)
C13—C12—C11	120.84 (19)	O5^iv—Zn1—O2	137.01 (7)
C12—C13—C14	119.37 (18)	O5^iv—Zn1—O3^ii	98.22 (6)
C15—C14—C13	120.96 (18)	O2—Zn1—O3^ii	110.00 (6)
C15—C14—O4	117.01 (18)	O5^iv—Zn1—N1	104.94 (6)
C13—C14—O4	121.95 (18)	O2—Zn1—N1	97.79 (6)
C16—C15—C14	119.04 (19)	O3^ii—Zn1—N1	106.02 (6)
C15—C16—C11	121.02 (18)
N1—C1—C2—C3	1.5 (3)	C18—C17—C22—C21	0.5 (4)
N1—C1—C2—N2	179.68 (16)	O4—C17—C22—C21	−175.4 (2)
C1—C2—C3—C4	−0.1 (3)	C20—C21—C22—C17	0.1 (4)
N2—C2—C3—C4	−178.42 (17)	C19—C20—C23—O6	−0.8 (3)
C2—C3—C4—C5	−1.2 (3)	C21—C20—C23—O6	175.85 (19)
C3—C4—C5—N1	1.4 (3)	C19—C20—C23—O5	−178.22 (18)
O1—C6—C7—C9	−161.1 (2)	C21—C20—C23—O5	−1.6 (3)
N2—C6—C7—C9	19.9 (3)	C4—C5—N1—C1	0.0 (3)
O1—C6—C7—C8	18.6 (3)	C4—C5—N1—Zn1	−175.04 (15)
N2—C6—C7—C8	−160.33 (17)	C2—C1—N1—C5	−1.4 (3)
C9—C7—C8—C9^i	−1.3 (3)	C2—C1—N1—Zn1	173.84 (14)
C6—C7—C8—C9^i	178.93 (16)	O1—C6—N2—C2	2.4 (3)
C8—C7—C9—C8^i	1.3 (3)	C7—C6—N2—C2	−178.70 (16)
C6—C7—C9—C8^i	−178.95 (17)	C3—C2—N2—C6	−172.86 (18)
O2—C10—C11—C16	5.4 (3)	C1—C2—N2—C6	8.9 (3)
O3—C10—C11—C16	−176.52 (18)	O3—C10—O2—Zn1	5.3 (2)
O2—C10—C11—C12	−173.37 (18)	C11—C10—O2—Zn1	−176.66 (12)
O3—C10—C11—C12	4.7 (3)	O2—C10—O3—Zn1^ii	−94.2 (2)
C16—C11—C12—C13	0.7 (3)	C11—C10—O3—Zn1^ii	87.7 (2)
C10—C11—C12—C13	179.45 (19)	C15—C14—O4—C17	147.9 (2)
C11—C12—C13—C14	−0.1 (3)	C13—C14—O4—C17	−35.3 (3)
C12—C13—C14—C15	−0.4 (3)	C22—C17—O4—C14	−47.1 (3)
C12—C13—C14—O4	−177.03 (19)	C18—C17—O4—C14	136.8 (2)
C13—C14—C15—C16	0.3 (3)	O6—C23—O5—Zn1^iii	−10.4 (3)
O4—C14—C15—C16	177.15 (18)	C20—C23—O5—Zn1^iii	166.89 (12)
C14—C15—C16—C11	0.2 (3)	C10—O2—Zn1—O5^iv	−72.64 (16)
C12—C11—C16—C15	−0.7 (3)	C10—O2—Zn1—O3^ii	55.20 (14)
C10—C11—C16—C15	−179.47 (18)	C10—O2—Zn1—N1	165.46 (13)
C22—C17—C18—C19	−0.6 (3)	C5—N1—Zn1—O5^iv	−152.51 (15)
O4—C17—C18—C19	175.49 (19)	C1—N1—Zn1—O5^iv	32.40 (15)
C17—C18—C19—C20	0.1 (3)	C5—N1—Zn1—O2	−9.32 (16)
C18—C19—C20—C21	0.5 (3)	C1—N1—Zn1—O2	175.59 (13)
C18—C19—C20—C23	177.24 (19)	C5—N1—Zn1—O3^ii	104.16 (15)
C19—C20—C21—C22	−0.6 (3)	C1—N1—Zn1—O3^ii	−70.93 (14)
C23—C20—C21—C22	−177.32 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6^v	0.86	2.05	2.862 (2)	158

Symmetry code: (v) x−1/2, y+1/2, z+1.

(2) Poly[[bis(µ₂-benzene-1,4-dicarboxylato)[µ₂-N⁴,N^4'-bis(pyridin-3-yl)-[1,1'-biphenyl]-4,4'-dicarboxamide]dicadmium(II)] dihydrate]

Crystal data

[Cd(C8H4O4)(C24N4H18O2)]·2H2O	F(000) = 1432
Mr = 706.97	Dx = 1.583 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.0043 (10) Å	Cell parameters from 4439 reflections
b = 7.9145 (3) Å	θ = 2.8–26.4°
c = 17.9803 (6) Å	µ = 0.80 mm^−1
β = 129.491 (2)°	T = 296 K
V = 2965.62 (19) Å^3	Block, colourless
Z = 4	0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2613 independent reflections
Radiation source: fine-focus sealed tube	2395 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −32→30
Tmin = 0.857, Tmax = 0.870	k = −9→9
10800 measured reflections	l = −20→21

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1281P)^2 + 11.8072P] where P = (Fo^2 + 2Fc^2)/3
2613 reflections	(Δ/σ)max < 0.001
212 parameters	Δρmax = 3.21 e Å^−3
3 restraints	Δρmin = −1.01 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	−0.0060 (2)	−0.2643 (7)	0.3717 (4)	0.0379 (12)
C2	−0.0032 (3)	−0.3850 (8)	0.4388 (4)	0.0396 (13)
C3	−0.0176 (3)	−0.5548 (8)	0.4129 (5)	0.0488 (15)
H3	−0.0295	−0.5915	0.3544	0.059*
C4	0.0139 (3)	−0.3314 (8)	0.5253 (4)	0.0481 (14)
H4	0.0232	−0.2180	0.5423	0.058*
C5	0.1085 (3)	0.1008 (7)	0.2666 (4)	0.0413 (13)
H5	0.0909	0.0334	0.2126	0.050*
C6	0.1601 (3)	0.2052 (8)	0.2973 (4)	0.0415 (12)
C7	0.1866 (3)	0.3010 (10)	0.3792 (5)	0.0558 (16)
H7	0.2217	0.3709	0.4035	0.067*
C8	0.1600 (4)	0.2907 (10)	0.4242 (5)	0.0624 (18)
H8	0.1767	0.3552	0.4788	0.075*
C9	0.1092 (3)	0.1854 (9)	0.3879 (4)	0.0527 (15)
H9	0.0922	0.1786	0.4194	0.063*
C10	0.2359 (3)	0.2648 (9)	0.2678 (4)	0.0487 (15)
C11	0.2394 (3)	0.2640 (8)	0.1879 (4)	0.0470 (14)
C12	0.1859 (3)	0.2873 (10)	0.0922 (5)	0.0592 (18)
H12	0.1463	0.3064	0.0765	0.071*
C13	0.1900 (3)	0.2829 (10)	0.0200 (5)	0.0546 (16)
H13	0.1530	0.3000	−0.0433	0.066*
C14	0.2475 (3)	0.2537 (8)	0.0385 (4)	0.0447 (13)
C15	0.3016 (3)	0.2328 (9)	0.1362 (4)	0.0525 (16)
H15	0.3415	0.2164	0.1521	0.063*
C16	0.2980 (3)	0.2356 (9)	0.2086 (4)	0.0524 (16)
H16	0.3348	0.2185	0.2720	0.063*
Cd1	0.0000	−0.08668 (6)	0.2500	0.0331 (3)
H1W	0.414 (4)	0.515 (11)	0.470 (3)	0.09 (3)*
H2W	0.368 (3)	0.418 (7)	0.413 (5)	0.06 (2)*
N1	0.0832 (2)	0.0923 (6)	0.3097 (4)	0.0413 (12)
N2	0.1800 (2)	0.2072 (7)	0.2421 (3)	0.0473 (12)
H2	0.1534	0.1666	0.1848	0.057*
O1	−0.0402 (2)	−0.3019 (6)	0.2844 (3)	0.0523 (11)
O2	0.0277 (2)	−0.1324 (6)	0.4041 (3)	0.0509 (11)
O3	0.2805 (2)	0.3117 (8)	0.3492 (3)	0.0691 (15)
O4	0.3948 (2)	0.4760 (7)	0.4140 (3)	0.0533 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.036 (3)	0.044 (3)	0.035 (3)	−0.002 (2)	0.023 (2)	0.007 (2)
C2	0.039 (3)	0.047 (3)	0.039 (3)	−0.002 (2)	0.028 (3)	0.009 (2)
C3	0.064 (4)	0.051 (3)	0.042 (3)	−0.012 (3)	0.039 (3)	0.001 (3)
C4	0.064 (4)	0.039 (3)	0.044 (3)	−0.011 (3)	0.036 (3)	0.001 (2)
C5	0.044 (3)	0.048 (3)	0.036 (3)	−0.006 (2)	0.028 (3)	−0.003 (2)
C6	0.040 (3)	0.050 (3)	0.037 (3)	−0.007 (2)	0.025 (2)	−0.002 (2)
C7	0.051 (3)	0.071 (4)	0.052 (3)	−0.021 (3)	0.035 (3)	−0.014 (3)
C8	0.070 (4)	0.071 (5)	0.057 (4)	−0.023 (4)	0.046 (4)	−0.026 (3)
C9	0.063 (4)	0.070 (4)	0.045 (3)	−0.012 (3)	0.044 (3)	−0.005 (3)
C10	0.048 (3)	0.066 (4)	0.046 (3)	−0.017 (3)	0.036 (3)	−0.007 (3)
C11	0.047 (3)	0.057 (4)	0.048 (3)	−0.015 (3)	0.035 (3)	−0.006 (3)
C12	0.049 (3)	0.089 (5)	0.058 (4)	−0.003 (3)	0.042 (3)	0.011 (3)
C13	0.045 (3)	0.082 (5)	0.046 (3)	0.004 (3)	0.033 (3)	0.014 (3)
C14	0.047 (3)	0.054 (3)	0.045 (3)	−0.012 (2)	0.035 (3)	−0.002 (2)
C15	0.037 (3)	0.081 (5)	0.047 (3)	−0.015 (3)	0.030 (3)	−0.013 (3)
C16	0.042 (3)	0.078 (5)	0.038 (3)	−0.017 (3)	0.026 (3)	−0.010 (3)
Cd1	0.0425 (4)	0.0344 (4)	0.0351 (4)	0.000	0.0306 (3)	0.000
N1	0.040 (3)	0.049 (3)	0.043 (3)	−0.0039 (18)	0.030 (2)	−0.0023 (18)
N2	0.043 (3)	0.068 (3)	0.040 (2)	−0.020 (2)	0.030 (2)	−0.014 (2)
O1	0.058 (2)	0.056 (3)	0.041 (2)	−0.013 (2)	0.031 (2)	0.0045 (18)
O2	0.059 (3)	0.055 (2)	0.039 (2)	−0.017 (2)	0.031 (2)	0.0042 (19)
O3	0.054 (3)	0.114 (5)	0.046 (3)	−0.036 (3)	0.034 (2)	−0.023 (3)
O4	0.050 (2)	0.067 (3)	0.048 (2)	−0.013 (2)	0.034 (2)	−0.006 (2)

Geometric parameters (Å, º)

C1—O1	1.250 (7)	C10—C11	1.498 (8)
C1—O2	1.259 (7)	C11—C12	1.385 (9)
C1—C2	1.503 (7)	C11—C16	1.396 (9)
C1—Cd1	2.691 (5)	C12—C13	1.371 (9)
C2—C4	1.378 (9)	C12—H12	0.9300
C2—C3	1.394 (9)	C13—C14	1.386 (9)
C3—C4^i	1.385 (8)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.409 (9)
C4—C3^i	1.385 (8)	C14—C14^ii	1.474 (12)
C4—H4	0.9300	C15—C16	1.366 (9)
C5—N1	1.321 (8)	C15—H15	0.9300
C5—C6	1.396 (8)	C16—H16	0.9300
C5—H5	0.9300	Cd1—N1^iii	2.268 (5)
C6—C7	1.383 (9)	Cd1—N1	2.268 (5)
C6—N2	1.399 (7)	Cd1—O1^iii	2.306 (4)
C7—C8	1.385 (10)	Cd1—O1	2.306 (4)
C7—H7	0.9300	Cd1—O2^iii	2.394 (4)
C8—C9	1.366 (9)	Cd1—O2	2.394 (4)
C8—H8	0.9300	Cd1—C1^iii	2.691 (5)
C9—N1	1.326 (8)	N2—H2	0.8600
C9—H9	0.9300	O4—H1W	0.849 (10)
C10—O3	1.220 (8)	O4—H2W	0.848 (10)
C10—N2	1.346 (8)
O1—C1—O2	121.2 (5)	C15—C14—C14^ii	121.6 (7)
O1—C1—C2	118.5 (5)	C16—C15—C14	122.7 (6)
O2—C1—C2	120.2 (5)	C16—C15—H15	118.6
O1—C1—Cd1	58.8 (3)	C14—C15—H15	118.6
O2—C1—Cd1	62.8 (3)	C15—C16—C11	120.3 (6)
C2—C1—Cd1	170.6 (4)	C15—C16—H16	119.8
C4—C2—C3	119.7 (6)	C11—C16—H16	119.8
C4—C2—C1	121.3 (5)	N1^iii—Cd1—N1	102.7 (2)
C3—C2—C1	118.9 (6)	N1^iii—Cd1—O1^iii	145.97 (17)
C4^i—C3—C2	119.8 (6)	N1—Cd1—O1^iii	95.41 (18)
C4^i—C3—H3	120.1	N1^iii—Cd1—O1	95.41 (18)
C2—C3—H3	120.1	N1—Cd1—O1	145.97 (17)
C2—C4—C3^i	120.5 (6)	O1^iii—Cd1—O1	84.8 (3)
C2—C4—H4	119.8	N1^iii—Cd1—O2^iii	93.47 (17)
C3^i—C4—H4	119.8	N1—Cd1—O2^iii	97.37 (19)
N1—C5—C6	123.7 (6)	O1^iii—Cd1—O2^iii	55.39 (15)
N1—C5—H5	118.1	O1—Cd1—O2^iii	110.17 (17)
C6—C5—H5	118.1	N1^iii—Cd1—O2	97.37 (19)
C7—C6—C5	117.3 (6)	N1—Cd1—O2	93.47 (17)
C7—C6—N2	125.1 (5)	O1^iii—Cd1—O2	110.17 (17)
C5—C6—N2	117.6 (5)	O1—Cd1—O2	55.39 (15)
C6—C7—C8	118.6 (6)	O2^iii—Cd1—O2	162.6 (2)
C6—C7—H7	120.7	N1^iii—Cd1—C1	99.02 (18)
C8—C7—H7	120.7	N1—Cd1—C1	119.73 (18)
C9—C8—C7	119.6 (6)	O1^iii—Cd1—C1	96.56 (17)
C9—C8—H8	120.2	O1—Cd1—C1	27.61 (16)
C7—C8—H8	120.2	O2^iii—Cd1—C1	136.55 (17)
N1—C9—C8	122.6 (6)	O2—Cd1—C1	27.88 (16)
N1—C9—H9	118.7	N1^iii—Cd1—C1^iii	119.73 (18)
C8—C9—H9	118.7	N1—Cd1—C1^iii	99.02 (18)
O3—C10—N2	123.4 (6)	O1^iii—Cd1—C1^iii	27.61 (16)
O3—C10—C11	122.4 (5)	O1—Cd1—C1^iii	96.57 (17)
N2—C10—C11	114.2 (5)	O2^iii—Cd1—C1^iii	27.89 (16)
C12—C11—C16	117.5 (6)	O2—Cd1—C1^iii	136.55 (17)
C12—C11—C10	122.7 (6)	C1—Cd1—C1^iii	117.0 (3)
C16—C11—C10	119.8 (6)	C5—N1—C9	118.2 (5)
C13—C12—C11	121.7 (6)	C5—N1—Cd1	118.7 (4)
C13—C12—H12	119.2	C9—N1—Cd1	123.0 (4)
C11—C12—H12	119.2	C10—N2—C6	127.9 (5)
C12—C13—C14	122.0 (6)	C10—N2—H2	116.1
C12—C13—H13	119.0	C6—N2—H2	116.1
C14—C13—H13	119.0	C1—O1—Cd1	93.6 (3)
C13—C14—C15	115.7 (6)	C1—O2—Cd1	89.3 (3)
C13—C14—C14^ii	122.6 (7)	H1W—O4—H2W	95.0 (15)
O1—C1—C2—C4	−157.4 (6)	O1—C1—Cd1—O2	173.1 (6)
O2—C1—C2—C4	25.7 (9)	C2—C1—Cd1—O2	−111 (2)
Cd1—C1—C2—C4	132 (2)	O1—C1—Cd1—C1^iii	−45.7 (3)
O1—C1—C2—C3	23.5 (9)	O2—C1—Cd1—C1^iii	141.2 (4)
O2—C1—C2—C3	−153.4 (6)	C2—C1—Cd1—C1^iii	30 (2)
Cd1—C1—C2—C3	−47 (3)	C6—C5—N1—C9	−1.6 (9)
C4—C2—C3—C4^i	−0.5 (11)	C6—C5—N1—Cd1	−179.5 (5)
C1—C2—C3—C4^i	178.6 (6)	C8—C9—N1—C5	1.1 (10)
C3—C2—C4—C3^i	0.5 (11)	C8—C9—N1—Cd1	178.9 (6)
C1—C2—C4—C3^i	−178.6 (6)	N1^iii—Cd1—N1—C5	−111.4 (5)
N1—C5—C6—C7	1.7 (9)	O1^iii—Cd1—N1—C5	39.6 (5)
N1—C5—C6—N2	−177.1 (6)	O1—Cd1—N1—C5	128.3 (5)
C5—C6—C7—C8	−1.3 (10)	O2^iii—Cd1—N1—C5	−16.1 (5)
N2—C6—C7—C8	177.4 (7)	O2—Cd1—N1—C5	150.3 (4)
C6—C7—C8—C9	0.9 (12)	C1—Cd1—N1—C5	140.4 (4)
C7—C8—C9—N1	−0.8 (12)	C1^iii—Cd1—N1—C5	12.0 (5)
O3—C10—C11—C12	−149.8 (8)	N1^iii—Cd1—N1—C9	70.9 (5)
N2—C10—C11—C12	31.2 (10)	O1^iii—Cd1—N1—C9	−138.2 (5)
O3—C10—C11—C16	31.5 (11)	O1—Cd1—N1—C9	−49.5 (6)
N2—C10—C11—C16	−147.5 (7)	O2^iii—Cd1—N1—C9	166.1 (5)
C16—C11—C12—C13	0.0 (11)	O2—Cd1—N1—C9	−27.5 (5)
C10—C11—C12—C13	−178.7 (7)	C1—Cd1—N1—C9	−37.4 (6)
C11—C12—C13—C14	0.5 (12)	C1^iii—Cd1—N1—C9	−165.8 (5)
C12—C13—C14—C15	−1.4 (11)	O3—C10—N2—C6	6.8 (12)
C12—C13—C14—C14^ii	179.2 (8)	C11—C10—N2—C6	−174.2 (6)
C13—C14—C15—C16	2.0 (10)	C7—C6—N2—C10	17.8 (11)
C14^ii—C14—C15—C16	−178.6 (8)	C5—C6—N2—C10	−163.5 (7)
C14—C15—C16—C11	−1.6 (11)	O2—C1—O1—Cd1	7.2 (6)
C12—C11—C16—C15	0.6 (10)	C2—C1—O1—Cd1	−169.7 (5)
C10—C11—C16—C15	179.3 (7)	N1^iii—Cd1—O1—C1	−99.1 (4)
O1—C1—Cd1—N1^iii	84.4 (4)	N1—Cd1—O1—C1	23.2 (5)
O2—C1—Cd1—N1^iii	−88.7 (4)	O1^iii—Cd1—O1—C1	115.0 (4)
C2—C1—Cd1—N1^iii	160 (2)	O2^iii—Cd1—O1—C1	165.2 (3)
O1—C1—Cd1—N1	−165.3 (3)	O2—Cd1—O1—C1	−3.9 (3)
O2—C1—Cd1—N1	21.6 (4)	C1^iii—Cd1—O1—C1	140.0 (3)
C2—C1—Cd1—N1	−90 (2)	O1—C1—O2—Cd1	−6.9 (6)
O1—C1—Cd1—O1^iii	−65.2 (4)	C2—C1—O2—Cd1	169.9 (5)
O2—C1—Cd1—O1^iii	121.6 (4)	N1^iii—Cd1—O2—C1	95.4 (4)
C2—C1—Cd1—O1^iii	10 (2)	N1—Cd1—O2—C1	−161.4 (4)
O2—C1—Cd1—O1	−173.1 (6)	O1^iii—Cd1—O2—C1	−64.3 (4)
C2—C1—Cd1—O1	76 (2)	O1—Cd1—O2—C1	3.9 (3)
O1—C1—Cd1—O2^iii	−20.5 (5)	O2^iii—Cd1—O2—C1	−32.8 (3)
O2—C1—Cd1—O2^iii	166.4 (2)	C1^iii—Cd1—O2—C1	−54.4 (5)
C2—C1—Cd1—O2^iii	55 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H2W···O3	0.85 (1)	2.04 (3)	2.829 (6)	154 (7)
O4—H1W···O2^iv	0.85 (1)	1.98 (2)	2.811 (6)	166 (7)
N2—H2···O4^v	0.86	2.05	2.845 (7)	154

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