{[mu]-6,6'-Dimeth­oxy-2,2'-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}-[mu]-nitrato-dinitratoterbium(III)zinc(II)

In the title heteronuclear Zn^II-Tb^III complex (systematic name: {6,6'-dimeth­oxy-2,2'-[ethane-1,2-diylbis(nitrilo­methyl­id­yne)]diphenolato-1[kappa]⁴O⁶,O¹,O^1',O^6'}:2[kappa]⁴O¹,N,N',O^1'-[mu]-nitrato-1:2[kappa]²O:O'-dinitrato-1[kappa]⁴O,O'-terbium(III)zinc(II)), [TbZn(C₁₈H₁₈N₂O₄)(NO₃)₃], with the hexa­dentate Schiff base compartmental ligand N,N'-bis­(3-methoxy­salicyl­idene)ethyl­enediamine (H₂L), the Tb and Zn atoms are triply bridged by two phenolate O atoms of the Schiff base ligand and one nitrate ion. The five-coordinate Zn atom is in a square-pyramidal geometry with the donor centers of two imine N atoms, two phenolate O atoms and one of the bridging nitrate O atoms. The Tb^III center has a ninefold coordination environment of O atoms, involving the phenolate O atoms, two meth­oxy O atoms, two O atoms from two nitrate ions and one from the bridging nitrate ion. Weak inter­molecular C-H...O inter­actions generate a two-dimensional layer structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.024
• wR factor = 0.069
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.93 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O6     -   N4      ..       5.68 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N4
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      31.00 A   3 

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The potential applications of trivalent lanthanide complexes as contrast agent for magnetic resonance imaging and stains for fluorescence imaging have prompted considerable interest in the preparation, magnetic and optical properties of 3 d-4f hetorometallic dinuclear complexes (Baggio et al., 2000; Caravan et al., 1999; Edder et al., 2000; Knoer et al., 2005). As part of our investigations into the structure and applications of 3 d-4f hetorometallic Schiff base complexes (Sui et al. 2006; Sui et al. 2007), we report here the synthesis and X-ray crystal structure analysis of the title complex, (I), a new Zn^II—Tb^III complex with salen-type Schiff base N,N'-bis(3-methoxysalicylidene) ethylenediamine (H₂L).

Complex (I) crystallizes in the space group P2₁/n, with zinc and terbium triply bridged by two phenolate O atoms provided by the Schiff base ligand and one nitrate ion. The inner salen-type cavity is occupied by zinc(II), while terbium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand.

The Tb^III center has a ninefold coordination environment of O atoms, involving the phenolate O atoms, two methoxy O atoms, two O atoms from two nitrate ions and one from the bridging nitrate ion. The four kinds of Tb—O bond distances are significantly different, the longest being the Tb—O (methoxy) separations and the shortest being the Tb—O (phenolate) and Tb—O5 (bridging nitrate).

The Zn^II is in a square-pyramidal geometry and is five-coordinated by two imine N atoms, two phenolate O atoms and one of the bridging nitrate O atoms. The Zn atom is 0.6062 (4) Å above the mean N₂O₂ plane with an average deviation from the plane of 0.0383 (3) Å, which construct the bottom of square-pyramid. The Zn—O6 (bridging nitrate) separation is 1.978 (3)Å and the angles of this Zn—O vector with the Zn—N or Zn—O bonds lie between 102.5 (5)° and 112.7 (6)°, which suggesting that the Zn^II is in a slightly distorted square-pyramidal conformation.

Adjacent molecules are held together by weak interactions (C5—H5···O11ⁱ = 3.376 (5) Å and C9—H9A···O13ⁱⁱ = 3.487 (6) Å; symmetry codes: (i) 1/2 + x, 1/2 - y, -1/2 + z; (ii) 1 - x, -y, 1 - z). These link the molecules into a two-dimensional layer structure (Fig 2).

Related literature

For related literature, see: Baggio et al. (2000); Caravan et al. (1999); Edder et al. (2000); Knoer et al. (2005); Sui et al. (2006, 2007).

S2. Experimental

H₂L was prepared by the 2:1 condensation of 3-methoxysalicylaldehyde and ethylenediamine in methanol. Complex (I) was obtained by the treatment of zinc(II) acetate dihydrate (0.188 g, 1 mmol) with H₂L (0.328 g, 1 mmol) in methanol solution (80 ml) under reflux for 3 h and then for another 3 h after the addition of terbium(III) nitrate hexahydrate (0.453 g, 1 mmol). The reaction mixture was cooled and the resulting precipitate was filtered off, washed with diethyl ether and dried in vacuo. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation at room temperature of a methanol solution. Analysis calculated for C₁₈H₁₈N₅O₁₃TbZn: C 29.35 H 2.46, N 9.51, Tb 21.57, Zn 8.88%; found: C 29.40, H 2.45, N 9.53, Tb 21.60, Zn 8.906%. IR (KBr, cm^-1): 1640 (C=N), 1386,1490(nitrate).

S3. Refinement

The H atoms were positioned geometrically and treated as riding on their parent atoms, with C—H distances of 0.97 (methylene), 0.96 Å (methyl) and 0.93 Å (aromaticmethyl), and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms. The main directions of movement of covalently bonded atoms N4, O5 and O6 are enforced to be the same.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: APEX2 (Bruker, 2004); software used to prepare material for publication: APEX2 (Bruker, 2004) and publCIF (Westrip, 2007).

Figures

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. All the H atoms on carbon have been omitted for clarity.
	Fig. 2. The packing diagram of (I), viewed along the b axis; hydrogen bonds are shown as dashed lines.

{6,6'-dimethoxy-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato- 1κ⁴O¹,O^1',O⁶,O^6':2κ⁴O¹, N,N',O^1'}-µ-nitrato-1:2κ²O:O'- dinitrato-1κ⁴O,O'-terbium(III)zinc(II)

Crystal data

[TbZn(C18H18N2O4)(NO3)3]	F(000) = 1440
Mr = 736.66	Dx = 1.883 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8984 reflections
a = 10.6818 (4) Å	θ = 1.9–25.0°
b = 16.5022 (6) Å	µ = 3.69 mm^−1
c = 14.9546 (6) Å	T = 293 K
β = 99.618 (1)°	Block, yellow
V = 2599.04 (17) Å^3	0.33 × 0.22 × 0.12 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	4431 independent reflections
Radiation source: fine-focus sealed tube	3722 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scan	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −12→12
Tmin = 0.375, Tmax = 0.666	k = −19→18
15507 measured reflections	l = −17→16

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 0.9659P] where P = (Fo^2 + 2Fc^2)/3
4431 reflections	(Δ/σ)max = 0.001
345 parameters	Δρmax = 0.56 e Å^−3
2 restraints	Δρmin = −0.52 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
Tb1	0.637703 (16)	0.109788 (10)	0.776551 (11)	0.04217 (8)
Zn1	0.77995 (4)	0.03607 (2)	0.61063 (3)	0.04267 (12)
C1	0.7286 (3)	0.2144 (2)	0.6077 (2)	0.0439 (8)
O3	0.6387 (3)	0.26176 (14)	0.72934 (18)	0.0516 (6)
O2	0.7099 (2)	0.14261 (15)	0.64411 (17)	0.0503 (6)
N2	0.8021 (3)	0.0844 (2)	0.4882 (2)	0.0527 (8)
O12	0.4281 (3)	0.12967 (19)	0.6805 (2)	0.0638 (8)
O4	0.5108 (2)	−0.02009 (15)	0.80424 (17)	0.0504 (6)
C16	0.5882 (3)	−0.0716 (2)	0.6797 (2)	0.0422 (8)
O11	0.4437 (3)	0.16395 (19)	0.8203 (2)	0.0628 (7)
O6	0.9420 (2)	0.02850 (16)	0.69642 (19)	0.0533 (6)
O1	0.6478 (2)	−0.00117 (14)	0.68386 (17)	0.0494 (6)
N1	0.7505 (3)	−0.06699 (19)	0.5360 (2)	0.0488 (7)
C15	0.5114 (3)	−0.0853 (2)	0.7453 (3)	0.0455 (8)
N3	0.3756 (3)	0.1600 (2)	0.7427 (3)	0.0645 (10)
C11	0.5965 (3)	−0.1320 (2)	0.6144 (3)	0.0473 (9)
C7	0.8020 (4)	0.1592 (3)	0.4688 (3)	0.0543 (10)
H7	0.8186	0.1729	0.4116	0.065*
N4	0.9460 (3)	0.0491 (2)	0.7789 (3)	0.0664 (9)
O5	0.8517 (3)	0.07391 (19)	0.81165 (19)	0.0608 (7)
C6	0.7784 (4)	0.2255 (2)	0.5279 (3)	0.0505 (9)
C10	0.6736 (4)	−0.1246 (2)	0.5428 (3)	0.0514 (10)
H10	0.6658	−0.1650	0.4988	0.062*
O13	0.2669 (3)	0.1838 (3)	0.7280 (3)	0.1126 (15)
O7	1.0729 (4)	0.0402 (3)	0.8425 (4)	0.1448 (19)
C12	0.5286 (4)	−0.2039 (2)	0.6189 (3)	0.0612 (11)
H12	0.5315	−0.2438	0.5754	0.073*
O8	0.6731 (3)	0.07585 (17)	0.94168 (19)	0.0623 (7)
O9	0.7154 (3)	0.19769 (16)	0.90722 (18)	0.0606 (7)
N5	0.7195 (4)	0.1437 (2)	0.9680 (2)	0.0634 (9)
C2	0.6904 (3)	0.2826 (2)	0.6531 (2)	0.0457 (8)
C17	0.4344 (4)	−0.0290 (3)	0.8748 (3)	0.0648 (12)
H17A	0.3470	−0.0361	0.8478	0.097*
H17B	0.4427	0.0187	0.9122	0.097*
H17C	0.4627	−0.0754	0.9113	0.097*
C9	0.8243 (4)	−0.0616 (3)	0.4619 (3)	0.0580 (11)
H9A	0.7976	−0.1036	0.4175	0.070*
H9B	0.9138	−0.0692	0.4854	0.070*
C3	0.7059 (4)	0.3594 (2)	0.6228 (3)	0.0563 (10)
H3	0.6813	0.4038	0.6540	0.068*
C5	0.7933 (4)	0.3058 (3)	0.4989 (3)	0.0651 (12)
H5	0.8278	0.3147	0.4466	0.078*
C14	0.4478 (4)	−0.1572 (2)	0.7495 (3)	0.0594 (11)
H14	0.3985	−0.1658	0.7943	0.071*
C13	0.4583 (4)	−0.2167 (3)	0.6858 (4)	0.0724 (13)
H13	0.4169	−0.2659	0.6886	0.087*
C8	0.8030 (4)	0.0213 (3)	0.4178 (3)	0.0604 (11)
H8A	0.8700	0.0327	0.3831	0.073*
H8B	0.7227	0.0218	0.3764	0.073*
C4	0.7583 (4)	0.3706 (3)	0.5456 (3)	0.0631 (12)
H4	0.7699	0.4228	0.5251	0.076*
C18	0.5764 (5)	0.3264 (2)	0.7697 (3)	0.0668 (12)
H18A	0.6343	0.3708	0.7842	0.100*
H18B	0.5497	0.3071	0.8241	0.100*
H18C	0.5037	0.3443	0.7277	0.100*
O10	0.7648 (4)	0.1569 (2)	1.0465 (2)	0.1072 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tb1	0.04948 (12)	0.04348 (12)	0.03743 (12)	−0.00214 (7)	0.01852 (8)	−0.00262 (7)
Zn1	0.0471 (2)	0.0457 (2)	0.0388 (2)	0.00041 (18)	0.01728 (18)	−0.00323 (17)
C1	0.0430 (19)	0.048 (2)	0.042 (2)	−0.0022 (16)	0.0099 (16)	0.0065 (16)
O3	0.0677 (16)	0.0417 (14)	0.0496 (16)	0.0050 (12)	0.0221 (13)	−0.0013 (11)
O2	0.0664 (17)	0.0405 (13)	0.0517 (16)	0.0042 (12)	0.0320 (13)	0.0052 (12)
N2	0.0564 (19)	0.066 (2)	0.0399 (19)	0.0074 (16)	0.0209 (15)	−0.0010 (15)
O12	0.0532 (16)	0.092 (2)	0.0479 (18)	0.0077 (15)	0.0122 (14)	−0.0148 (15)
O4	0.0574 (15)	0.0521 (15)	0.0474 (16)	−0.0096 (12)	0.0253 (12)	−0.0004 (12)
C16	0.0383 (18)	0.0426 (19)	0.046 (2)	−0.0018 (15)	0.0084 (16)	−0.0010 (16)
O11	0.0608 (17)	0.085 (2)	0.0482 (18)	0.0038 (15)	0.0240 (15)	−0.0143 (14)
O6	0.0474 (14)	0.0574 (15)	0.0565 (15)	0.0035 (12)	0.0126 (12)	−0.0068 (12)
O1	0.0631 (16)	0.0427 (14)	0.0500 (16)	−0.0133 (11)	0.0315 (13)	−0.0112 (11)
N1	0.0485 (17)	0.0564 (19)	0.0447 (19)	0.0008 (15)	0.0172 (14)	−0.0107 (15)
C15	0.045 (2)	0.0453 (19)	0.047 (2)	−0.0030 (16)	0.0111 (17)	0.0012 (16)
N3	0.053 (2)	0.076 (3)	0.069 (3)	0.0059 (18)	0.022 (2)	−0.0088 (19)
C11	0.045 (2)	0.044 (2)	0.054 (2)	−0.0018 (16)	0.0091 (18)	−0.0069 (17)
C7	0.054 (2)	0.071 (3)	0.043 (2)	−0.002 (2)	0.0225 (18)	0.0113 (19)
N4	0.062 (2)	0.067 (2)	0.071 (2)	0.0024 (17)	0.0139 (18)	−0.0074 (18)
O5	0.0519 (15)	0.081 (2)	0.0492 (17)	0.0075 (14)	0.0077 (12)	−0.0072 (14)
C6	0.052 (2)	0.056 (2)	0.044 (2)	−0.0040 (18)	0.0114 (18)	0.0131 (17)
C10	0.052 (2)	0.052 (2)	0.050 (2)	0.0066 (18)	0.0060 (18)	−0.0182 (17)
O13	0.059 (2)	0.178 (4)	0.103 (3)	0.033 (2)	0.020 (2)	−0.033 (3)
O7	0.105 (3)	0.164 (5)	0.147 (4)	0.014 (3)	−0.031 (3)	−0.013 (4)
C12	0.057 (2)	0.049 (2)	0.078 (3)	−0.0045 (19)	0.013 (2)	−0.016 (2)
O8	0.087 (2)	0.0564 (17)	0.0460 (17)	−0.0187 (15)	0.0187 (15)	−0.0008 (13)
O9	0.085 (2)	0.0527 (16)	0.0463 (17)	−0.0165 (14)	0.0161 (14)	−0.0020 (13)
N5	0.077 (2)	0.072 (2)	0.045 (2)	−0.023 (2)	0.0195 (18)	−0.0063 (18)
C2	0.051 (2)	0.0432 (19)	0.043 (2)	−0.0007 (16)	0.0092 (17)	0.0035 (16)
C17	0.070 (3)	0.074 (3)	0.061 (3)	−0.014 (2)	0.039 (2)	0.001 (2)
C9	0.050 (2)	0.073 (3)	0.053 (3)	0.003 (2)	0.0170 (19)	−0.022 (2)
C3	0.065 (3)	0.045 (2)	0.056 (3)	−0.0018 (19)	0.001 (2)	0.0043 (18)
C5	0.068 (3)	0.077 (3)	0.051 (3)	−0.013 (2)	0.012 (2)	0.022 (2)
C14	0.053 (2)	0.058 (2)	0.071 (3)	−0.0129 (19)	0.021 (2)	0.007 (2)
C13	0.070 (3)	0.051 (2)	0.101 (4)	−0.023 (2)	0.025 (3)	−0.008 (2)
C8	0.065 (3)	0.081 (3)	0.040 (2)	0.005 (2)	0.0209 (19)	−0.010 (2)
C4	0.080 (3)	0.052 (2)	0.056 (3)	−0.011 (2)	0.006 (2)	0.016 (2)
C18	0.088 (3)	0.048 (2)	0.069 (3)	0.012 (2)	0.029 (2)	−0.008 (2)
O10	0.156 (4)	0.118 (3)	0.043 (2)	−0.058 (3)	0.005 (2)	−0.0054 (19)

Geometric parameters (Å, º)

Tb1—O1	2.310 (2)	C11—C12	1.398 (5)
Tb1—O2	2.307 (2)	C11—C10	1.462 (5)
Tb1—O3	2.606 (2)	C7—C6	1.456 (6)
Tb1—O4	2.606 (2)	C7—H7	0.9300
Tb1—O5	2.335 (3)	N4—O5	1.260 (4)
Tb1—O8	2.498 (3)	N4—O7	1.528 (5)
Tb1—O9	2.464 (3)	C6—C5	1.411 (5)
Tb1—O11	2.444 (3)	C10—H10	0.9300
Tb1—O12	2.472 (3)	C12—C13	1.363 (6)
Zn1—O1	2.021 (2)	C12—H12	0.9300
Zn1—O2	2.007 (2)	O8—N5	1.261 (4)
Zn1—O6	1.978 (3)	O9—N5	1.269 (4)
Zn1—N1	2.030 (3)	N5—O10	1.212 (5)
Zn1—N2	2.046 (3)	C2—C3	1.367 (5)
C1—O2	1.333 (4)	C17—H17A	0.9600
C1—C6	1.398 (5)	C17—H17B	0.9600
C1—C2	1.409 (5)	C17—H17C	0.9600
O3—C2	1.390 (4)	C9—C8	1.520 (6)
O3—C18	1.442 (4)	C9—H9A	0.9700
N2—C7	1.267 (5)	C9—H9B	0.9700
N2—C8	1.483 (5)	C3—C4	1.377 (6)
O12—N3	1.266 (4)	C3—H3	0.9300
O4—C15	1.391 (4)	C5—C4	1.363 (6)
O4—C17	1.446 (4)	C5—H5	0.9300
C16—O1	1.322 (4)	C14—C13	1.386 (6)
C16—C15	1.399 (5)	C14—H14	0.9300
C16—C11	1.408 (5)	C13—H13	0.9300
O11—N3	1.264 (4)	C8—H8A	0.9700
O6—N4	1.273 (4)	C8—H8B	0.9700
N1—C10	1.271 (5)	C4—H4	0.9300
N1—C9	1.466 (5)	C18—H18A	0.9600
C15—C14	1.373 (5)	C18—H18B	0.9600
N3—O13	1.211 (5)	C18—H18C	0.9600
O2—Tb1—O1	67.35 (9)	C14—C15—O4	125.8 (3)
O2—Tb1—O5	78.32 (10)	C14—C15—C16	121.6 (4)
O1—Tb1—O5	77.97 (10)	O4—C15—C16	112.6 (3)
O2—Tb1—O11	124.32 (10)	O13—N3—O11	122.5 (4)
O1—Tb1—O11	125.26 (9)	O13—N3—O12	121.6 (4)
O5—Tb1—O11	151.00 (10)	O11—N3—O12	116.0 (3)
O2—Tb1—O9	115.22 (9)	C12—C11—C16	118.3 (4)
O1—Tb1—O9	154.06 (10)	C12—C11—C10	117.8 (3)
O5—Tb1—O9	77.49 (10)	C16—C11—C10	123.8 (3)
O11—Tb1—O9	76.16 (10)	N2—C7—C6	125.9 (3)
O2—Tb1—O12	82.53 (10)	N2—C7—H7	117.0
O1—Tb1—O12	83.41 (10)	C6—C7—H7	117.0
O5—Tb1—O12	157.24 (10)	O5—N4—O6	124.3 (3)
O11—Tb1—O12	51.74 (9)	O5—N4—O7	118.2 (4)
O9—Tb1—O12	122.37 (10)	O6—N4—O7	117.4 (4)
O2—Tb1—O8	152.16 (10)	N4—O5—Tb1	144.2 (3)
O1—Tb1—O8	113.64 (9)	C1—C6—C5	117.7 (4)
O5—Tb1—O8	74.94 (10)	C1—C6—C7	123.3 (3)
O11—Tb1—O8	79.19 (10)	C5—C6—C7	118.6 (4)
O9—Tb1—O8	51.15 (9)	N1—C10—C11	124.9 (3)
O12—Tb1—O8	125.24 (10)	N1—C10—H10	117.6
O2—Tb1—O4	125.94 (9)	C11—C10—H10	117.6
O1—Tb1—O4	61.39 (8)	C13—C12—C11	121.4 (4)
O5—Tb1—O4	105.75 (10)	C13—C12—H12	119.3
O11—Tb1—O4	76.80 (9)	C11—C12—H12	119.3
O9—Tb1—O4	118.27 (8)	N5—O8—Tb1	95.5 (2)
O12—Tb1—O4	75.93 (10)	N5—O9—Tb1	97.0 (2)
O8—Tb1—O4	69.84 (8)	O10—N5—O8	122.4 (4)
O2—Tb1—O3	61.59 (8)	O10—N5—O9	121.9 (4)
O1—Tb1—O3	126.69 (8)	O8—N5—O9	115.8 (3)
O5—Tb1—O3	104.88 (10)	C3—C2—O3	126.0 (4)
O11—Tb1—O3	76.27 (9)	C3—C2—C1	121.4 (4)
O9—Tb1—O3	68.42 (9)	O3—C2—C1	112.6 (3)
O12—Tb1—O3	76.06 (10)	O4—C17—H17A	109.5
O8—Tb1—O3	118.47 (9)	O4—C17—H17B	109.5
O4—Tb1—O3	149.37 (8)	H17A—C17—H17B	109.5
O6—Zn1—O2	102.47 (11)	O4—C17—H17C	109.5
O6—Zn1—O1	104.10 (11)	H17A—C17—H17C	109.5
O2—Zn1—O1	78.92 (10)	H17B—C17—H17C	109.5
O6—Zn1—N1	110.00 (12)	N1—C9—C8	108.8 (3)
O2—Zn1—N1	147.27 (12)	N1—C9—H9A	109.9
O1—Zn1—N1	89.14 (11)	C8—C9—H9A	109.9
O6—Zn1—N2	112.68 (12)	N1—C9—H9B	109.9
O2—Zn1—N2	89.16 (12)	C8—C9—H9B	109.9
O1—Zn1—N2	143.00 (12)	H9A—C9—H9B	108.3
N1—Zn1—N2	82.26 (13)	C2—C3—C4	119.4 (4)
O2—C1—C6	124.7 (3)	C2—C3—H3	120.3
O2—C1—C2	116.0 (3)	C4—C3—H3	120.3
C6—C1—C2	119.2 (3)	C4—C5—C6	121.6 (4)
C2—O3—C18	115.8 (3)	C4—C5—H5	119.2
C2—O3—Tb1	118.7 (2)	C6—C5—H5	119.2
C18—O3—Tb1	125.1 (2)	C15—C14—C13	118.9 (4)
C1—O2—Zn1	126.1 (2)	C15—C14—H14	120.6
C1—O2—Tb1	130.8 (2)	C13—C14—H14	120.6
Zn1—O2—Tb1	101.57 (10)	C12—C13—C14	120.8 (4)
C7—N2—C8	121.4 (3)	C12—C13—H13	119.6
C7—N2—Zn1	126.1 (3)	C14—C13—H13	119.6
C8—N2—Zn1	112.2 (3)	N2—C8—C9	110.0 (3)
N3—O12—Tb1	95.4 (2)	N2—C8—H8A	109.7
C15—O4—C17	116.5 (3)	C9—C8—H8A	109.7
C15—O4—Tb1	118.6 (2)	N2—C8—H8B	109.7
C17—O4—Tb1	124.9 (2)	C9—C8—H8B	109.7
O1—C16—C15	116.3 (3)	H8A—C8—H8B	108.2
O1—C16—C11	124.7 (3)	C5—C4—C3	120.7 (4)
C15—C16—C11	119.0 (3)	C5—C4—H4	119.7
N3—O11—Tb1	96.8 (2)	C3—C4—H4	119.7
N4—O6—Zn1	119.7 (2)	O3—C18—H18A	109.5
C16—O1—Zn1	128.1 (2)	O3—C18—H18B	109.5
C16—O1—Tb1	130.9 (2)	H18A—C18—H18B	109.5
Zn1—O1—Tb1	101.02 (9)	O3—C18—H18C	109.5
C10—N1—C9	122.8 (3)	H18A—C18—H18C	109.5
C10—N1—Zn1	128.7 (3)	H18B—C18—H18C	109.5
C9—N1—Zn1	108.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O11^i	0.93	2.45	3.376 (5)	173
C9—H9A···O13^ii	0.97	2.54	3.487 (6)	165

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