Crystal structure of di-μ-hydroxido-bis{[N,N'-bis-(2,6-di-methyl-phen-yl)pentane-2,4-diiminato(1-)]zinc}.

The title compound, [Zn2(C21H25N2)2(OH)2], is a binuclear zinc complex formed by two bidentate β-diketiminate (nacnac) ligands and two μ-hydroxide O atoms, bridging two mononuclear units into a centrosymmetric dimeric unit. Each Zn(2+) cation is coordinated by two N-donor atoms from the nacnac ligand and two O-donor atoms of hydroxide anions to give a distorted tetra-hedral coordination environment. The Zn-O bond lengths are 1.9643 (13) and 2.0022 (14) Å, and the two Zn-N bond lengths are 1.9696 (14) and 1.9823 (14) Å. The distance between the two Zn(2+) cations in the dimer is 2.9420 (4) Å. Although hydroxide groups are present in the complex, no classical hydrogen-bonding inter-ations are observed because of the bulky β-diketiminate ligands.

Related literature

For similar compounds with a [Zn2(OH)2] diamond core structure supported by β-diketiminate ligands, see: Cheng et al. (2001 ▶); Chisholm et al. (2002 ▶); Gondzik et al. (2014 ▶); Schulz et al. (2011 ▶). For the geometry index of four-coordinated metal cations, see: Yang et al. (2007 ▶).

Experimental

Crystal data

[Zn2(C21H25N2)2(OH)2]

M = 775.61

Monoclinic,

a = 12.8736 (4) Å

b = 8.7682 (3) Å

c = 17.4530 (5) Å

β = 105.222 (2)°

V = 1900.95 (10) Å3

Z = 2

Mo Kα radiation

μ = 1.30 mm−1

T = 100 K

0.46 × 0.23 × 0.23 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.586, T max = 0.754

22627 measured reflections

3730 independent reflections

3576 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.079

S = 0.99

3730 reflections

230 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.06 e Å−3

Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL2012 (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S160053681401736X/wm5037sup1.cif

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681401736X/wm5037Isup2.docx

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401736X/wm5037Isup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681401736X/wm5037Isup5.cdx

Click here for additional data file.

. DOI: 10.1107/S160053681401736X/wm5037fig1.tif

The mol­ecular structure of the title complex. Anisotropic displacement ellipsoids were drawn at the 30% probability level. Hydrogen atoms, except for the two oxygen donor atoms, have been omitted for clarity. [Symmetry code A: −x+2, −y+2, −z+2.]

CCDC reference: 1013307

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Zn2(C21H25N2)2(OH)2]	F(000) = 816
Mr = 775.61	Dx = 1.355 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.8736 (4) Å	Cell parameters from 7335 reflections
b = 8.7682 (3) Å	θ = 2.3–28.3°
c = 17.4530 (5) Å	µ = 1.30 mm−1
β = 105.222 (2)°	T = 100 K
V = 1900.95 (10) Å3	Block, colorless
Z = 2	0.46 × 0.23 × 0.23 mm

Bruker APEX CCD diffractometer	3576 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.016
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θmax = 26.0°, θmin = 1.8°
Tmin = 0.586, Tmax = 0.754	h = −15→15
22627 measured reflections	k = −10→10
3730 independent reflections	l = −21→21

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029	Hydrogen site location: mixed
wR(F2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.050P)2 + 1.390P] where P = (Fo2 + 2Fc2)/3
3730 reflections	(Δ/σ)max = 0.002
230 parameters	Δρmax = 1.06 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

	x	y	z	Uiso*/Ueq
Zn1	0.95859 (2)	0.92266 (2)	0.92324 (2)	0.02197 (9)
N1	1.01789 (11)	0.88907 (16)	0.83143 (8)	0.0201 (3)
N2	0.81321 (11)	0.83790 (17)	0.87559 (8)	0.0228 (3)
O1	0.96361 (10)	1.13369 (16)	0.96789 (7)	0.0259 (3)
H1	0.9667 (18)	1.209 (3)	0.9400 (15)	0.038 (7)*
C3	0.95099 (13)	0.87215 (19)	0.75919 (10)	0.0210 (3)
C4	0.83960 (13)	0.8525 (2)	0.74383 (10)	0.0223 (3)
H4	0.8007	0.8593	0.6896	0.027*
C5	0.77700 (13)	0.8241 (2)	0.79754 (10)	0.0225 (3)
C6	0.99662 (14)	0.8736 (2)	0.68752 (10)	0.0262 (4)
H6A	1.0405	0.9654	0.6889	0.039*
H6B	0.9375	0.8735	0.6389	0.039*
H6C	1.0414	0.7829	0.6884	0.039*
C7	0.66271 (13)	0.7706 (2)	0.76132 (10)	0.0267 (4)
H7A	0.6537	0.6674	0.7802	0.040*
H7B	0.6483	0.7698	0.7033	0.040*
H7C	0.6123	0.8399	0.7770	0.040*
C8	0.74730 (13)	0.7795 (2)	0.92370 (10)	0.0241 (4)
C9	0.76109 (14)	0.6264 (2)	0.94808 (10)	0.0259 (4)
C10	0.69362 (16)	0.5658 (2)	0.99114 (11)	0.0305 (4)
H10	0.7011	0.4621	1.0074	0.037*
C11	0.61560 (15)	0.6562 (3)	1.01037 (11)	0.0335 (4)
H11	0.5684	0.6135	1.0383	0.040*
C12	0.60651 (14)	0.8085 (3)	0.98893 (11)	0.0333 (4)
H12	0.5541	0.8698	1.0037	0.040*
C13	0.67270 (14)	0.8742 (2)	0.94604 (11)	0.0294 (4)
C14	0.84837 (15)	0.5304 (2)	0.92859 (12)	0.0309 (4)
H14A	0.8418	0.4248	0.9451	0.046*
H14B	0.9191	0.5707	0.9568	0.046*
H14C	0.8408	0.5334	0.8712	0.046*
C15	0.66482 (18)	1.0416 (3)	0.92477 (14)	0.0394 (5)
H15A	0.7365	1.0880	0.9413	0.059*
H15B	0.6168	1.0925	0.9520	0.059*
H15C	0.6360	1.0530	0.8672	0.059*
C16	1.13079 (13)	0.8705 (2)	0.83836 (9)	0.0205 (3)
C17	1.17176 (14)	0.7214 (2)	0.84038 (10)	0.0238 (3)
C18	1.28096 (14)	0.7028 (2)	0.84487 (11)	0.0281 (4)
H18	1.3101	0.6030	0.8463	0.034*
C19	1.34732 (14)	0.8281 (2)	0.84731 (11)	0.0290 (4)
H19	1.4212	0.8140	0.8494	0.035*
C20	1.30597 (14)	0.9738 (2)	0.84663 (10)	0.0277 (4)
H20	1.3522	1.0591	0.8488	0.033*
C21	1.19747 (14)	0.9978 (2)	0.84288 (10)	0.0228 (3)
C22	1.09984 (17)	0.5850 (2)	0.83697 (13)	0.0314 (4)
H22A	1.0652	0.5902	0.8806	0.047*
H22B	1.1429	0.4916	0.8419	0.047*
H22C	1.0446	0.5843	0.7862	0.047*
C23	1.15467 (15)	1.1575 (2)	0.84357 (11)	0.0285 (4)
H23A	1.0852	1.1661	0.8038	0.043*
H23B	1.2058	1.2301	0.8311	0.043*
H23C	1.1452	1.1803	0.8963	0.043*

	U11	U22	U33	U12	U13	U23
Zn1	0.01621 (12)	0.03297 (14)	0.01712 (12)	0.00048 (7)	0.00511 (8)	−0.00413 (7)
N1	0.0170 (7)	0.0258 (7)	0.0179 (7)	0.0004 (5)	0.0054 (5)	−0.0020 (5)
N2	0.0172 (6)	0.0314 (8)	0.0201 (7)	0.0002 (6)	0.0056 (5)	0.0005 (6)
O1	0.0264 (6)	0.0323 (7)	0.0186 (6)	0.0012 (5)	0.0052 (5)	−0.0017 (5)
C3	0.0231 (8)	0.0214 (8)	0.0196 (8)	0.0010 (6)	0.0074 (6)	−0.0003 (6)
C4	0.0212 (8)	0.0272 (9)	0.0179 (8)	0.0000 (6)	0.0039 (6)	0.0015 (6)
C5	0.0190 (8)	0.0248 (8)	0.0226 (8)	0.0014 (6)	0.0037 (6)	0.0023 (7)
C6	0.0239 (8)	0.0366 (10)	0.0191 (8)	−0.0015 (7)	0.0073 (7)	−0.0002 (7)
C7	0.0204 (8)	0.0353 (10)	0.0227 (8)	−0.0037 (7)	0.0028 (7)	0.0038 (7)
C8	0.0164 (7)	0.0375 (10)	0.0177 (8)	−0.0011 (7)	0.0033 (6)	0.0005 (7)
C9	0.0215 (8)	0.0347 (9)	0.0201 (8)	−0.0020 (7)	0.0029 (7)	−0.0022 (7)
C10	0.0296 (10)	0.0388 (11)	0.0216 (9)	−0.0083 (8)	0.0040 (7)	0.0017 (7)
C11	0.0255 (9)	0.0542 (13)	0.0217 (9)	−0.0101 (9)	0.0081 (7)	−0.0004 (8)
C12	0.0205 (8)	0.0561 (13)	0.0243 (9)	0.0028 (8)	0.0078 (7)	−0.0023 (8)
C13	0.0208 (8)	0.0431 (11)	0.0242 (9)	0.0042 (8)	0.0057 (7)	0.0024 (8)
C14	0.0295 (9)	0.0311 (10)	0.0318 (10)	0.0015 (8)	0.0077 (8)	−0.0006 (8)
C15	0.0364 (11)	0.0441 (12)	0.0418 (12)	0.0127 (9)	0.0177 (9)	0.0040 (10)
C16	0.0187 (8)	0.0280 (9)	0.0157 (7)	0.0011 (6)	0.0062 (6)	−0.0011 (6)
C17	0.0251 (8)	0.0276 (9)	0.0204 (8)	0.0023 (7)	0.0087 (6)	−0.0009 (7)
C18	0.0274 (9)	0.0340 (10)	0.0248 (9)	0.0089 (7)	0.0102 (7)	0.0017 (7)
C19	0.0185 (8)	0.0461 (11)	0.0235 (9)	0.0032 (7)	0.0071 (7)	−0.0007 (8)
C20	0.0220 (8)	0.0392 (10)	0.0226 (9)	−0.0064 (7)	0.0072 (7)	−0.0025 (8)
C21	0.0243 (8)	0.0281 (9)	0.0167 (8)	−0.0002 (7)	0.0066 (6)	−0.0006 (6)
C22	0.0341 (10)	0.0249 (9)	0.0386 (11)	0.0014 (7)	0.0154 (9)	−0.0015 (7)
C23	0.0315 (9)	0.0258 (9)	0.0296 (9)	−0.0016 (7)	0.0104 (7)	−0.0007 (7)

Zn1—O1i	1.9643 (13)	C11—H11	0.9500
Zn1—N1	1.9696 (14)	C12—C13	1.397 (3)
Zn1—N2	1.9823 (14)	C12—H12	0.9500
Zn1—O1	2.0022 (14)	C13—C15	1.511 (3)
N1—C3	1.335 (2)	C14—H14A	0.9800
N1—C16	1.436 (2)	C14—H14B	0.9800
N2—C5	1.324 (2)	C14—H14C	0.9800
N2—C8	1.436 (2)	C15—H15A	0.9800
O1—H1	0.83 (3)	C15—H15B	0.9800
C3—C4	1.398 (2)	C15—H15C	0.9800
C3—C6	1.515 (2)	C16—C21	1.398 (2)
C4—C5	1.410 (2)	C16—C17	1.407 (2)
C4—H4	0.9500	C17—C18	1.397 (2)
C5—C7	1.515 (2)	C17—C22	1.504 (3)
C6—H6A	0.9800	C18—C19	1.386 (3)
C6—H6B	0.9800	C18—H18	0.9500
C6—H6C	0.9800	C19—C20	1.383 (3)
C7—H7A	0.9800	C19—H19	0.9500
C7—H7B	0.9800	C20—C21	1.397 (2)
C7—H7C	0.9800	C20—H20	0.9500
C8—C13	1.400 (3)	C21—C23	1.506 (3)
C8—C9	1.406 (3)	C22—H22A	0.9800
C9—C10	1.394 (3)	C22—H22B	0.9800
C9—C14	1.512 (3)	C22—H22C	0.9800
C10—C11	1.388 (3)	C23—H23A	0.9800
C10—H10	0.9500	C23—H23B	0.9800
C11—C12	1.383 (3)	C23—H23C	0.9800
O1i—Zn1—N1	122.77 (6)	C11—C12—C13	121.50 (18)
O1i—Zn1—N2	119.80 (6)	C11—C12—H12	119.2
N1—Zn1—N2	97.33 (6)	C13—C12—H12	119.2
O1i—Zn1—O1	84.25 (6)	C12—C13—C8	117.67 (19)
N1—Zn1—O1	118.36 (6)	C12—C13—C15	121.39 (18)
N2—Zn1—O1	116.11 (6)	C8—C13—C15	120.94 (17)
C3—N1—C16	117.04 (14)	C9—C14—H14A	109.5
C3—N1—Zn1	119.54 (11)	C9—C14—H14B	109.5
C16—N1—Zn1	123.26 (11)	H14A—C14—H14B	109.5
C5—N2—C8	117.81 (14)	C9—C14—H14C	109.5
C5—N2—Zn1	120.29 (11)	H14A—C14—H14C	109.5
C8—N2—Zn1	121.74 (11)	H14B—C14—H14C	109.5
Zn1i—O1—Zn1	95.75 (6)	C13—C15—H15A	109.5
Zn1i—O1—H1	132.7 (17)	C13—C15—H15B	109.5
Zn1—O1—H1	120.8 (17)	H15A—C15—H15B	109.5
N1—C3—C4	124.70 (15)	C13—C15—H15C	109.5
N1—C3—C6	118.99 (15)	H15A—C15—H15C	109.5
C4—C3—C6	116.30 (15)	H15B—C15—H15C	109.5
C3—C4—C5	129.11 (15)	C21—C16—C17	121.33 (15)
C3—C4—H4	115.4	C21—C16—N1	120.49 (15)
C5—C4—H4	115.4	C17—C16—N1	118.17 (15)
N2—C5—C4	124.02 (15)	C18—C17—C16	118.38 (16)
N2—C5—C7	119.89 (15)	C18—C17—C22	120.61 (17)
C4—C5—C7	116.07 (15)	C16—C17—C22	121.01 (15)
C3—C6—H6A	109.5	C19—C18—C17	120.81 (17)
C3—C6—H6B	109.5	C19—C18—H18	119.6
H6A—C6—H6B	109.5	C17—C18—H18	119.6
C3—C6—H6C	109.5	C20—C19—C18	119.98 (16)
H6A—C6—H6C	109.5	C20—C19—H19	120.0
H6B—C6—H6C	109.5	C18—C19—H19	120.0
C5—C7—H7A	109.5	C19—C20—C21	121.15 (18)
C5—C7—H7B	109.5	C19—C20—H20	119.4
H7A—C7—H7B	109.5	C21—C20—H20	119.4
C5—C7—H7C	109.5	C20—C21—C16	118.32 (17)
H7A—C7—H7C	109.5	C20—C21—C23	120.18 (17)
H7B—C7—H7C	109.5	C16—C21—C23	121.50 (16)
C13—C8—C9	121.56 (16)	C17—C22—H22A	109.5
C13—C8—N2	120.37 (17)	C17—C22—H22B	109.5
C9—C8—N2	118.06 (15)	H22A—C22—H22B	109.5
C10—C9—C8	118.67 (17)	C17—C22—H22C	109.5
C10—C9—C14	120.93 (18)	H22A—C22—H22C	109.5
C8—C9—C14	120.39 (16)	H22B—C22—H22C	109.5
C11—C10—C9	120.38 (19)	C21—C23—H23A	109.5
C11—C10—H10	119.8	C21—C23—H23B	109.5
C9—C10—H10	119.8	H23A—C23—H23B	109.5
C12—C11—C10	120.06 (17)	C21—C23—H23C	109.5
C12—C11—H11	120.0	H23A—C23—H23C	109.5
C10—C11—H11	120.0	H23B—C23—H23C	109.5
C16—N1—C3—C4	165.14 (16)	C11—C12—C13—C8	1.5 (3)
Zn1—N1—C3—C4	−10.5 (2)	C11—C12—C13—C15	−178.18 (19)
C16—N1—C3—C6	−14.8 (2)	C9—C8—C13—C12	−4.5 (3)
Zn1—N1—C3—C6	169.60 (12)	N2—C8—C13—C12	176.31 (16)
N1—C3—C4—C5	−10.3 (3)	C9—C8—C13—C15	175.20 (17)
C6—C3—C4—C5	169.62 (18)	N2—C8—C13—C15	−4.0 (3)
C8—N2—C5—C4	−169.09 (16)	C3—N1—C16—C21	100.95 (19)
Zn1—N2—C5—C4	6.4 (2)	Zn1—N1—C16—C21	−83.61 (18)
C8—N2—C5—C7	9.1 (2)	C3—N1—C16—C17	−79.0 (2)
Zn1—N2—C5—C7	−175.34 (12)	Zn1—N1—C16—C17	96.43 (16)
C3—C4—C5—N2	12.6 (3)	C21—C16—C17—C18	−1.7 (2)
C3—C4—C5—C7	−165.64 (18)	N1—C16—C17—C18	178.23 (15)
C5—N2—C8—C13	−91.7 (2)	C21—C16—C17—C22	178.88 (17)
Zn1—N2—C8—C13	92.82 (17)	N1—C16—C17—C22	−1.2 (2)
C5—N2—C8—C9	89.03 (19)	C16—C17—C18—C19	0.0 (3)
Zn1—N2—C8—C9	−86.44 (18)	C22—C17—C18—C19	179.42 (17)
C13—C8—C9—C10	4.2 (3)	C17—C18—C19—C20	1.1 (3)
N2—C8—C9—C10	−176.53 (15)	C18—C19—C20—C21	−0.5 (3)
C13—C8—C9—C14	−175.09 (16)	C19—C20—C21—C16	−1.1 (3)
N2—C8—C9—C14	4.2 (2)	C19—C20—C21—C23	179.00 (16)
C8—C9—C10—C11	−0.9 (3)	C17—C16—C21—C20	2.3 (2)
C14—C9—C10—C11	178.37 (17)	N1—C16—C21—C20	−177.69 (15)
C9—C10—C11—C12	−2.0 (3)	C17—C16—C21—C23	−177.87 (16)
C10—C11—C12—C13	1.7 (3)	N1—C16—C21—C23	2.2 (2)