Chlorido{6,6'-dimethyl-2,2'-[1,2-phenyl-enebis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O'}manganese(III) mono-hydrate.

In the title complex, [Mn(C(22)H(18)N(2)O(2))Cl]·H(2)O, the Mn(III) center is in a distorted square-pyramidal configuration, with the N(2)O(2) dianionic tetra-dentate Schiff base ligand in the basal plane and the chloride ion in the apical position. The dihedral angle between the two outer phenolate rings of the tetra-dentate ligand is 8.25 (8)°. The central benzene ring makes dihedral angles of 4.31 (8) and 7.37 (8)° with the two outer phenolate rings. The water mol-ecule links to the complex via an O-H⋯Cl hydrogen bond. In addition, in the crystal structure, weak C-H⋯O inter-actions link the mol-ecules into infinite one-dimensional chains along [010]. The crystal is further stabilized by O-H⋯O and O-H⋯Cl hydrogen bonds, together with weak C-H⋯π inter-actions.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For details of ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see for example: Eltayeb et al. (2007 ▶); Habibi et al. (2007 ▶); Mitra et al. (2006 ▶); Naskar et al. (2004 ▶). For background to the application of manganese complexes, see for example: Dixit & Srinivasan (1988 ▶); Glatzel et al. (2004 ▶); Lu et al. (2006 ▶); Stallings et al. (1985 ▶).

Experimental

Crystal data

[Mn(C22H18N2O2)Cl]·H2O

M = 450.79

Monoclinic,

a = 27.1836 (6) Å

b = 6.8033 (1) Å

c = 21.8896 (4) Å

β = 108.976 (1)°

V = 3828.22 (12) Å3

Z = 8

Mo Kα radiation

μ = 0.86 mm−1

T = 100.0 (1) K

0.42 × 0.26 × 0.11 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.714, T max = 0.915

24765 measured reflections

5586 independent reflections

4459 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.100

S = 1.10

5586 reflections

264 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800620X/sj2469sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800620X/sj2469Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Mn(C22H18N2O2)Cl]·H2O	F000 = 1856
Mr = 450.79	Dx = 1.564 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5586 reflections
a = 27.1836 (6) Å	θ = 2.1–30.0º
b = 6.8033 (1) Å	µ = 0.86 mm−1
c = 21.8896 (4) Å	T = 100.0 (1) K
β = 108.976 (1)º	Block, brown
V = 3828.22 (12) Å3	0.42 × 0.26 × 0.11 mm
Z = 8

Bruker SMART APEX2 CCD area-detector diffractometer	5586 independent reflections
Radiation source: fine-focus sealed tube	4459 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
Detector resolution: 8.33 pixels mm-1	θmax = 30.0º
T = 100.0(1) K	θmin = 2.1º
ω scans	h = −38→38
Absorption correction: multi-scan(SADABS; Bruker, 2005)	k = −9→9
Tmin = 0.714, Tmax = 0.915	l = −30→30
24765 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.049P)2 + 1.3516P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
5586 reflections	Δρmax = 0.49 e Å−3
264 parameters	Δρmin = −0.38 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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.

	x	y	z	Uiso*/Ueq
Mn1	0.132825 (10)	0.85182 (4)	0.049972 (11)	0.01683 (8)
Cl1	0.174472 (18)	0.53896 (6)	0.07957 (2)	0.02546 (11)
O1	0.17748 (5)	1.01562 (18)	0.11197 (5)	0.0196 (3)
O2	0.08842 (5)	0.8545 (2)	0.09903 (6)	0.0257 (3)
N1	0.16961 (6)	0.9072 (2)	−0.01268 (6)	0.0174 (3)
N2	0.07481 (6)	0.7877 (2)	−0.03041 (6)	0.0169 (3)
C1	0.22593 (6)	1.0630 (2)	0.11779 (8)	0.0177 (3)
C2	0.25769 (7)	1.1380 (2)	0.17830 (8)	0.0185 (3)
C3	0.30824 (7)	1.1903 (3)	0.18499 (8)	0.0216 (4)
H3A	0.3294	1.2374	0.2247	0.026*
C4	0.32889 (7)	1.1756 (3)	0.13454 (9)	0.0226 (4)
H4A	0.3630	1.2136	0.1408	0.027*
C5	0.29856 (7)	1.1049 (3)	0.07576 (8)	0.0207 (3)
H5A	0.3121	1.0960	0.0419	0.025*
C6	0.24664 (7)	1.0451 (2)	0.06635 (8)	0.0181 (3)
C7	0.21695 (7)	0.9778 (2)	0.00333 (8)	0.0178 (3)
H7A	0.2324	0.9846	−0.0288	0.021*
C8	0.14187 (7)	0.8456 (2)	−0.07694 (8)	0.0175 (3)
C9	0.16154 (7)	0.8447 (2)	−0.12824 (8)	0.0207 (3)
H9A	0.1953	0.8873	−0.1223	0.025*
C10	0.13042 (8)	0.7801 (3)	−0.18802 (8)	0.0237 (4)
H10A	0.1434	0.7798	−0.2225	0.028*
C11	0.08000 (8)	0.7153 (3)	−0.19751 (8)	0.0240 (4)
H11A	0.0596	0.6715	−0.2381	0.029*
C12	0.05992 (7)	0.7154 (3)	−0.14702 (8)	0.0219 (4)
H12A	0.0262	0.6722	−0.1535	0.026*
C13	0.09089 (7)	0.7810 (2)	−0.08629 (7)	0.0178 (3)
C14	0.02675 (7)	0.7584 (2)	−0.03375 (7)	0.0175 (3)
H14A	0.0030	0.7334	−0.0744	0.021*
C15	0.00722 (6)	0.7612 (2)	0.01947 (7)	0.0165 (3)
C16	−0.04602 (7)	0.7183 (2)	0.00705 (8)	0.0194 (3)
H16A	−0.0668	0.6882	−0.0348	0.023*
C17	−0.06737 (7)	0.7204 (3)	0.05540 (8)	0.0209 (3)
H17A	−0.1025	0.6931	0.0466	0.025*
C18	−0.03579 (7)	0.7639 (3)	0.11849 (8)	0.0228 (4)
H18A	−0.0505	0.7646	0.1514	0.027*
C19	0.01650 (7)	0.8058 (3)	0.13328 (8)	0.0226 (4)
C20	0.03867 (7)	0.8075 (2)	0.08341 (8)	0.0181 (3)
C21	0.23506 (7)	1.1618 (3)	0.23208 (8)	0.0228 (4)
H21A	0.2627	1.1804	0.2722	0.034*
H21B	0.2156	1.0462	0.2348	0.034*
H21C	0.2124	1.2741	0.2236	0.034*
C22	0.05095 (8)	0.8465 (4)	0.20117 (9)	0.0432 (6)
H22A	0.0299	0.8682	0.2282	0.065*
H22B	0.0716	0.9612	0.2016	0.065*
H22C	0.0734	0.7359	0.2171	0.065*
O1W	0.10173 (6)	0.3038 (2)	0.15433 (6)	0.0365 (4)
H1W1	0.1210	0.3909	0.1437	0.055*
H2W1	0.1124	0.1985	0.1426	0.055*

	U11	U22	U33	U12	U13	U23
Mn1	0.01223 (13)	0.02391 (14)	0.01463 (12)	−0.00348 (10)	0.00478 (9)	−0.00113 (9)
Cl1	0.0266 (2)	0.0250 (2)	0.0228 (2)	0.00082 (18)	0.00529 (17)	0.00321 (15)
O1	0.0134 (6)	0.0263 (6)	0.0202 (5)	−0.0048 (5)	0.0070 (5)	−0.0047 (5)
O2	0.0138 (6)	0.0470 (8)	0.0169 (5)	−0.0103 (6)	0.0060 (5)	−0.0055 (5)
N1	0.0156 (7)	0.0198 (6)	0.0170 (6)	−0.0003 (6)	0.0056 (5)	−0.0001 (5)
N2	0.0163 (7)	0.0194 (6)	0.0147 (6)	−0.0012 (6)	0.0049 (5)	0.0005 (5)
C1	0.0132 (8)	0.0184 (8)	0.0218 (7)	−0.0005 (6)	0.0061 (6)	0.0010 (6)
C2	0.0143 (8)	0.0195 (8)	0.0215 (7)	−0.0001 (6)	0.0053 (6)	−0.0002 (6)
C3	0.0133 (8)	0.0227 (8)	0.0264 (8)	−0.0020 (7)	0.0030 (7)	−0.0015 (6)
C4	0.0122 (8)	0.0242 (9)	0.0314 (9)	−0.0012 (7)	0.0072 (7)	0.0019 (7)
C5	0.0164 (8)	0.0219 (8)	0.0267 (8)	0.0008 (7)	0.0108 (7)	0.0035 (6)
C6	0.0134 (8)	0.0191 (8)	0.0221 (7)	0.0003 (6)	0.0063 (6)	0.0022 (6)
C7	0.0154 (8)	0.0191 (8)	0.0207 (7)	0.0009 (6)	0.0082 (6)	0.0017 (6)
C8	0.0191 (8)	0.0174 (7)	0.0162 (7)	0.0012 (6)	0.0060 (6)	0.0011 (6)
C9	0.0222 (9)	0.0201 (8)	0.0218 (8)	0.0017 (7)	0.0100 (7)	0.0031 (6)
C10	0.0291 (10)	0.0254 (8)	0.0192 (7)	0.0043 (8)	0.0113 (7)	0.0020 (6)
C11	0.0276 (10)	0.0270 (9)	0.0158 (7)	0.0013 (8)	0.0047 (7)	−0.0002 (6)
C12	0.0213 (9)	0.0254 (8)	0.0181 (7)	−0.0004 (7)	0.0054 (7)	0.0002 (6)
C13	0.0192 (8)	0.0197 (8)	0.0152 (7)	0.0012 (7)	0.0065 (6)	0.0011 (6)
C14	0.0158 (8)	0.0187 (8)	0.0159 (7)	−0.0013 (6)	0.0024 (6)	−0.0010 (6)
C15	0.0138 (8)	0.0174 (7)	0.0178 (7)	−0.0004 (6)	0.0044 (6)	−0.0006 (6)
C16	0.0161 (8)	0.0209 (8)	0.0195 (7)	−0.0023 (7)	0.0032 (6)	−0.0016 (6)
C17	0.0123 (8)	0.0248 (8)	0.0256 (8)	−0.0037 (7)	0.0060 (6)	−0.0015 (7)
C18	0.0153 (9)	0.0325 (9)	0.0221 (8)	−0.0043 (7)	0.0081 (7)	−0.0007 (7)
C19	0.0151 (8)	0.0346 (9)	0.0184 (7)	−0.0055 (7)	0.0061 (6)	−0.0022 (7)
C20	0.0131 (8)	0.0236 (8)	0.0177 (7)	−0.0040 (6)	0.0051 (6)	−0.0011 (6)
C21	0.0173 (9)	0.0272 (9)	0.0232 (8)	−0.0018 (7)	0.0056 (7)	−0.0018 (7)
C22	0.0216 (10)	0.0924 (19)	0.0182 (8)	−0.0194 (11)	0.0100 (8)	−0.0081 (10)
O1W	0.0398 (9)	0.0460 (8)	0.0237 (6)	0.0046 (7)	0.0105 (6)	0.0020 (6)

Mn1—O2	1.8585 (13)	C10—C11	1.389 (3)
Mn1—O1	1.8671 (11)	C10—H10A	0.9300
Mn1—N1	1.9786 (14)	C11—C12	1.383 (3)
Mn1—N2	1.9921 (13)	C11—H11A	0.9300
Mn1—Cl1	2.3989 (5)	C12—C13	1.396 (2)
O1—C1	1.321 (2)	C12—H12A	0.9300
O2—C20	1.322 (2)	C14—C15	1.429 (2)
N1—C7	1.310 (2)	C14—H14A	0.9300
N1—C8	1.426 (2)	C15—C16	1.413 (2)
N2—C14	1.300 (2)	C15—C20	1.418 (2)
N2—C13	1.427 (2)	C16—C17	1.363 (2)
C1—C6	1.418 (2)	C16—H16A	0.9300
C1—C2	1.420 (2)	C17—C18	1.400 (2)
C2—C3	1.380 (2)	C17—H17A	0.9300
C2—C21	1.504 (2)	C18—C19	1.381 (2)
C3—C4	1.396 (3)	C18—H18A	0.9300
C3—H3A	0.9300	C19—C20	1.408 (2)
C4—C5	1.370 (2)	C19—C22	1.502 (2)
C4—H4A	0.9300	C21—H21A	0.9600
C5—C6	1.418 (2)	C21—H21B	0.9600
C5—H5A	0.9300	C21—H21C	0.9600
C6—C7	1.428 (2)	C22—H22A	0.9600
C7—H7A	0.9300	C22—H22B	0.9600
C8—C9	1.392 (2)	C22—H22C	0.9600
C8—C13	1.404 (2)	O1W—H1W1	0.8718
C9—C10	1.379 (2)	O1W—H2W1	0.8438
C9—H9A	0.9300
O2—Mn1—O1	88.00 (5)	C9—C10—H10A	119.5
O2—Mn1—N1	165.54 (6)	C11—C10—H10A	119.5
O1—Mn1—N1	91.97 (5)	C12—C11—C10	120.46 (16)
O2—Mn1—N2	92.07 (6)	C12—C11—H11A	119.8
O1—Mn1—N2	156.00 (6)	C10—C11—H11A	119.8
N1—Mn1—N2	82.12 (6)	C11—C12—C13	119.28 (17)
O2—Mn1—Cl1	101.00 (4)	C11—C12—H12A	120.4
O1—Mn1—Cl1	101.25 (4)	C13—C12—H12A	120.4
N1—Mn1—Cl1	93.19 (4)	C12—C13—C8	120.00 (16)
N2—Mn1—Cl1	102.29 (4)	C12—C13—N2	124.66 (16)
C1—O1—Mn1	127.44 (11)	C8—C13—N2	115.34 (14)
C20—O2—Mn1	130.55 (11)	N2—C14—C15	125.81 (14)
C7—N1—C8	122.01 (15)	N2—C14—H14A	117.1
C7—N1—Mn1	123.94 (11)	C15—C14—H14A	117.1
C8—N1—Mn1	113.79 (11)	C16—C15—C20	119.12 (15)
C14—N2—C13	121.95 (13)	C16—C15—C14	117.97 (14)
C14—N2—Mn1	125.15 (11)	C20—C15—C14	122.91 (15)
C13—N2—Mn1	112.88 (11)	C17—C16—C15	121.10 (15)
O1—C1—C6	122.88 (14)	C17—C16—H16A	119.4
O1—C1—C2	117.53 (15)	C15—C16—H16A	119.4
C6—C1—C2	119.58 (15)	C16—C17—C18	119.26 (16)
C3—C2—C1	118.29 (16)	C16—C17—H17A	120.4
C3—C2—C21	122.38 (15)	C18—C17—H17A	120.4
C1—C2—C21	119.32 (15)	C19—C18—C17	121.95 (17)
C2—C3—C4	122.69 (16)	C19—C18—H18A	119.0
C2—C3—H3A	118.7	C17—C18—H18A	119.0
C4—C3—H3A	118.7	C18—C19—C20	119.16 (15)
C5—C4—C3	119.62 (17)	C18—C19—C22	122.21 (17)
C5—C4—H4A	120.2	C20—C19—C22	118.63 (16)
C3—C4—H4A	120.2	O2—C20—C19	117.46 (14)
C4—C5—C6	120.24 (16)	O2—C20—C15	123.15 (15)
C4—C5—H5A	119.9	C19—C20—C15	119.39 (15)
C6—C5—H5A	119.9	C2—C21—H21A	109.5
C5—C6—C1	119.56 (15)	C2—C21—H21B	109.5
C5—C6—C7	117.09 (15)	H21A—C21—H21B	109.5
C1—C6—C7	123.28 (15)	C2—C21—H21C	109.5
N1—C7—C6	124.99 (15)	H21A—C21—H21C	109.5
N1—C7—H7A	117.5	H21B—C21—H21C	109.5
C6—C7—H7A	117.5	C19—C22—H22A	109.5
C9—C8—C13	120.07 (15)	C19—C22—H22B	109.5
C9—C8—N1	125.34 (16)	H22A—C22—H22B	109.5
C13—C8—N1	114.59 (14)	C19—C22—H22C	109.5
C10—C9—C8	119.27 (17)	H22A—C22—H22C	109.5
C10—C9—H9A	120.4	H22B—C22—H22C	109.5
C8—C9—H9A	120.4	H1W1—O1W—H2W1	101.5
C9—C10—C11	120.92 (17)
O2—Mn1—O1—C1	168.47 (14)	C5—C6—C7—N1	175.99 (16)
N1—Mn1—O1—C1	−26.00 (14)	C1—C6—C7—N1	−7.1 (3)
N2—Mn1—O1—C1	−100.93 (18)	C7—N1—C8—C9	2.8 (3)
Cl1—Mn1—O1—C1	67.65 (13)	Mn1—N1—C8—C9	−171.59 (13)
O1—Mn1—O2—C20	162.44 (16)	C7—N1—C8—C13	−177.59 (15)
N1—Mn1—O2—C20	72.3 (3)	Mn1—N1—C8—C13	8.05 (18)
N2—Mn1—O2—C20	6.45 (16)	C13—C8—C9—C10	0.0 (2)
Cl1—Mn1—O2—C20	−96.49 (15)	N1—C8—C9—C10	179.64 (16)
O2—Mn1—N1—C7	109.0 (2)	C8—C9—C10—C11	−0.3 (3)
O1—Mn1—N1—C7	19.33 (14)	C9—C10—C11—C12	0.3 (3)
N2—Mn1—N1—C7	175.97 (14)	C10—C11—C12—C13	−0.1 (3)
Cl1—Mn1—N1—C7	−82.06 (13)	C11—C12—C13—C8	−0.1 (2)
O2—Mn1—N1—C8	−76.8 (2)	C11—C12—C13—N2	−179.76 (15)
O1—Mn1—N1—C8	−166.43 (11)	C9—C8—C13—C12	0.2 (2)
N2—Mn1—N1—C8	−9.80 (11)	N1—C8—C13—C12	−179.47 (15)
Cl1—Mn1—N1—C8	92.18 (11)	C9—C8—C13—N2	179.84 (14)
O2—Mn1—N2—C14	−2.08 (14)	N1—C8—C13—N2	0.2 (2)
O1—Mn1—N2—C14	−91.82 (19)	C14—N2—C13—C12	−10.0 (3)
N1—Mn1—N2—C14	−168.78 (14)	Mn1—N2—C13—C12	171.41 (13)
Cl1—Mn1—N2—C14	99.64 (13)	C14—N2—C13—C8	170.41 (15)
O2—Mn1—N2—C13	176.49 (11)	Mn1—N2—C13—C8	−8.22 (18)
O1—Mn1—N2—C13	86.76 (17)	C13—N2—C14—C15	179.65 (15)
N1—Mn1—N2—C13	9.79 (11)	Mn1—N2—C14—C15	−1.9 (2)
Cl1—Mn1—N2—C13	−81.78 (11)	N2—C14—C15—C16	−177.54 (16)
Mn1—O1—C1—C6	20.1 (2)	N2—C14—C15—C20	3.3 (3)
Mn1—O1—C1—C2	−161.02 (11)	C20—C15—C16—C17	−0.2 (2)
O1—C1—C2—C3	−179.27 (15)	C14—C15—C16—C17	−179.31 (15)
C6—C1—C2—C3	−0.3 (2)	C15—C16—C17—C18	−0.6 (3)
O1—C1—C2—C21	−0.6 (2)	C16—C17—C18—C19	0.3 (3)
C6—C1—C2—C21	178.32 (15)	C17—C18—C19—C20	0.8 (3)
C1—C2—C3—C4	1.1 (3)	C17—C18—C19—C22	−178.0 (2)
C21—C2—C3—C4	−177.49 (16)	Mn1—O2—C20—C19	173.81 (12)
C2—C3—C4—C5	−0.6 (3)	Mn1—O2—C20—C15	−6.8 (3)
C3—C4—C5—C6	−0.6 (3)	C18—C19—C20—O2	177.84 (17)
C4—C5—C6—C1	1.4 (2)	C22—C19—C20—O2	−3.2 (3)
C4—C5—C6—C7	178.40 (15)	C18—C19—C20—C15	−1.6 (3)
O1—C1—C6—C5	178.01 (15)	C22—C19—C20—C15	177.32 (18)
C2—C1—C6—C5	−0.9 (2)	C16—C15—C20—O2	−178.13 (16)
O1—C1—C6—C7	1.2 (3)	C14—C15—C20—O2	1.0 (3)
C2—C1—C6—C7	−177.73 (15)	C16—C15—C20—C19	1.3 (2)
C8—N1—C7—C6	178.93 (15)	C14—C15—C20—C19	−179.62 (16)
Mn1—N1—C7—C6	−7.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···Cl1	0.87	2.54	3.3544 (16)	157
O1W—H2W1···O1i	0.84	2.43	3.191 (2)	151
O1W—H2W1···O2i	0.84	2.53	3.2642 (19)	146
C16—H16A···O1Wii	0.93	2.48	3.364 (2)	160
C7—H7A···Cg1iii	0.93	3.39	3.9811 (17)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯Cl1	0.87	2.54	3.3544 (16)	157
O1W—H2W1⋯O1i	0.84	2.43	3.191 (2)	151
O1W—H2W1⋯O2i	0.84	2.53	3.2642 (19)	146
C16—H16A⋯O1Wii	0.93	2.48	3.364 (2)	160
C7—H7A⋯Cg1iii	0.93	3.39	3.9811 (17)	123

Symmetry codes: (i) ; (ii) ; (iii) . Cg1 is the centroid of the C1–C6 benzene ring.