Zn/Mn–MOFs with `S-shaped' packing modes

Two novel polymers exhibiting metal–organic frameworks (MOFs) have been synthesized by the combination of a metal ion with a benzene-1,3,5-tri­carboxyl­ate ligand (BTC) and 1,10-phenanthroline (phen) under hydro­thermal conditions. The first compound, poly[[(μ₄-benzene-1,3,5-tri­carboxyl­ato-κ⁴O:O′:O′′:O′′′)(μ-hydroxido-κ²O:O)bis­(1,10-phenanthroline-κ²N,N′)dizinc(II)] 0.32-hydrate], {[Zn₂(C₉H₃O₆)(OH)(C₁₂H₈N₂)₂]·0.32H₂O}_n, denoted Zn–MOF, forms a two-dimensional network in which a binuclear Zn₂ cluster serves as a 3-connecting node; the BTC trianion also acts as a 3-connecting centre. The overall topology is that of a 6³ net. The phen ligands serve as appendages to the network and inter­digitate with phen ligands belonging to adjacent parallel sheets. The second compound, poly[[­(μ₆-benzene-1,3,5-tri­carboxyl­ato-κ⁷O¹,O^1′:O¹:O³:O^3′:O⁵:O^5′)­(μ₃-hydroxido-κ²O:O:O)(1,10-phenanthroline-κ²N,N′)di­manganese(II)] 1.26-hydrate], {[Mn₂(C₉H₃O₆)(OH)(C₁₂H₈N₂)]·1.26H₂O}_n, denoted Mn–MOF, exists as a three-dimensional network in which an Mn₄ cluster serves as a 6-connecting unit, while the BTC trianion again plays the role of a 3-connecting centre. The overall topology is that of the rutile net. Phen ligands act as appendages to the network and form the `S-shaped' packing mode.

Computing details

Data collection: CrystalClear-SM Expert (Rigaku, 2009) for HUT-13; CrysAlis PRO (Oxford Diffraction, 2010) for HUT-14. Cell refinement: CrystalClear-SM Expert (Rigaku, 2009) for HUT-13; CrysAlis PRO (Oxford Diffraction, 2010) for HUT-14. Data reduction: CrystalClear-SM Expert (Rigaku, 2009) for HUT-13; CrysAlis PRO (Oxford Diffraction, 2010) for HUT-14. For both structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Poly[[(µ₄-benzene-1,3,5-tricarboxylato-κ⁴O:O':O'':O''')(µ-hydroxido-κ²O:O')bis(1,10-phenanthroline-κ²N,N')dizinc(II)] monohydrate] (HUT-13)

Crystal data

[Zn2(C9H3O6)(OH)(C12H8N2)2]·0.32H2O	F(000) = 1464
Mr = 723.27	Dx = 1.671 Mg m^−3
Monoclinic, P21/n	Synchrotron radiation, λ = 0.6889 Å
Hall symbol: -P 2yn	Cell parameters from 10993 reflections
a = 11.9003 (1) Å	θ = 1.8–29.5°
b = 17.6185 (3) Å	µ = 1.59 mm^−1
c = 13.7173 (2) Å	T = 100 K
β = 91.157 (1)°	Prism, colourless
V = 2875.46 (7) Å^3	0.1 × 0.05 × 0.03 mm
Z = 4

Data collection

Dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images diffractometer	5228 reflections with I > 2σ(I)
Synchrotron monochromator	Rint = 0.037
ω scans	θmax = 25.5°, θmin = 5.0°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −14→14
Tmin = 0.568, Tmax = 1	k = −22→22
23044 measured reflections	l = −13→17
5681 independent reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ^2(Fo^2) + (0.062P)^2 + 4.8591P] where P = (Fo^2 + 2Fc^2)/3
5681 reflections	(Δ/σ)max = 0.001
429 parameters	Δρmax = 0.76 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Zn1	0.76234 (3)	0.34704 (2)	0.67610 (3)	0.01928 (13)
Zn2	0.76462 (3)	0.343444 (19)	0.91459 (3)	0.01930 (13)
N2	0.5908 (2)	0.39526 (15)	0.9175 (2)	0.0239 (6)
N3	0.5822 (2)	0.39791 (16)	0.6597 (2)	0.0265 (6)
N4	0.7878 (2)	0.46036 (16)	0.6362 (2)	0.0262 (6)
N1	0.7940 (2)	0.46096 (15)	0.8973 (2)	0.0231 (6)
O1	0.7158 (2)	0.28990 (13)	0.79240 (18)	0.0224 (5)
H50	0.644 (4)	0.287 (2)	0.796 (3)	0.029 (10)*
O2	0.9284 (2)	0.33818 (13)	0.72358 (19)	0.0257 (5)
O3	0.93052 (18)	0.32019 (14)	0.88727 (17)	0.0242 (5)
O4	0.7386 (2)	0.28113 (13)	0.03337 (17)	0.0245 (5)
O5	0.7465 (2)	0.28737 (14)	0.55590 (18)	0.0255 (5)
O6	0.8990 (3)	0.3293 (2)	0.4789 (2)	0.0491 (8)
O7	0.8292 (2)	0.37397 (16)	0.1124 (2)	0.0378 (7)
C1	0.8947 (3)	0.4940 (2)	0.8948 (3)	0.0336 (8)
H1	0.9595	0.4638	0.9076	0.040*
C2	0.9094 (3)	0.5717 (2)	0.8738 (3)	0.0423 (10)
H2	0.9825	0.5935	0.8745	0.051*
C3	0.8167 (3)	0.6152 (2)	0.8523 (3)	0.0393 (9)
H3	0.8253	0.6673	0.8362	0.047*
C4	0.7084 (3)	0.5827 (2)	0.8541 (3)	0.0320 (8)
C5	0.7016 (3)	0.50485 (18)	0.8796 (2)	0.0242 (7)
C6	0.6063 (3)	0.6239 (2)	0.8339 (3)	0.0356 (9)
H6	0.6104	0.6755	0.8144	0.043*
C7	0.5053 (3)	0.5908 (2)	0.8422 (3)	0.0357 (9)
H7	0.4394	0.6196	0.8283	0.043*
C8	0.4942 (3)	0.5123 (2)	0.8718 (3)	0.0300 (8)
C9	0.5928 (3)	0.46906 (19)	0.8892 (3)	0.0255 (7)
C10	0.3903 (3)	0.4755 (2)	0.8864 (3)	0.0359 (9)
H10	0.3218	0.5024	0.8762	0.043*
C11	0.3887 (3)	0.4011 (2)	0.9152 (3)	0.0359 (9)
H11	0.3193	0.3759	0.9255	0.043*
C12	0.4910 (3)	0.3625 (2)	0.9293 (3)	0.0313 (8)
H12	0.4890	0.3106	0.9482	0.038*
C13	0.8891 (3)	0.4893 (2)	0.6205 (3)	0.0344 (8)
H13	0.9531	0.4580	0.6314	0.041*
C14	0.9054 (4)	0.5646 (2)	0.5883 (3)	0.0413 (10)
H14	0.9790	0.5831	0.5772	0.050*
C15	0.8133 (4)	0.6107 (2)	0.5733 (3)	0.0404 (9)
H15	0.8229	0.6616	0.5520	0.049*
C16	0.7043 (3)	0.5819 (2)	0.5898 (3)	0.0329 (8)
C17	0.6958 (3)	0.50536 (19)	0.6195 (3)	0.0283 (7)
C18	0.6028 (4)	0.6259 (2)	0.5751 (3)	0.0396 (9)
H18	0.6082	0.6775	0.5556	0.048*
C19	0.5009 (4)	0.5949 (2)	0.5887 (3)	0.0397 (9)
H19	0.4357	0.6253	0.5787	0.048*
C20	0.4884 (3)	0.5167 (2)	0.6181 (3)	0.0346 (8)
C21	0.5862 (3)	0.4720 (2)	0.6334 (3)	0.0280 (7)
C22	0.3836 (3)	0.4815 (3)	0.6323 (3)	0.0406 (9)
H22	0.3160	0.5096	0.6238	0.049*
C23	0.3799 (3)	0.4062 (2)	0.6584 (3)	0.0388 (9)
H23	0.3100	0.3816	0.6682	0.047*
C24	0.4815 (3)	0.3664 (2)	0.6705 (3)	0.0336 (8)
H24	0.4781	0.3142	0.6872	0.040*
C31	0.5898 (2)	0.21746 (17)	0.2991 (2)	0.0205 (6)
C32	0.6468 (3)	0.23587 (17)	0.3856 (2)	0.0211 (6)
H32	0.6165	0.2208	0.4461	0.025*
C33	0.7481 (3)	0.27617 (18)	0.3847 (3)	0.0224 (7)
C34	0.7902 (3)	0.29957 (18)	0.2941 (2)	0.0221 (7)
H34	0.8574	0.3286	0.2924	0.027*
C35	0.7348 (2)	0.28076 (18)	0.2073 (2)	0.0217 (7)
C36	0.6352 (3)	0.23770 (17)	0.2092 (2)	0.0214 (6)
H36	0.5990	0.2225	0.1501	0.026*
C37	0.9735 (3)	0.31716 (18)	0.8033 (2)	0.0220 (7)
C38	0.8046 (3)	0.30024 (19)	0.4794 (3)	0.0270 (7)
C39	0.7732 (3)	0.31423 (19)	0.1114 (3)	0.0240 (7)
OW1	0.1444 (10)	0.5005 (9)	0.7536 (13)	0.089 (7)	0.316 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0181 (2)	0.0219 (2)	0.0178 (2)	0.00046 (13)	−0.00019 (16)	0.00089 (13)
Zn2	0.0183 (2)	0.0220 (2)	0.0178 (2)	0.00187 (13)	0.00397 (16)	0.00098 (13)
N2	0.0235 (14)	0.0242 (13)	0.0241 (16)	0.0007 (11)	0.0062 (12)	−0.0015 (11)
N3	0.0250 (14)	0.0287 (14)	0.0259 (16)	0.0017 (11)	0.0004 (12)	0.0033 (12)
N4	0.0256 (14)	0.0250 (14)	0.0280 (17)	−0.0016 (11)	−0.0004 (13)	0.0008 (12)
N1	0.0211 (13)	0.0255 (14)	0.0229 (15)	0.0000 (11)	0.0031 (12)	−0.0011 (11)
O1	0.0214 (12)	0.0256 (11)	0.0204 (13)	−0.0013 (9)	0.0026 (10)	0.0000 (9)
O2	0.0169 (11)	0.0380 (13)	0.0222 (14)	0.0040 (9)	0.0007 (10)	0.0062 (10)
O3	0.0175 (11)	0.0340 (12)	0.0212 (13)	0.0060 (9)	0.0028 (10)	−0.0013 (10)
O4	0.0288 (12)	0.0279 (12)	0.0169 (12)	−0.0012 (9)	0.0033 (10)	0.0019 (9)
O5	0.0254 (12)	0.0334 (13)	0.0178 (12)	−0.0068 (10)	0.0012 (10)	−0.0021 (10)
O6	0.0354 (16)	0.081 (2)	0.0309 (17)	−0.0322 (15)	0.0040 (13)	−0.0067 (15)
O7	0.0401 (15)	0.0451 (15)	0.0284 (15)	−0.0187 (12)	0.0052 (12)	0.0035 (12)
C1	0.0237 (17)	0.0363 (19)	0.041 (2)	−0.0012 (14)	0.0041 (16)	−0.0015 (16)
C2	0.0323 (19)	0.0337 (19)	0.061 (3)	−0.0100 (16)	0.0127 (19)	−0.0042 (18)
C3	0.044 (2)	0.0277 (18)	0.047 (3)	−0.0057 (16)	0.0132 (19)	−0.0009 (16)
C4	0.0366 (19)	0.0265 (17)	0.033 (2)	0.0025 (14)	0.0084 (16)	−0.0009 (14)
C5	0.0251 (16)	0.0251 (15)	0.0226 (17)	0.0014 (12)	0.0044 (14)	−0.0001 (13)
C6	0.045 (2)	0.0262 (17)	0.036 (2)	0.0083 (15)	0.0045 (18)	0.0019 (15)
C7	0.036 (2)	0.0340 (19)	0.037 (2)	0.0122 (15)	−0.0029 (17)	−0.0030 (16)
C8	0.0264 (18)	0.0318 (17)	0.032 (2)	0.0059 (14)	0.0017 (15)	−0.0054 (14)
C9	0.0252 (16)	0.0278 (16)	0.0237 (18)	0.0026 (13)	0.0044 (14)	−0.0036 (13)
C10	0.0234 (17)	0.044 (2)	0.041 (2)	0.0063 (15)	0.0022 (16)	−0.0095 (17)
C11	0.0262 (18)	0.042 (2)	0.039 (2)	−0.0057 (15)	0.0067 (16)	−0.0115 (17)
C12	0.0301 (18)	0.0303 (17)	0.034 (2)	−0.0036 (14)	0.0090 (16)	−0.0051 (15)
C13	0.0295 (18)	0.0338 (19)	0.040 (2)	−0.0050 (14)	−0.0017 (17)	0.0054 (16)
C14	0.041 (2)	0.038 (2)	0.045 (3)	−0.0125 (17)	0.0000 (19)	0.0069 (18)
C15	0.055 (2)	0.0288 (18)	0.037 (2)	−0.0067 (17)	−0.0013 (19)	0.0036 (16)
C16	0.044 (2)	0.0284 (17)	0.0263 (19)	0.0016 (15)	−0.0037 (16)	−0.0004 (14)
C17	0.0337 (18)	0.0274 (16)	0.0236 (18)	0.0015 (14)	−0.0011 (15)	0.0008 (13)
C18	0.058 (3)	0.0265 (18)	0.034 (2)	0.0101 (17)	−0.0009 (19)	0.0033 (15)
C19	0.049 (2)	0.035 (2)	0.036 (2)	0.0175 (17)	−0.0023 (19)	−0.0017 (16)
C20	0.0333 (19)	0.0374 (19)	0.033 (2)	0.0099 (15)	0.0014 (17)	−0.0006 (15)
C21	0.0290 (17)	0.0319 (17)	0.0230 (18)	0.0053 (14)	−0.0011 (14)	−0.0016 (14)
C22	0.0291 (19)	0.055 (2)	0.038 (2)	0.0125 (17)	0.0019 (17)	−0.0024 (18)
C23	0.0258 (18)	0.054 (2)	0.037 (2)	0.0005 (16)	0.0024 (16)	0.0002 (18)
C24	0.0308 (19)	0.0390 (19)	0.031 (2)	−0.0007 (15)	0.0009 (16)	0.0025 (16)
C31	0.0172 (14)	0.0206 (14)	0.0237 (17)	0.0013 (11)	0.0025 (13)	−0.0014 (12)
C32	0.0188 (14)	0.0230 (14)	0.0217 (17)	0.0011 (11)	0.0035 (13)	0.0014 (12)
C33	0.0192 (15)	0.0255 (15)	0.0225 (17)	0.0018 (12)	0.0020 (13)	−0.0003 (12)
C34	0.0188 (14)	0.0260 (15)	0.0217 (17)	−0.0021 (12)	0.0025 (13)	0.0000 (12)
C35	0.0195 (15)	0.0247 (15)	0.0211 (17)	0.0031 (11)	0.0039 (13)	0.0004 (12)
C36	0.0198 (15)	0.0245 (15)	0.0200 (16)	0.0039 (12)	0.0004 (13)	−0.0007 (12)
C37	0.0196 (15)	0.0237 (15)	0.0229 (17)	−0.0004 (12)	0.0023 (13)	0.0006 (12)
C38	0.0231 (16)	0.0322 (17)	0.0257 (19)	−0.0065 (13)	0.0014 (14)	−0.0019 (14)
C39	0.0186 (15)	0.0288 (16)	0.0248 (18)	0.0017 (12)	0.0047 (13)	0.0036 (13)
OW1	0.048 (8)	0.091 (11)	0.128 (15)	0.003 (6)	0.010 (8)	−0.043 (9)

Geometric parameters (Å, º)

Zn1—O5	1.961 (2)	C5—C9	1.448 (5)
Zn1—O1	1.975 (2)	C6—C7	1.343 (6)
Zn1—O2	2.074 (2)	C7—C8	1.447 (5)
Zn1—N4	2.094 (3)	C8—C10	1.414 (5)
Zn1—N3	2.330 (3)	C8—C9	1.416 (5)
Zn2—O4^i	1.994 (2)	C10—C11	1.370 (6)
Zn2—O1	2.000 (2)	C11—C12	1.405 (5)
Zn2—O3	2.058 (2)	C13—C14	1.413 (5)
Zn2—N1	2.114 (3)	C14—C15	1.377 (6)
Zn2—N2	2.262 (3)	C15—C16	1.416 (6)
N2—C12	1.334 (4)	C16—C17	1.412 (5)
N2—C9	1.357 (4)	C16—C18	1.445 (6)
N3—C24	1.332 (5)	C17—C21	1.448 (5)
N3—C21	1.355 (4)	C18—C19	1.346 (6)
N4—C13	1.330 (4)	C19—C20	1.444 (6)
N4—C17	1.368 (5)	C20—C22	1.410 (6)
N1—C1	1.333 (4)	C20—C21	1.418 (5)
N1—C5	1.363 (4)	C22—C23	1.375 (6)
O2—C37	1.264 (4)	C23—C24	1.404 (5)
O3—C37	1.271 (4)	C31—C32	1.393 (5)
O4—C39	1.280 (4)	C31—C36	1.402 (4)
O4—Zn2^ii	1.994 (2)	C31—C37^iii	1.514 (4)
O5—C38	1.288 (4)	C32—C33	1.399 (4)
O6—C38	1.235 (4)	C33—C34	1.411 (4)
O7—C39	1.246 (4)	C33—C38	1.512 (5)
C1—C2	1.410 (5)	C34—C35	1.389 (5)
C2—C3	1.372 (6)	C35—C36	1.408 (4)
C3—C4	1.411 (5)	C35—C39	1.520 (4)
C4—C5	1.417 (5)	C37—C31^iv	1.514 (4)
C4—C6	1.438 (5)
O5—Zn1—O1	112.46 (10)	C10—C8—C7	124.2 (3)
O5—Zn1—O2	107.35 (10)	C9—C8—C7	118.8 (3)
O1—Zn1—O2	89.39 (10)	N2—C9—C8	123.0 (3)
O5—Zn1—N4	107.67 (11)	N2—C9—C5	117.6 (3)
O1—Zn1—N4	137.85 (11)	C8—C9—C5	119.3 (3)
O2—Zn1—N4	90.66 (11)	C11—C10—C8	119.8 (3)
O5—Zn1—N3	93.03 (11)	C10—C11—C12	119.1 (3)
O1—Zn1—N3	90.07 (10)	N2—C12—C11	123.0 (3)
O2—Zn1—N3	158.13 (10)	N4—C13—C14	122.8 (4)
N4—Zn1—N3	75.28 (11)	C15—C14—C13	119.2 (4)
O4^i—Zn2—O1	112.20 (10)	C14—C15—C16	119.6 (4)
O4^i—Zn2—O3	101.81 (10)	C17—C16—C15	117.3 (4)
O1—Zn2—O3	90.99 (10)	C17—C16—C18	119.2 (4)
O4^i—Zn2—N1	131.26 (11)	C15—C16—C18	123.4 (4)
O1—Zn2—N1	114.47 (11)	N4—C17—C16	122.7 (3)
O3—Zn2—N1	90.75 (10)	N4—C17—C21	117.6 (3)
O4^i—Zn2—N2	92.91 (10)	C16—C17—C21	119.7 (3)
O1—Zn2—N2	87.39 (10)	C19—C18—C16	121.0 (3)
O3—Zn2—N2	164.66 (10)	C18—C19—C20	121.6 (4)
N1—Zn2—N2	76.12 (10)	C22—C20—C21	117.4 (4)
C12—N2—C9	118.1 (3)	C22—C20—C19	123.7 (4)
C12—N2—Zn2	130.1 (2)	C21—C20—C19	118.9 (4)
C9—N2—Zn2	111.1 (2)	N3—C21—C20	122.8 (3)
C24—N3—C21	117.8 (3)	N3—C21—C17	117.6 (3)
C24—N3—Zn1	131.1 (2)	C20—C21—C17	119.6 (3)
C21—N3—Zn1	111.1 (2)	C23—C22—C20	119.6 (4)
C13—N4—C17	118.4 (3)	C22—C23—C24	118.7 (4)
C13—N4—Zn1	123.0 (2)	N3—C24—C23	123.6 (4)
C17—N4—Zn1	118.5 (2)	C32—C31—C36	120.0 (3)
C1—N1—C5	118.1 (3)	C32—C31—C37^iii	119.5 (3)
C1—N1—Zn2	125.5 (2)	C36—C31—C37^iii	120.3 (3)
C5—N1—Zn2	116.2 (2)	C31—C32—C33	121.1 (3)
Zn1—O1—Zn2	110.79 (11)	C32—C33—C34	118.5 (3)
C37—O2—Zn1	132.7 (2)	C32—C33—C38	120.2 (3)
C37—O3—Zn2	125.4 (2)	C34—C33—C38	121.0 (3)
C39—O4—Zn2^ii	112.3 (2)	C35—C34—C33	120.9 (3)
C38—O5—Zn1	123.1 (2)	C34—C35—C36	119.8 (3)
N1—C1—C2	123.0 (3)	C34—C35—C39	120.2 (3)
C3—C2—C1	119.0 (3)	C36—C35—C39	119.5 (3)
C2—C3—C4	120.0 (3)	C31—C36—C35	119.6 (3)
C3—C4—C5	117.1 (3)	O2—C37—O3	126.9 (3)
C3—C4—C6	124.0 (3)	O2—C37—C31^iv	117.2 (3)
C5—C4—C6	118.9 (3)	O3—C37—C31^iv	115.9 (3)
N1—C5—C4	122.9 (3)	O6—C38—O5	125.5 (3)
N1—C5—C9	117.2 (3)	O6—C38—C33	120.0 (3)
C4—C5—C9	120.0 (3)	O5—C38—C33	114.5 (3)
C7—C6—C4	121.3 (3)	O7—C39—O4	123.8 (3)
C6—C7—C8	121.7 (3)	O7—C39—C35	119.3 (3)
C10—C8—C9	117.0 (3)	O4—C39—C35	116.7 (3)

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

Poly[[bis(µ₆-benzene-1,3,5-tricarboxylato-κ⁴O:O':O'':O''')bis(µ₃-hydroxido-κ²O:O:O)bis(µ₂-hydroxido-κ²O:O)bis(1,10-phenanthroline-κ²N,N')tetramanganese(II)] 1.32-hydrate] (HUT-14)

Crystal data

[Mn2(C9H3O6)(OH)(C12H8N2)]·1.26H2O	F(000) = 1056
Mr = 528.29	Dx = 1.739 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 16326 reflections
a = 10.0433 (1) Å	θ = 4.1–76.1°
b = 10.8307 (1) Å	µ = 10.71 mm^−1
c = 18.5159 (1) Å	T = 150 K
β = 93.779 (1)°	Block, yellow
V = 2009.71 (3) Å^3	0.10 × 0.08 × 0.03 mm
Z = 4

Data collection

Oxford SuperNova Dual diffractometer (Cu at zero) with an Atlas detector	3807 independent reflections
Graphite monochromator	3540 reflections with I > 2σ(I)
Detector resolution: 10.4102 pixels mm^-1	Rint = 0.040
ω scans	θmax = 70.1°, θmin = 6.0°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −12→12
Tmin = 0.703, Tmax = 1	k = −13→13
32065 measured reflections	l = −22→22

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0373P)^2 + 1.574P] where P = (Fo^2 + 2Fc^2)/3
3807 reflections	(Δ/σ)max = 0.001
283 parameters	Δρmax = 0.56 e Å^−3
39 restraints	Δρmin = −0.38 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.38 (release 10-08-2010 CrysAlis171 .NET) (compiled Aug 10 2010,17:59:35) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Mn1	0.27665 (3)	0.82104 (3)	0.524677 (17)	0.02440 (10)
Mn2	0.46630 (3)	1.01549 (3)	0.410433 (16)	0.02304 (10)
O1	0.47220 (13)	0.87375 (14)	0.49193 (7)	0.0247 (3)
H1	0.5325	0.8028	0.4826	0.03*
O2	0.54482 (15)	0.81213 (16)	0.64935 (9)	0.0351 (4)
O3	0.35623 (18)	0.71283 (19)	0.61295 (9)	0.0451 (5)
O4	0.68861 (15)	0.54367 (16)	0.94854 (8)	0.0328 (4)
O5	0.79427 (15)	0.54255 (17)	0.84685 (9)	0.0359 (4)
O6	0.19497 (16)	0.48099 (19)	0.90574 (9)	0.0411 (4)
O7	0.08759 (15)	0.60227 (19)	0.82919 (10)	0.0457 (5)
C1	0.4498 (2)	0.67468 (19)	0.73041 (11)	0.0234 (4)
C2	0.56871 (19)	0.64562 (19)	0.77022 (11)	0.0230 (4)
H2	0.652	0.6627	0.7508	0.028*
C3	0.56516 (19)	0.59171 (19)	0.83819 (11)	0.0217 (4)
C4	0.44334 (19)	0.56856 (19)	0.86725 (11)	0.0232 (4)
H4	0.4411	0.5356	0.9147	0.028*
C5	0.32478 (19)	0.5938 (2)	0.82666 (11)	0.0238 (4)
C6	0.32878 (19)	0.6470 (2)	0.75863 (11)	0.0252 (4)
H6	0.2478	0.6647	0.7311	0.03*
C7	0.4513 (2)	0.7382 (2)	0.65822 (11)	0.0283 (4)
C8	0.6920 (2)	0.55701 (19)	0.88113 (12)	0.0253 (4)
C9	0.1947 (2)	0.5585 (2)	0.85525 (11)	0.0274 (4)
N1A	0.2393 (6)	0.6862 (5)	0.4348 (3)	0.0291 (15)*	0.449 (6)
N2A	0.0695 (6)	0.7451 (7)	0.5380 (4)	0.032 (2)*	0.449 (6)
C10A	0.0577 (7)	0.5782 (6)	0.3652 (3)	0.0377 (15)*	0.449 (6)
C11A	0.0233 (6)	0.6747 (5)	0.4796 (4)	0.0272 (15)*	0.449 (6)
C12A	0.1105 (7)	0.6459 (5)	0.4254 (3)	0.0251 (14)*	0.449 (6)
C13A	−0.1634 (7)	0.5671 (5)	0.4126 (4)	0.0345 (14)*	0.449 (6)
H13A	−0.254	0.5414	0.4078	0.041*	0.449 (6)
C14A	−0.1122 (6)	0.6356 (6)	0.4744 (4)	0.0395 (16)*	0.449 (6)
C15A	−0.0763 (8)	0.5396 (7)	0.3600 (4)	0.0516 (18)*	0.449 (6)
H15A	−0.108	0.4929	0.319	0.062*	0.449 (6)
C16A	−0.0138 (7)	0.7710 (6)	0.5898 (4)	0.0376 (17)*	0.449 (6)
H16A	0.0209	0.8183	0.63	0.045*	0.449 (6)
C17A	0.3201 (8)	0.6609 (6)	0.3827 (3)	0.0425 (16)*	0.449 (6)
H17A	0.4097	0.6893	0.3876	0.051*	0.449 (6)
C18A	−0.1495 (7)	0.7337 (6)	0.5896 (5)	0.0412 (15)*	0.449 (6)
H18A	−0.2051	0.7532	0.6276	0.049*	0.449 (6)
C19A	0.2769 (9)	0.5935 (7)	0.3207 (4)	0.0487 (18)*	0.449 (6)
H19A	0.3367	0.5753	0.2845	0.058*	0.449 (6)
C20A	0.1456 (9)	0.5541 (5)	0.3135 (3)	0.0353 (14)*	0.449 (6)
H20A	0.1156	0.509	0.2715	0.042*	0.449 (6)
C21A	−0.1932 (7)	0.6671 (7)	0.5296 (5)	0.0456 (16)*	0.449 (6)
H21A	−0.2837	0.6411	0.5255	0.055*	0.449 (6)
N1B	0.2037 (6)	0.6767 (4)	0.4373 (2)	0.0291 (12)*	0.551 (6)
N2B	0.0703 (5)	0.7492 (5)	0.5524 (3)	0.0295 (16)*	0.551 (6)
C10B	0.0089 (6)	0.5842 (4)	0.3793 (3)	0.0365 (12)*	0.551 (6)
C11B	0.0008 (5)	0.6872 (4)	0.4984 (3)	0.0242 (11)*	0.551 (6)
C12B	0.0719 (6)	0.6498 (4)	0.4382 (3)	0.0259 (11)*	0.551 (6)
C13B	−0.1973 (6)	0.5896 (5)	0.4399 (4)	0.0479 (14)*	0.551 (6)
H13B	−0.2896	0.5702	0.4399	0.057*	0.551 (6)
C14B	−0.1347 (5)	0.6545 (4)	0.4991 (3)	0.0323 (11)*	0.551 (6)
C15B	−0.1255 (6)	0.5540 (5)	0.3821 (3)	0.0374 (12)*	0.551 (6)
H15B	−0.1687	0.5082	0.3435	0.045*	0.551 (6)
C16B	0.0088 (5)	0.7760 (5)	0.6106 (3)	0.0343 (13)*	0.551 (6)
H16B	0.058	0.8144	0.6501	0.041*	0.551 (6)
C17B	0.2729 (6)	0.6438 (5)	0.3809 (3)	0.0357 (12)*	0.551 (6)
H17B	0.3647	0.6656	0.3818	0.043*	0.551 (6)
C18B	−0.1270 (5)	0.7503 (5)	0.6171 (4)	0.0421 (13)*	0.551 (6)
H18B	−0.1697	0.7727	0.6594	0.05*	0.551 (6)
C19B	0.2168 (7)	0.5783 (5)	0.3196 (3)	0.0361 (11)*	0.551 (6)
H19B	0.2683	0.5554	0.2805	0.043*	0.551 (6)
C20B	0.0828 (7)	0.5499 (5)	0.3205 (3)	0.0433 (13)*	0.551 (6)
H20B	0.0399	0.5066	0.2809	0.052*	0.551 (6)
C21B	−0.1971 (5)	0.6912 (5)	0.5597 (4)	0.0398 (12)*	0.551 (6)
H21B	−0.2897	0.6758	0.5624	0.048*	0.551 (6)
O1W	0.5470 (8)	0.6539 (8)	0.2833 (5)	0.124 (4)*	0.523 (10)
O2W	0	0	0	0.18 (2)*	0.21 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02117 (16)	0.03535 (19)	0.01631 (16)	−0.00438 (13)	−0.00138 (11)	0.00062 (13)
Mn2	0.01591 (15)	0.03624 (19)	0.01676 (16)	−0.00384 (12)	−0.00053 (11)	0.00365 (13)
O1	0.0210 (7)	0.0338 (8)	0.0194 (7)	0.0030 (6)	0.0029 (5)	0.0027 (6)
O2	0.0254 (7)	0.0472 (10)	0.0321 (8)	−0.0084 (7)	−0.0035 (6)	0.0183 (7)
O3	0.0415 (9)	0.0621 (12)	0.0293 (9)	−0.0217 (9)	−0.0150 (7)	0.0203 (8)
O4	0.0333 (8)	0.0407 (9)	0.0228 (8)	−0.0065 (7)	−0.0099 (6)	0.0059 (7)
O5	0.0206 (7)	0.0543 (10)	0.0319 (8)	0.0090 (7)	−0.0051 (6)	−0.0015 (8)
O6	0.0298 (8)	0.0604 (12)	0.0336 (9)	−0.0025 (8)	0.0054 (7)	0.0232 (8)
O7	0.0200 (8)	0.0656 (12)	0.0518 (11)	0.0037 (8)	0.0044 (7)	0.0240 (10)
C1	0.0219 (9)	0.0275 (10)	0.0206 (10)	−0.0032 (8)	−0.0004 (7)	0.0045 (8)
C2	0.0172 (9)	0.0293 (10)	0.0224 (10)	−0.0019 (7)	0.0007 (7)	0.0015 (8)
C3	0.0185 (9)	0.0252 (10)	0.0207 (9)	0.0003 (7)	−0.0031 (7)	−0.0003 (8)
C4	0.0232 (9)	0.0271 (10)	0.0190 (9)	−0.0001 (8)	−0.0012 (7)	0.0032 (8)
C5	0.0194 (9)	0.0293 (10)	0.0225 (10)	−0.0014 (8)	0.0004 (7)	0.0032 (8)
C6	0.0183 (9)	0.0320 (11)	0.0248 (10)	−0.0003 (8)	−0.0034 (7)	0.0059 (8)
C7	0.0232 (10)	0.0378 (12)	0.0234 (10)	−0.0026 (9)	−0.0017 (8)	0.0084 (9)
C8	0.0217 (9)	0.0261 (10)	0.0270 (11)	−0.0017 (8)	−0.0070 (8)	−0.0004 (8)
C9	0.0225 (10)	0.0377 (12)	0.0222 (10)	−0.0023 (9)	0.0022 (8)	0.0029 (9)

Geometric parameters (Å, º)

Mn1—O3	2.1241 (17)	C5—C6	1.388 (3)
Mn1—O6^i	2.1665 (18)	C5—C9	1.491 (3)
Mn1—O1	2.1697 (14)	N1A—C17A	1.329 (8)
Mn1—O4^ii	2.1799 (16)	N1A—C12A	1.365 (8)
Mn1—N1A	2.227 (5)	N2A—C16A	1.343 (8)
Mn1—N2A	2.266 (6)	N2A—C11A	1.378 (9)
Mn1—N2B	2.303 (5)	C10A—C20A	1.369 (9)
Mn1—N1B	2.332 (4)	C10A—C15A	1.406 (9)
Mn2—O5^ii	2.1209 (15)	C10A—C12A	1.408 (7)
Mn2—O1	2.1508 (15)	C11A—C12A	1.410 (8)
Mn2—O2^iii	2.1696 (16)	C11A—C14A	1.423 (7)
Mn2—O1^iii	2.2229 (15)	C13A—C15A	1.384 (9)
Mn2—O6^iv	2.3043 (16)	C13A—C14A	1.430 (9)
Mn2—O7^iv	2.3695 (17)	C14A—C21A	1.390 (9)
O1—Mn2^iii	2.2229 (15)	C16A—C18A	1.422 (9)
O2—C7	1.253 (3)	C17A—C19A	1.405 (9)
O2—Mn2^iii	2.1696 (16)	C18A—C21A	1.373 (10)
O3—C7	1.259 (3)	C19A—C20A	1.385 (9)
O4—C8	1.259 (3)	N1B—C17B	1.342 (6)
O4—Mn1^v	2.1799 (16)	N1B—C12B	1.356 (7)
O5—C8	1.253 (3)	N2B—C16B	1.311 (7)
O5—Mn2^v	2.1209 (15)	N2B—C11B	1.358 (7)
O6—C9	1.257 (3)	C10B—C15B	1.392 (8)
O6—Mn1^vi	2.1665 (17)	C10B—C20B	1.407 (7)
O6—Mn2^vii	2.3043 (16)	C10B—C12B	1.415 (6)
O7—C9	1.244 (3)	C11B—C14B	1.408 (6)
O7—Mn2^vii	2.3695 (17)	C11B—C12B	1.422 (7)
C1—C6	1.387 (3)	C13B—C15B	1.386 (7)
C1—C2	1.397 (3)	C13B—C14B	1.413 (7)
C1—C7	1.504 (3)	C14B—C21B	1.380 (8)
C2—C3	1.390 (3)	C16B—C18B	1.404 (7)
C3—C4	1.391 (3)	C17B—C19B	1.422 (7)
C3—C8	1.504 (3)	C18B—C21B	1.391 (8)
C4—C5	1.393 (3)	C19B—C20B	1.382 (7)
O3—Mn1—O6^i	87.45 (8)	C4—C5—C9	119.74 (18)
O3—Mn1—O1	93.36 (6)	C1—C6—C5	120.65 (18)
O6^i—Mn1—O1	82.52 (6)	O2—C7—O3	126.5 (2)
O3—Mn1—O4^ii	169.92 (7)	O2—C7—C1	117.41 (18)
O6^i—Mn1—O4^ii	83.05 (7)	O3—C7—C1	116.11 (19)
O1—Mn1—O4^ii	88.77 (6)	O5—C8—O4	124.36 (19)
O3—Mn1—N1A	104.44 (15)	O5—C8—C3	117.24 (19)
O6^i—Mn1—N1A	167.89 (15)	O4—C8—C3	118.40 (19)
O1—Mn1—N1A	94.30 (17)	O7—C9—O6	120.2 (2)
O4^ii—Mn1—N1A	85.21 (14)	O7—C9—C5	121.4 (2)
O3—Mn1—N2A	90.99 (19)	O6—C9—C5	118.45 (19)
O6^i—Mn1—N2A	108.13 (18)	C17A—N1A—C12A	117.4 (6)
O1—Mn1—N2A	168.68 (18)	C17A—N1A—Mn1	126.6 (5)
O4^ii—Mn1—N2A	88.77 (19)	C12A—N1A—Mn1	114.7 (4)
N1A—Mn1—N2A	74.5 (2)	C16A—N2A—C11A	118.9 (6)
O3—Mn1—N2B	86.60 (15)	C16A—N2A—Mn1	128.4 (5)
O6^i—Mn1—N2B	102.88 (15)	C11A—N2A—Mn1	112.3 (5)
O1—Mn1—N2B	174.59 (15)	C20A—C10A—C15A	123.6 (6)
O4^ii—Mn1—N2B	92.21 (15)	C20A—C10A—C12A	115.2 (6)
N1A—Mn1—N2B	80.5 (2)	C15A—C10A—C12A	121.2 (7)
N2A—Mn1—N2B	6.7 (2)	N2A—C11A—C12A	119.3 (5)
O3—Mn1—N1B	104.40 (12)	N2A—C11A—C14A	119.3 (7)
O6^i—Mn1—N1B	166.24 (12)	C12A—C11A—C14A	121.4 (6)
O1—Mn1—N1B	103.39 (14)	N1A—C12A—C10A	124.9 (6)
O4^ii—Mn1—N1B	84.64 (11)	N1A—C12A—C11A	117.7 (5)
N1A—Mn1—N1B	9.13 (16)	C10A—C12A—C11A	117.4 (6)
N2A—Mn1—N1B	65.4 (2)	C15A—C13A—C14A	117.6 (6)
N2B—Mn1—N1B	71.42 (19)	C21A—C14A—C11A	118.7 (6)
O5^ii—Mn2—O1	99.30 (6)	C21A—C14A—C13A	121.2 (6)
O5^ii—Mn2—O2^iii	87.66 (7)	C11A—C14A—C13A	120.1 (7)
O1—Mn2—O2^iii	166.01 (6)	C13A—C15A—C10A	122.3 (6)
O5^ii—Mn2—O1^iii	141.62 (6)	N2A—C16A—C18A	125.5 (7)
O1—Mn2—O1^iii	79.70 (6)	N1A—C17A—C19A	122.0 (7)
O2^iii—Mn2—O1^iii	87.29 (6)	C21A—C18A—C16A	114.0 (6)
O5^ii—Mn2—O6^iv	139.59 (6)	C20A—C19A—C17A	118.7 (7)
O1—Mn2—O6^iv	93.26 (6)	C10A—C20A—C19A	121.8 (6)
O2^iii—Mn2—O6^iv	89.11 (7)	C18A—C21A—C14A	123.6 (6)
O1^iii—Mn2—O6^iv	78.32 (5)	C17B—N1B—C12B	120.5 (5)
O5^ii—Mn2—O7^iv	85.53 (6)	C17B—N1B—Mn1	124.2 (4)
O1—Mn2—O7^iv	93.99 (7)	C12B—N1B—Mn1	113.5 (3)
O2^iii—Mn2—O7^iv	98.66 (7)	C16B—N2B—C11B	117.9 (5)
O1^iii—Mn2—O7^iv	132.83 (5)	C16B—N2B—Mn1	126.0 (4)
O6^iv—Mn2—O7^iv	55.22 (6)	C11B—N2B—Mn1	115.4 (4)
Mn2—O1—Mn1	113.60 (6)	C15B—C10B—C20B	121.9 (5)
Mn2—O1—Mn2^iii	100.30 (6)	C15B—C10B—C12B	118.3 (6)
Mn1—O1—Mn2^iii	97.06 (5)	C20B—C10B—C12B	119.7 (5)
C7—O2—Mn2^iii	127.09 (14)	N2B—C11B—C14B	124.6 (5)
C7—O3—Mn1	128.50 (16)	N2B—C11B—C12B	117.3 (4)
C8—O4—Mn1^v	121.85 (14)	C14B—C11B—C12B	118.1 (5)
C8—O5—Mn2^v	114.91 (14)	N1B—C12B—C10B	119.1 (6)
C9—O6—Mn1^vi	166.07 (17)	N1B—C12B—C11B	119.2 (4)
C9—O6—Mn2^vii	93.67 (13)	C10B—C12B—C11B	121.7 (5)
Mn1^vi—O6—Mn2^vii	94.77 (6)	C15B—C13B—C14B	120.6 (5)
C9—O7—Mn2^vii	90.95 (14)	C21B—C14B—C11B	115.2 (5)
C6—C1—C2	119.50 (19)	C21B—C14B—C13B	124.8 (5)
C6—C1—C7	119.60 (18)	C11B—C14B—C13B	120.0 (6)
C2—C1—C7	120.88 (18)	C13B—C15B—C10B	121.2 (5)
C3—C2—C1	120.01 (18)	N2B—C16B—C18B	122.6 (6)
C2—C3—C4	120.10 (18)	N1B—C17B—C19B	123.7 (6)
C2—C3—C8	120.81 (18)	C21B—C18B—C16B	118.1 (5)
C4—C3—C8	119.08 (18)	C20B—C19B—C17B	115.9 (5)
C3—C4—C5	119.88 (18)	C19B—C20B—C10B	121.0 (5)
C6—C5—C4	119.76 (18)	C14B—C21B—C18B	121.3 (5)
C6—C5—C9	120.46 (18)

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