Two new Ni^II and Zn^II metal–organic frameworks of glutarate and 1,4-bis­[(2-methyl-1H-imidazol-1-yl)meth­yl]benzene ligands: syntheses, structures and luminescence sensing properties

Two new metal–organic frameworks (MOFs), namely, three-dimensional poly[di­aqua­bis­{μ₂-1,4-bis­[(2-methyl-1H-imidazol-1-yl)meth­yl]benzene}bis(μ₂-glu­tarato)dinickel(II)] monohydrate], {[Ni₂(C₅H₆O₄)₂(C₁₆H₁₈N₄)₂(H₂O)₂]·H₂O}_n or {[Ni₂(Glu)₂(1,4-mbix)₂(H₂O)₂]·H₂O}_n, (I), and two-dimensional poly[[{μ₂-1,4-bis­[(2-methyl-1H-imidazol-1-yl)meth­yl]benzene}(μ₂-glutarato)zinc(II)] tetra­hy­drate], {[Zn(C₅H₆O₄)(C₁₆H₁₈N₄)]·4H₂O}_n or {[Zn(Glu)(1,4-mbix)]·4H₂O}_n (II), have been synthesized hydro­thermally using glutarate (Glu²⁻) mixed with 1,4-bis­[(2-methyl-1H-imidazol-1-yl)meth­yl]benzene (1,4-mbix), and characterized by single-crystal X-ray diffraction, IR and UV–Vis spectroscopy, powder X-ray diffraction, and thermogravimetric and photoluminescence analyses. Ni^II MOF (I) shows a 4-connected 3D framework with point symbol 6⁶, but is not a typical dia network. Zn^II MOF (II) displays a two-dimensional 4⁴-sql network with one-dimensional water chains penetrating the grids along the c direction. The solid-state photoluminescence analysis of (II) was performed at room temperature and the MOF exhibits highly selective sensing toward Fe³⁺ and Cr₂O₇²⁻ ions in aqueous solution.

Computing details

For both structures, data collection: SMART (Bruker, 2016); cell refinement: SMART (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2016); software used to prepare material for publication: SHELXTL (Bruker, 2016).

Poly[diaquabis{µ₂-1,4-bis[(2-methyl-1H-imidazol-1-yl)methyl]benzene}bis(µ₂-glutarato)dinickel(II)] monohydrate] (1)

Crystal data

[Ni2(C5H6O4)2(C16H18N4)2(H2O)2]·H2O	F(000) = 2024
Mr = 964.35	Dx = 1.484 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.188 (1) Å	Cell parameters from 9972 reflections
b = 15.6516 (10) Å	θ = 2.2–26.4°
c = 22.7466 (19) Å	µ = 0.94 mm^−1
β = 95.989 (3)°	T = 153 K
V = 4315.5 (6) Å^3	Block, green
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area detector diffractometer	Rint = 0.041
phi and ω scans	θmax = 26.4°, θmin = 2.2°
31530 measured reflections	h = −15→15
4437 independent reflections	k = −19→19
3873 reflections with I > 2σ(I)	l = −28→28

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0433P)^2 + 11.7921P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
4437 reflections	Δρmax = 0.92 e Å^−3
287 parameters	Δρmin = −0.49 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.24387 (18)	0.06356 (13)	0.22946 (10)	0.0169 (4)
C2	0.1795 (2)	0.03640 (15)	0.17219 (10)	0.0231 (5)
H2A	0.2317	0.0253	0.1425	0.028*
H2B	0.1306	0.0839	0.1573	0.028*
C3	0.3905 (2)	0.45638 (14)	0.32142 (10)	0.0193 (5)
H3A	0.4437	0.4678	0.2923	0.023*
H3B	0.4332	0.4437	0.3599	0.023*
C4	0.3214 (2)	0.37859 (15)	0.30151 (12)	0.0284 (6)
H4A	0.2985	0.3837	0.2586	0.034*
H4B	0.2536	0.3789	0.3220	0.034*
C5	0.3795 (2)	0.29295 (14)	0.31307 (10)	0.0201 (5)
C6	0.1355 (2)	0.18932 (18)	0.39624 (13)	0.0321 (6)
H6A	0.1577	0.2127	0.3593	0.048*
H6B	0.1039	0.2350	0.4187	0.048*
H6C	0.0803	0.1444	0.3872	0.048*
C7	0.2338 (2)	0.15268 (15)	0.43199 (11)	0.0234 (5)
C8	0.3420 (2)	0.10487 (17)	0.50810 (12)	0.0305 (6)
H8	0.3707	0.0892	0.5470	0.037*
C9	0.3921 (2)	0.09672 (16)	0.45896 (11)	0.0259 (5)
H9	0.4635	0.0732	0.4572	0.031*
C10	0.1480 (2)	0.14476 (17)	0.52737 (11)	0.0276 (5)
H10A	0.1070	0.1989	0.5197	0.033*
H10B	0.1774	0.1437	0.5696	0.033*
C11	0.0705 (2)	0.06963 (16)	0.51408 (10)	0.0220 (5)
C12	−0.0394 (2)	0.08282 (16)	0.49313 (11)	0.0252 (5)
H12	−0.0671	0.1394	0.4883	0.030*
C13	−0.1091 (2)	0.01379 (17)	0.47920 (10)	0.0248 (5)
H13	−0.1840	0.0237	0.4649	0.030*
C14	0.1837 (2)	−0.05222 (15)	0.37851 (11)	0.0248 (5)
H14A	0.1930	−0.0418	0.4212	0.037*
H14B	0.1303	−0.0985	0.3696	0.037*
H14C	0.1567	−0.0001	0.3579	0.037*
C15	0.29122 (18)	−0.07686 (14)	0.35848 (9)	0.0166 (4)
C16	0.45185 (19)	−0.07636 (15)	0.32541 (10)	0.0214 (5)
H16	0.5177	−0.0565	0.3111	0.026*
C17	0.4265 (2)	−0.15921 (16)	0.33369 (11)	0.0246 (5)
H17	0.4700	−0.2077	0.3263	0.029*
C18	0.2633 (2)	−0.23363 (14)	0.37256 (10)	0.0241 (5)
H18A	0.2987	−0.2858	0.3588	0.029*
H18B	0.1874	−0.2311	0.3524	0.029*
C19	0.25740 (19)	−0.24064 (14)	0.43884 (10)	0.0188 (5)
C20	0.3251 (2)	−0.19379 (15)	0.48008 (11)	0.0234 (5)
H20	0.3771	−0.1549	0.4669	0.028*
C21	0.1823 (2)	−0.29695 (15)	0.45978 (11)	0.0229 (5)
H21	0.1352	−0.3296	0.4325	0.027*
N1	0.32406 (17)	0.12776 (13)	0.41059 (9)	0.0233 (4)
N2	0.23899 (19)	0.14107 (14)	0.49083 (9)	0.0278 (5)
N3	0.36720 (15)	−0.02482 (11)	0.34099 (8)	0.0160 (4)
N4	0.32452 (16)	−0.15905 (11)	0.35517 (8)	0.0184 (4)
Ni1	0.35165 (2)	0.10492 (2)	0.32341 (2)	0.01340 (9)
O1	0.34783 (13)	0.07068 (10)	0.23281 (7)	0.0193 (3)
O2	0.19381 (12)	0.07799 (10)	0.27437 (7)	0.0183 (3)
O3	0.32132 (14)	0.22832 (10)	0.29864 (8)	0.0268 (4)
O4	0.47570 (15)	0.29124 (11)	0.33788 (9)	0.0317 (4)
O5	0.51657 (12)	0.12815 (10)	0.34470 (7)	0.0165 (3)
H5A	0.5126	0.1826	0.3445	0.025*
H5B	0.5607	0.1072	0.3215	0.025*
O6	0.0000	0.17771 (16)	0.2500	0.0360 (7)
H6D	0.0536	0.1440	0.2591	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0210 (11)	0.0091 (10)	0.0196 (11)	−0.0029 (8)	−0.0021 (9)	0.0035 (8)
C2	0.0283 (12)	0.0201 (12)	0.0195 (12)	−0.0082 (9)	−0.0045 (9)	0.0027 (9)
C3	0.0225 (11)	0.0146 (11)	0.0200 (11)	0.0029 (9)	−0.0018 (9)	0.0014 (8)
C4	0.0316 (14)	0.0163 (11)	0.0339 (14)	0.0012 (10)	−0.0130 (11)	0.0029 (10)
C5	0.0251 (12)	0.0141 (11)	0.0204 (11)	0.0000 (9)	−0.0015 (9)	0.0014 (8)
C6	0.0286 (14)	0.0306 (14)	0.0364 (15)	0.0071 (11)	−0.0001 (11)	−0.0002 (11)
C7	0.0301 (13)	0.0188 (11)	0.0228 (12)	−0.0083 (9)	0.0093 (10)	−0.0063 (9)
C8	0.0297 (14)	0.0368 (15)	0.0242 (13)	−0.0046 (11)	−0.0009 (10)	0.0021 (11)
C9	0.0223 (12)	0.0289 (13)	0.0252 (13)	0.0013 (10)	−0.0040 (10)	−0.0031 (10)
C10	0.0306 (13)	0.0326 (14)	0.0216 (12)	−0.0087 (11)	0.0120 (10)	−0.0081 (10)
C11	0.0262 (12)	0.0274 (12)	0.0139 (11)	−0.0041 (10)	0.0099 (9)	−0.0033 (9)
C12	0.0297 (13)	0.0254 (12)	0.0221 (12)	0.0007 (10)	0.0109 (10)	0.0008 (10)
C13	0.0224 (12)	0.0336 (13)	0.0195 (12)	−0.0005 (10)	0.0075 (9)	−0.0003 (10)
C14	0.0249 (12)	0.0200 (11)	0.0316 (13)	−0.0040 (9)	0.0136 (10)	0.0011 (10)
C15	0.0221 (11)	0.0135 (10)	0.0139 (10)	−0.0017 (8)	0.0003 (8)	−0.0005 (8)
C16	0.0197 (11)	0.0215 (11)	0.0234 (12)	0.0026 (9)	0.0040 (9)	0.0016 (9)
C17	0.0280 (13)	0.0217 (12)	0.0240 (12)	0.0073 (10)	0.0024 (10)	0.0012 (9)
C18	0.0382 (14)	0.0132 (10)	0.0201 (12)	−0.0078 (10)	−0.0002 (10)	0.0020 (9)
C19	0.0253 (12)	0.0114 (10)	0.0183 (11)	−0.0015 (8)	−0.0043 (9)	0.0032 (8)
C20	0.0274 (13)	0.0174 (11)	0.0241 (12)	−0.0087 (9)	−0.0040 (10)	0.0050 (9)
C21	0.0281 (13)	0.0176 (11)	0.0208 (12)	−0.0078 (9)	−0.0077 (9)	0.0028 (9)
N1	0.0243 (10)	0.0220 (10)	0.0238 (10)	−0.0038 (8)	0.0038 (8)	−0.0043 (8)
N2	0.0329 (12)	0.0278 (11)	0.0243 (11)	−0.0084 (9)	0.0111 (9)	−0.0084 (9)
N3	0.0180 (9)	0.0152 (9)	0.0151 (9)	−0.0006 (7)	0.0023 (7)	0.0009 (7)
N4	0.0260 (10)	0.0123 (9)	0.0166 (9)	−0.0022 (7)	0.0004 (8)	0.0017 (7)
Ni1	0.01322 (15)	0.01142 (15)	0.01584 (15)	−0.00161 (10)	0.00288 (10)	−0.00095 (10)
O1	0.0186 (8)	0.0211 (8)	0.0182 (8)	−0.0024 (6)	0.0027 (6)	0.0024 (6)
O2	0.0152 (8)	0.0174 (8)	0.0219 (8)	−0.0010 (6)	0.0006 (6)	−0.0019 (6)
O3	0.0259 (9)	0.0140 (8)	0.0378 (10)	−0.0021 (7)	−0.0104 (8)	0.0013 (7)
O4	0.0245 (9)	0.0149 (8)	0.0531 (12)	0.0000 (7)	−0.0090 (8)	−0.0037 (8)
O5	0.0161 (7)	0.0156 (7)	0.0182 (8)	0.0004 (6)	0.0030 (6)	−0.0032 (6)
O6	0.0214 (13)	0.0247 (13)	0.0595 (19)	0.000	−0.0066 (12)	0.000

Geometric parameters (Å, º)

C1—O2	1.264 (3)	C12—H12	0.9500
C1—O1	1.266 (3)	C13—C11^iii	1.391 (4)
C1—C2	1.510 (3)	C13—H13	0.9500
C1—Ni1	2.475 (2)	C14—C15	1.482 (3)
C2—C3^i	1.531 (3)	C14—H14A	0.9800
C2—H2A	0.9900	C14—H14B	0.9800
C2—H2B	0.9900	C14—H14C	0.9800
C3—C4	1.522 (3)	C15—N3	1.325 (3)
C3—C2^ii	1.531 (3)	C15—N4	1.353 (3)
C3—H3A	0.9900	C16—C17	1.351 (4)
C3—H3B	0.9900	C16—N3	1.385 (3)
C4—C5	1.526 (3)	C16—H16	0.9500
C4—H4A	0.9900	C17—N4	1.383 (3)
C4—H4B	0.9900	C17—H17	0.9500
C5—O4	1.247 (3)	C18—N4	1.462 (3)
C5—O3	1.259 (3)	C18—C19	1.521 (3)
C6—C7	1.490 (4)	C18—H18A	0.9900
C6—H6A	0.9800	C18—H18B	0.9900
C6—H6B	0.9800	C19—C21	1.391 (3)
C6—H6C	0.9800	C19—C20	1.392 (3)
C7—N1	1.308 (3)	C20—C21^iv	1.388 (3)
C7—N2	1.346 (3)	C20—H20	0.9500
C8—C9	1.334 (4)	C21—C20^iv	1.388 (3)
C8—N2	1.396 (4)	C21—H21	0.9500
C8—H8	0.9500	N1—Ni1	2.077 (2)
C9—N1	1.394 (3)	N3—Ni1	2.0746 (18)
C9—H9	0.9500	Ni1—O3	2.0350 (16)
C10—N2	1.454 (3)	Ni1—O5	2.0503 (15)
C10—C11	1.519 (3)	Ni1—O1	2.1252 (16)
C10—H10A	0.9900	Ni1—O2	2.1622 (15)
C10—H10B	0.9900	O5—H5A	0.8535
C11—C12	1.389 (4)	O5—H5B	0.8559
C11—C13^iii	1.391 (4)	O6—H6D	0.8484
C12—C13	1.390 (4)
O2—C1—O1	120.0 (2)	N3—C15—N4	110.2 (2)
O2—C1—C2	119.8 (2)	N3—C15—C14	126.9 (2)
O1—C1—C2	120.2 (2)	N4—C15—C14	123.0 (2)
O2—C1—Ni1	60.84 (11)	C17—C16—N3	109.7 (2)
O1—C1—Ni1	59.16 (11)	C17—C16—H16	125.2
C2—C1—Ni1	178.69 (17)	N3—C16—H16	125.2
C1—C2—C3^i	113.14 (19)	C16—C17—N4	105.9 (2)
C1—C2—H2A	109.0	C16—C17—H17	127.0
C3^i—C2—H2A	109.0	N4—C17—H17	127.0
C1—C2—H2B	109.0	N4—C18—C19	113.85 (19)
C3^i—C2—H2B	109.0	N4—C18—H18A	108.8
H2A—C2—H2B	107.8	C19—C18—H18A	108.8
C4—C3—C2^ii	112.7 (2)	N4—C18—H18B	108.8
C4—C3—H3A	109.0	C19—C18—H18B	108.8
C2^ii—C3—H3A	109.0	H18A—C18—H18B	107.7
C4—C3—H3B	109.0	C21—C19—C20	117.9 (2)
C2^ii—C3—H3B	109.0	C21—C19—C18	119.1 (2)
H3A—C3—H3B	107.8	C20—C19—C18	122.9 (2)
C3—C4—C5	114.7 (2)	C21^iv—C20—C19	121.0 (2)
C3—C4—H4A	108.6	C21^iv—C20—H20	119.5
C5—C4—H4A	108.6	C19—C20—H20	119.5
C3—C4—H4B	108.6	C20^iv—C21—C19	121.1 (2)
C5—C4—H4B	108.6	C20^iv—C21—H21	119.4
H4A—C4—H4B	107.6	C19—C21—H21	119.4
O4—C5—O3	125.3 (2)	C7—N1—C9	105.3 (2)
O4—C5—C4	119.6 (2)	C7—N1—Ni1	129.26 (18)
O3—C5—C4	114.9 (2)	C9—N1—Ni1	123.46 (17)
C7—C6—H6A	109.5	C7—N2—C8	106.4 (2)
C7—C6—H6B	109.5	C7—N2—C10	127.1 (2)
H6A—C6—H6B	109.5	C8—N2—C10	124.9 (2)
C7—C6—H6C	109.5	C15—N3—C16	106.35 (19)
H6A—C6—H6C	109.5	C15—N3—Ni1	127.36 (15)
H6B—C6—H6C	109.5	C16—N3—Ni1	125.20 (15)
N1—C7—N2	112.1 (2)	C15—N4—C17	107.90 (19)
N1—C7—C6	124.8 (2)	C15—N4—C18	125.4 (2)
N2—C7—C6	123.1 (2)	C17—N4—C18	126.7 (2)
C9—C8—N2	106.2 (2)	O3—Ni1—O5	92.43 (7)
C9—C8—H8	126.9	O3—Ni1—N3	173.08 (7)
N2—C8—H8	126.9	O5—Ni1—N3	93.47 (7)
C8—C9—N1	110.0 (2)	O3—Ni1—N1	93.34 (8)
C8—C9—H9	125.0	O5—Ni1—N1	89.79 (7)
N1—C9—H9	125.0	N3—Ni1—N1	90.29 (8)
N2—C10—C11	110.55 (19)	O3—Ni1—O1	89.19 (7)
N2—C10—H10A	109.5	O5—Ni1—O1	101.27 (6)
C11—C10—H10A	109.5	N3—Ni1—O1	86.12 (7)
N2—C10—H10B	109.5	N1—Ni1—O1	168.54 (7)
C11—C10—H10B	109.5	O3—Ni1—O2	85.18 (6)
H10A—C10—H10B	108.1	O5—Ni1—O2	162.55 (6)
C12—C11—C13^iii	118.7 (2)	N3—Ni1—O2	88.11 (7)
C12—C11—C10	120.7 (2)	N1—Ni1—O2	107.59 (7)
C13^iii—C11—C10	120.6 (2)	O1—Ni1—O2	61.46 (6)
C11—C12—C13	120.5 (2)	O3—Ni1—C1	86.82 (7)
C11—C12—H12	119.8	O5—Ni1—C1	132.01 (7)
C13—C12—H12	119.8	N3—Ni1—C1	86.56 (7)
C12—C13—C11^iii	120.9 (2)	N1—Ni1—C1	138.19 (8)
C12—C13—H13	119.6	O1—Ni1—C1	30.77 (7)
C11^iii—C13—H13	119.6	O2—Ni1—C1	30.69 (7)
C15—C14—H14A	109.5	C1—O1—Ni1	90.06 (13)
C15—C14—H14B	109.5	C1—O2—Ni1	88.47 (13)
H14A—C14—H14B	109.5	C5—O3—Ni1	127.51 (15)
C15—C14—H14C	109.5	Ni1—O5—H5A	97.0
H14A—C14—H14C	109.5	Ni1—O5—H5B	116.7
H14B—C14—H14C	109.5	H5A—O5—H5B	114.7
O2—C1—C2—C3^i	−56.0 (3)	N1—C7—N2—C10	−166.5 (2)
O1—C1—C2—C3^i	123.0 (2)	C6—C7—N2—C10	13.2 (4)
C2^ii—C3—C4—C5	−161.4 (2)	C9—C8—N2—C7	−0.2 (3)
C3—C4—C5—O4	1.0 (4)	C9—C8—N2—C10	166.3 (2)
C3—C4—C5—O3	177.5 (2)	C11—C10—N2—C7	68.9 (3)
N2—C8—C9—N1	0.7 (3)	C11—C10—N2—C8	−94.8 (3)
N2—C10—C11—C12	−119.4 (2)	N4—C15—N3—C16	0.6 (2)
N2—C10—C11—C13^iii	58.4 (3)	C14—C15—N3—C16	−178.8 (2)
C13^iii—C11—C12—C13	0.0 (4)	N4—C15—N3—Ni1	169.04 (14)
C10—C11—C12—C13	177.9 (2)	C14—C15—N3—Ni1	−10.3 (3)
C11—C12—C13—C11^iii	0.0 (4)	C17—C16—N3—C15	−0.1 (3)
N3—C16—C17—N4	−0.4 (3)	C17—C16—N3—Ni1	−168.90 (16)
N4—C18—C19—C21	165.9 (2)	N3—C15—N4—C17	−0.8 (3)
N4—C18—C19—C20	−14.9 (3)	C14—C15—N4—C17	178.6 (2)
C21—C19—C20—C21^iv	0.0 (4)	N3—C15—N4—C18	178.1 (2)
C18—C19—C20—C21^iv	−179.2 (2)	C14—C15—N4—C18	−2.5 (3)
C20—C19—C21—C20^iv	0.0 (4)	C16—C17—N4—C15	0.7 (3)
C18—C19—C21—C20^iv	179.2 (2)	C16—C17—N4—C18	−178.2 (2)
N2—C7—N1—C9	0.8 (3)	C19—C18—N4—C15	−69.1 (3)
C6—C7—N1—C9	−178.9 (2)	C19—C18—N4—C17	109.6 (3)
N2—C7—N1—Ni1	165.07 (16)	O2—C1—O1—Ni1	0.3 (2)
C6—C7—N1—Ni1	−14.6 (4)	C2—C1—O1—Ni1	−178.66 (18)
C8—C9—N1—C7	−0.9 (3)	O1—C1—O2—Ni1	−0.31 (19)
C8—C9—N1—Ni1	−166.32 (17)	C2—C1—O2—Ni1	178.67 (18)
N1—C7—N2—C8	−0.4 (3)	O4—C5—O3—Ni1	12.1 (4)
C6—C7—N2—C8	179.3 (2)	C4—C5—O3—Ni1	−164.25 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4	0.85	1.76	2.602 (2)	168
O5—H5B···O1^v	0.86	1.84	2.694 (2)	175
O6—H6D···O2	0.85	2.00	2.837 (2)	171

Symmetry code: (v) −x+1, y, −z+1/2.

Poly[[{µ₂-1,4-bis[(2-methyl-1H-imidazol-1-yl)methyl]benzene}(µ₂-glutarato)zinc(II)] tetrahydrate] (2)

Crystal data

[Zn(C5H6O4)(C16H18N4)]·4H2O	F(000) = 1120
Mr = 533.87	Dx = 1.399 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.6488 (5) Å	Cell parameters from 9985 reflections
b = 17.7245 (12) Å	θ = 2.7–26.4°
c = 14.9109 (10) Å	µ = 1.02 mm^−1
β = 96.470 (2)°	T = 153 K
V = 2533.8 (3) Å^3	Block, yellow
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area detector diffractometer	Rint = 0.058
phi and ω scans	θmax = 26.4°, θmin = 2.3°
48372 measured reflections	h = −12→10
5192 independent reflections	k = −22→22
4250 reflections with I > 2σ(I)	l = −18→18

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 2.5686P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
5192 reflections	Δρmax = 0.42 e Å^−3
309 parameters	Δρmin = −0.42 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.4978 (2)	−0.13516 (13)	0.72047 (14)	0.0180 (4)
C2	0.6126 (2)	−0.19220 (13)	0.71341 (15)	0.0200 (5)
H2A	0.6006	−0.2144	0.6521	0.024*
H2B	0.6022	−0.2335	0.7569	0.024*
C3	0.7595 (2)	−0.16064 (13)	0.73130 (15)	0.0196 (5)
H3A	0.7782	−0.1274	0.6807	0.024*
H3B	0.7674	−0.1299	0.7871	0.024*
C4	−0.1332 (2)	−0.22344 (13)	0.74156 (15)	0.0199 (5)
H4A	−0.1516	−0.2551	0.7936	0.024*
H4B	−0.1468	−0.2556	0.6870	0.024*
C5	0.0176 (2)	−0.19864 (13)	0.75522 (14)	0.0185 (4)
C6	0.0311 (2)	0.06867 (14)	0.68859 (17)	0.0273 (5)
H6A	0.0518	0.0399	0.7446	0.041*
H6B	−0.0679	0.0631	0.6663	0.041*
H6C	0.0523	0.1221	0.7002	0.041*
C7	0.1173 (2)	0.03982 (13)	0.62001 (15)	0.0212 (5)
C8	0.2610 (2)	−0.02752 (14)	0.55012 (16)	0.0256 (5)
H8	0.3276	−0.0647	0.5385	0.031*
C9	0.2063 (3)	0.02435 (14)	0.49115 (17)	0.0295 (6)
H9	0.2260	0.0305	0.4306	0.035*
C10	0.0436 (2)	0.13459 (13)	0.49878 (17)	0.0273 (5)
H10A	−0.0420	0.1421	0.5286	0.033*
H10B	0.0148	0.1267	0.4336	0.033*
C11	0.1323 (2)	0.20514 (13)	0.51076 (14)	0.0206 (5)
C12	0.0695 (2)	0.27467 (13)	0.49135 (16)	0.0245 (5)
H12	−0.0281	0.2771	0.4738	0.029*
C13	0.1474 (2)	0.34040 (13)	0.49732 (16)	0.0260 (5)
H13	0.1029	0.3875	0.4837	0.031*
C14	0.2905 (2)	0.33805 (13)	0.52314 (15)	0.0222 (5)
C15	0.3532 (2)	0.26898 (14)	0.54289 (15)	0.0236 (5)
H15	0.4508	0.2666	0.5605	0.028*
C16	0.2753 (2)	0.20320 (13)	0.53736 (16)	0.0234 (5)
H16	0.3198	0.1563	0.5519	0.028*
C17	0.3801 (3)	0.09166 (14)	1.03323 (17)	0.0297 (6)
H17A	0.4741	0.1039	1.0168	0.036*
H17B	0.3906	0.0759	1.0973	0.036*
C18	0.2518 (3)	−0.03186 (14)	1.00758 (17)	0.0310 (6)
H18	0.2327	−0.0412	1.0677	0.037*
C19	0.2143 (3)	−0.07527 (14)	0.93433 (17)	0.0283 (5)
H19	0.1640	−0.1213	0.9344	0.034*
C20	0.3262 (2)	0.02117 (12)	0.88750 (15)	0.0200 (5)
C21	0.3902 (3)	0.07732 (13)	0.83099 (16)	0.0265 (5)
H21A	0.3922	0.0570	0.7700	0.040*
H21B	0.4856	0.0882	0.8577	0.040*
H21C	0.3350	0.1239	0.8279	0.040*
N1	0.20437 (19)	−0.01819 (11)	0.63150 (13)	0.0214 (4)
N2	0.1151 (2)	0.06730 (11)	0.53570 (13)	0.0243 (4)
N3	0.26085 (19)	−0.04195 (10)	0.85923 (12)	0.0202 (4)
N4	0.3232 (2)	0.02870 (11)	0.97759 (13)	0.0245 (4)
O1	0.37261 (15)	−0.16221 (9)	0.70795 (11)	0.0219 (3)
O2	0.52141 (16)	−0.06823 (9)	0.73858 (12)	0.0278 (4)
O3	0.04370 (15)	−0.13169 (9)	0.73117 (12)	0.0261 (4)
O4	0.10728 (17)	−0.24431 (10)	0.78700 (13)	0.0330 (4)
O5	0.1837 (2)	0.63348 (11)	0.67748 (13)	0.0428 (5)
H5A	0.2387	0.6553	0.6459	0.064*
H5B	0.1495	0.6641	0.7129	0.064*
O6	0.3323 (2)	0.72546 (12)	0.57719 (14)	0.0518 (6)
H6D	0.3308	0.7425	0.5238	0.078*
H6E	0.3333	0.7629	0.6128	0.078*
O7	0.3091 (3)	0.80210 (14)	0.41424 (16)	0.0709 (8)
H7A	0.3352	0.8440	0.3930	0.106*
H7B	0.2572	0.7749	0.3770	0.106*
O8	0.3387 (2)	0.94059 (13)	0.32155 (14)	0.0556 (6)
H8A	0.3917	0.9772	0.3103	0.083*
H8B	0.3030	0.9162	0.2747	0.083*
Zn1	0.23267 (2)	−0.08933 (2)	0.73666 (2)	0.01675 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0149 (10)	0.0215 (12)	0.0176 (10)	0.0011 (9)	0.0015 (8)	0.0010 (9)
C2	0.0138 (10)	0.0202 (11)	0.0260 (12)	0.0015 (9)	0.0024 (9)	−0.0036 (9)
C3	0.0140 (10)	0.0197 (11)	0.0253 (11)	0.0006 (8)	0.0032 (9)	0.0016 (9)
C4	0.0141 (10)	0.0207 (11)	0.0252 (11)	0.0000 (9)	0.0036 (9)	0.0021 (9)
C5	0.0163 (10)	0.0212 (12)	0.0185 (10)	0.0022 (9)	0.0038 (8)	−0.0031 (9)
C6	0.0254 (12)	0.0267 (13)	0.0305 (13)	0.0029 (10)	0.0064 (10)	−0.0038 (10)
C7	0.0202 (11)	0.0184 (11)	0.0242 (11)	−0.0056 (9)	−0.0011 (9)	0.0014 (9)
C8	0.0274 (12)	0.0242 (12)	0.0262 (12)	−0.0015 (10)	0.0083 (10)	−0.0029 (10)
C9	0.0409 (15)	0.0238 (13)	0.0256 (12)	−0.0050 (11)	0.0115 (11)	−0.0012 (10)
C10	0.0270 (12)	0.0218 (13)	0.0310 (13)	−0.0045 (10)	−0.0065 (10)	0.0062 (10)
C11	0.0242 (11)	0.0208 (12)	0.0164 (10)	−0.0029 (9)	0.0015 (9)	0.0029 (9)
C12	0.0201 (11)	0.0250 (12)	0.0271 (12)	0.0001 (9)	−0.0028 (9)	0.0031 (10)
C13	0.0285 (13)	0.0180 (12)	0.0303 (13)	0.0022 (10)	−0.0019 (10)	0.0046 (10)
C14	0.0266 (12)	0.0219 (12)	0.0175 (11)	−0.0050 (9)	0.0007 (9)	0.0036 (9)
C15	0.0190 (11)	0.0269 (13)	0.0243 (12)	−0.0010 (9)	0.0007 (9)	0.0029 (10)
C16	0.0241 (12)	0.0187 (12)	0.0267 (12)	0.0027 (9)	−0.0006 (9)	0.0029 (9)
C17	0.0338 (13)	0.0262 (13)	0.0267 (12)	0.0102 (11)	−0.0068 (10)	−0.0071 (10)
C18	0.0431 (15)	0.0265 (13)	0.0246 (12)	0.0076 (11)	0.0095 (11)	0.0055 (10)
C19	0.0327 (13)	0.0238 (13)	0.0297 (13)	−0.0004 (10)	0.0099 (10)	0.0046 (10)
C20	0.0202 (11)	0.0188 (11)	0.0208 (11)	0.0055 (9)	0.0013 (9)	−0.0026 (9)
C21	0.0297 (13)	0.0211 (12)	0.0292 (13)	−0.0047 (10)	0.0049 (10)	−0.0015 (10)
N1	0.0215 (9)	0.0195 (10)	0.0237 (10)	−0.0011 (8)	0.0041 (8)	−0.0001 (8)
N2	0.0263 (10)	0.0192 (10)	0.0264 (10)	−0.0045 (8)	−0.0014 (8)	0.0035 (8)
N3	0.0200 (9)	0.0185 (10)	0.0224 (10)	0.0017 (7)	0.0031 (7)	−0.0001 (8)
N4	0.0320 (11)	0.0185 (10)	0.0224 (10)	0.0064 (8)	0.0001 (8)	−0.0024 (8)
O1	0.0121 (7)	0.0219 (8)	0.0316 (9)	−0.0009 (6)	0.0023 (6)	−0.0058 (7)
O2	0.0180 (8)	0.0207 (9)	0.0444 (10)	−0.0009 (6)	0.0026 (7)	−0.0059 (7)
O3	0.0144 (8)	0.0242 (9)	0.0394 (10)	−0.0019 (7)	0.0024 (7)	0.0031 (7)
O4	0.0180 (8)	0.0322 (10)	0.0480 (11)	0.0065 (7)	−0.0001 (8)	0.0080 (8)
O5	0.0566 (13)	0.0346 (11)	0.0403 (11)	0.0072 (9)	0.0188 (10)	0.0036 (9)
O6	0.0689 (15)	0.0473 (13)	0.0419 (12)	−0.0270 (11)	0.0184 (10)	−0.0191 (10)
O7	0.0906 (19)	0.0507 (15)	0.0599 (15)	−0.0202 (13)	−0.0419 (14)	0.0082 (12)
O8	0.0687 (15)	0.0553 (14)	0.0470 (13)	−0.0366 (12)	0.0251 (11)	−0.0152 (11)
Zn1	0.01253 (12)	0.01537 (13)	0.02229 (13)	0.00008 (10)	0.00168 (9)	−0.00060 (10)

Geometric parameters (Å, º)

C1—O2	1.232 (3)	C13—C14	1.392 (3)
C1—O1	1.293 (3)	C13—H13	0.9500
C1—C2	1.512 (3)	C14—C15	1.382 (3)
C2—C3	1.519 (3)	C14—C17^iii	1.514 (3)
C2—H2A	0.9900	C15—C16	1.385 (3)
C2—H2B	0.9900	C15—H15	0.9500
C3—C4^i	1.516 (3)	C16—H16	0.9500
C3—H3A	0.9900	C17—N4	1.460 (3)
C3—H3B	0.9900	C17—C14^iv	1.514 (3)
C4—C5	1.511 (3)	C17—H17A	0.9900
C4—C3^ii	1.516 (3)	C17—H17B	0.9900
C4—H4A	0.9900	C18—C19	1.352 (4)
C4—H4B	0.9900	C18—N4	1.377 (3)
C5—O4	1.240 (3)	C18—H18	0.9500
C5—O3	1.273 (3)	C19—N3	1.385 (3)
C6—C7	1.480 (3)	C19—H19	0.9500
C6—H6A	0.9800	C20—N3	1.329 (3)
C6—H6B	0.9800	C20—N4	1.353 (3)
C6—H6C	0.9800	C20—C21	1.483 (3)
C7—N1	1.327 (3)	C21—H21A	0.9800
C7—N2	1.346 (3)	C21—H21B	0.9800
C8—C9	1.339 (3)	C21—H21C	0.9800
C8—N1	1.396 (3)	N1—Zn1	2.0065 (19)
C8—H8	0.9500	N3—Zn1	2.0019 (19)
C9—N2	1.388 (3)	O1—Zn1	1.9507 (15)
C9—H9	0.9500	O3—Zn1	1.9651 (15)
C10—N2	1.455 (3)	O5—H5A	0.8415
C10—C11	1.515 (3)	O5—H5B	0.8500
C10—H10A	0.9900	O6—H6D	0.8501
C10—H10B	0.9900	O6—H6E	0.8499
C11—C12	1.389 (3)	O7—H7A	0.8556
C11—C16	1.392 (3)	O7—H7B	0.8542
C12—C13	1.384 (3)	O8—H8A	0.8545
C12—H12	0.9500	O8—H8B	0.8600
O2—C1—O1	122.3 (2)	C15—C14—C13	118.8 (2)
O2—C1—C2	122.70 (19)	C15—C14—C17^iii	118.4 (2)
O1—C1—C2	114.94 (19)	C13—C14—C17^iii	122.7 (2)
C1—C2—C3	114.69 (19)	C14—C15—C16	120.8 (2)
C1—C2—H2A	108.6	C14—C15—H15	119.6
C3—C2—H2A	108.6	C16—C15—H15	119.6
C1—C2—H2B	108.6	C15—C16—C11	120.7 (2)
C3—C2—H2B	108.6	C15—C16—H16	119.7
H2A—C2—H2B	107.6	C11—C16—H16	119.7
C4^i—C3—C2	111.12 (18)	N4—C17—C14^iv	113.47 (19)
C4^i—C3—H3A	109.4	N4—C17—H17A	108.9
C2—C3—H3A	109.4	C14^iv—C17—H17A	108.9
C4^i—C3—H3B	109.4	N4—C17—H17B	108.9
C2—C3—H3B	109.4	C14^iv—C17—H17B	108.9
H3A—C3—H3B	108.0	H17A—C17—H17B	107.7
C5—C4—C3^ii	115.87 (18)	C19—C18—N4	106.2 (2)
C5—C4—H4A	108.3	C19—C18—H18	126.9
C3^ii—C4—H4A	108.3	N4—C18—H18	126.9
C5—C4—H4B	108.3	C18—C19—N3	109.2 (2)
C3^ii—C4—H4B	108.3	C18—C19—H19	125.4
H4A—C4—H4B	107.4	N3—C19—H19	125.4
O4—C5—O3	124.4 (2)	N3—C20—N4	109.6 (2)
O4—C5—C4	118.8 (2)	N3—C20—C21	126.7 (2)
O3—C5—C4	116.82 (19)	N4—C20—C21	123.7 (2)
C7—C6—H6A	109.5	C20—C21—H21A	109.5
C7—C6—H6B	109.5	C20—C21—H21B	109.5
H6A—C6—H6B	109.5	H21A—C21—H21B	109.5
C7—C6—H6C	109.5	C20—C21—H21C	109.5
H6A—C6—H6C	109.5	H21A—C21—H21C	109.5
H6B—C6—H6C	109.5	H21B—C21—H21C	109.5
N1—C7—N2	110.1 (2)	C7—N1—C8	106.48 (19)
N1—C7—C6	125.1 (2)	C7—N1—Zn1	128.06 (16)
N2—C7—C6	124.7 (2)	C8—N1—Zn1	124.95 (16)
C9—C8—N1	109.0 (2)	C7—N2—C9	107.7 (2)
C9—C8—H8	125.5	C7—N2—C10	127.4 (2)
N1—C8—H8	125.5	C9—N2—C10	124.6 (2)
C8—C9—N2	106.7 (2)	C20—N3—C19	106.74 (19)
C8—C9—H9	126.7	C20—N3—Zn1	130.79 (15)
N2—C9—H9	126.7	C19—N3—Zn1	122.43 (16)
N2—C10—C11	113.24 (19)	C20—N4—C18	108.2 (2)
N2—C10—H10A	108.9	C20—N4—C17	126.2 (2)
C11—C10—H10A	108.9	C18—N4—C17	125.5 (2)
N2—C10—H10B	108.9	C1—O1—Zn1	112.41 (14)
C11—C10—H10B	108.9	C5—O3—Zn1	123.83 (14)
H10A—C10—H10B	107.7	H5A—O5—H5B	111.6
C12—C11—C16	118.4 (2)	H6D—O6—H6E	107.7
C12—C11—C10	118.7 (2)	H7A—O7—H7B	115.0
C16—C11—C10	122.8 (2)	H8A—O8—H8B	114.6
C13—C12—C11	120.8 (2)	O1—Zn1—O3	113.56 (7)
C13—C12—H12	119.6	O1—Zn1—N3	116.87 (7)
C11—C12—H12	119.6	O3—Zn1—N3	103.19 (7)
C12—C13—C14	120.5 (2)	O1—Zn1—N1	106.34 (7)
C12—C13—H13	119.8	O3—Zn1—N1	99.42 (7)
C14—C13—H13	119.8	N3—Zn1—N1	116.25 (8)
O2—C1—C2—C3	0.6 (3)	C6—C7—N2—C9	−178.1 (2)
O1—C1—C2—C3	−178.03 (18)	N1—C7—N2—C10	−173.9 (2)
C1—C2—C3—C4^i	168.53 (19)	C6—C7—N2—C10	8.1 (4)
C3^ii—C4—C5—O4	161.4 (2)	C8—C9—N2—C7	−0.2 (3)
C3^ii—C4—C5—O3	−19.9 (3)	C8—C9—N2—C10	173.7 (2)
N1—C8—C9—N2	0.5 (3)	C11—C10—N2—C7	90.0 (3)
N2—C10—C11—C12	−170.0 (2)	C11—C10—N2—C9	−82.8 (3)
N2—C10—C11—C16	12.3 (3)	N4—C20—N3—C19	0.3 (2)
C16—C11—C12—C13	0.7 (3)	C21—C20—N3—C19	−178.0 (2)
C10—C11—C12—C13	−177.1 (2)	N4—C20—N3—Zn1	−177.43 (15)
C11—C12—C13—C14	−0.1 (4)	C21—C20—N3—Zn1	4.3 (3)
C12—C13—C14—C15	−0.2 (4)	C18—C19—N3—C20	0.1 (3)
C12—C13—C14—C17^iii	−178.3 (2)	C18—C19—N3—Zn1	178.07 (16)
C13—C14—C15—C16	−0.1 (3)	N3—C20—N4—C18	−0.6 (3)
C17^iii—C14—C15—C16	178.1 (2)	C21—C20—N4—C18	177.8 (2)
C14—C15—C16—C11	0.7 (4)	N3—C20—N4—C17	−178.1 (2)
C12—C11—C16—C15	−1.0 (3)	C21—C20—N4—C17	0.3 (4)
C10—C11—C16—C15	176.6 (2)	C19—C18—N4—C20	0.6 (3)
N4—C18—C19—N3	−0.4 (3)	C19—C18—N4—C17	178.1 (2)
N2—C7—N1—C8	0.4 (2)	C14^iv—C17—N4—C20	76.2 (3)
C6—C7—N1—C8	178.4 (2)	C14^iv—C17—N4—C18	−100.9 (3)
N2—C7—N1—Zn1	−171.59 (15)	O2—C1—O1—Zn1	−7.6 (3)
C6—C7—N1—Zn1	6.4 (3)	C2—C1—O1—Zn1	170.97 (14)
C9—C8—N1—C7	−0.6 (3)	O4—C5—O3—Zn1	1.9 (3)
C9—C8—N1—Zn1	171.76 (16)	C4—C5—O3—Zn1	−176.64 (14)
N1—C7—N2—C9	−0.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6	0.84	1.90	2.727 (3)	166
O5—H5B···O4^v	0.85	2.03	2.859 (3)	165
O6—H6D···O7	0.85	1.94	2.771 (3)	167
O6—H6E···O1^v	0.85	1.95	2.783 (2)	167
O7—H7A···O8	0.86	2.02	2.847 (3)	163
O7—H7B···O4^iii	0.85	1.94	2.758 (3)	161
O8—H8A···O2^vi	0.85	1.99	2.831 (3)	167
O8—H8B···O5^vii	0.86	1.96	2.802 (3)	168

Symmetry codes: (iii) x, −y+1/2, z−1/2; (v) x, y+1, z; (vi) −x+1, −y+1, −z+1; (vii) x, −y+3/2, z−1/2.