catena-Poly[[[diaqua-bis[4-(diethyl-amino)benzoato-κO]manganese(II)]-μ-aqua] dihydrate].

In the crystal structure of the title complex, {[Mn(C(11)H(14)NO(2))(2)(H(2)O)(3)]·2H(2)O}(n), the two independent Mn(II) atoms are located on a centre of symmetry and coordinated by two 4-(diethyl-amino)benzoate (DEAB) anions and two water mol-ecules in the basal plane while another water mol-ecule bridges the Mn atoms in the apical directions, forming polymeric chains. The dihedral angles between the carboxyl-ate groups and the adjacent benzene rings are 11.33 (13) and 10.90 (9)° and the benzene rings are oriented at a dihedral angle of 67.88 (6)°. The uncoordinated water mol-ecules link the carboxyl-ate groups and coordinated water mol-ecules via O-H⋯O hydrogen bonding. Weak C-H⋯π inter-actions are also found in the crystal structure.

Related literature

For the applications of transition metal complexes with biochemical mol­ecules in biological systems, see: Antolini et al. (1982 ▶). Benzoic acid derivatives such as 4-amino­benzoic acid are used extensively as bifunctional organic ligands in coordination chemistry due to their various coordination modes, see: Chen & Chen (2002 ▶); Amiraslanov et al. (1979 ▶); Hauptmann et al. (2000 ▶). In pellagra disease, niacin deficiency leads to loss of copper from the body with high serum and urinary copper levels (Krishnamachari, 1974 ▶). The nicotinic acid derivative N,N-Diethyl­nicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972 ▶). For structure–function–coordination relationships of the aryl­carboxyl­ate ion in MnII complexes of benzoic acid derivatives, see: Shnulin et al. (1981 ▶); Antsyshkina et al. (1980 ▶); Adiwidjaja et al. (1978 ▶); Catterick et al. (1974 ▶); Bigoli et al. (1972 ▶). For related structures, see: Hökelek et al. (1995 ▶, 2007 ▶, 2008 ▶); Hökelek & Necefoğlu (1996 ▶, 1997 ▶, 1998 ▶, 2007 ▶).

Experimental

Crystal data

[Mn(C11H14NO2)2(H2O)3]·2H2O

M = 529.48

Monoclinic,

a = 8.1585 (2) Å

b = 11.2907 (2) Å

c = 27.8738 (3) Å

β = 95.644 (2)°

V = 2555.15 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.57 mm−1

T = 100 K

0.50 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.870, T max = 0.920

22676 measured reflections

6299 independent reflections

4556 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.091

S = 1.02

6299 reflections

354 parameters

15 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.66 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021060/xu2525sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021060/xu2525Isup2.hkl

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

[Mn(C11H14NO2)2(H2O)3]·2H2O	F(000) = 1124
Mr = 529.48	Dx = 1.376 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6515 reflections
a = 8.1585 (2) Å	θ = 2.3–28.0°
b = 11.2907 (2) Å	µ = 0.57 mm−1
c = 27.8738 (3) Å	T = 100 K
β = 95.644 (2)°	Block, yellow
V = 2555.15 (8) Å3	0.50 × 0.20 × 0.15 mm
Z = 4

Bruker Kappa APEXII CCD area-detector diffractometer	6299 independent reflections
Radiation source: fine-focus sealed tube	4556 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 28.4°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→10
Tmin = 0.870, Tmax = 0.920	k = −11→15
22676 measured reflections	l = −37→35

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0367P)2 + 1.1841P] where P = (Fo2 + 2Fc2)/3
6299 reflections	(Δ/σ)max < 0.001
354 parameters	Δρmax = 0.66 e Å−3
15 restraints	Δρmin = −0.41 e Å−3

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	0.5000	0.0000	0.0000	0.01208 (10)
Mn2	1.0000	0.0000	0.0000	0.01215 (10)
O1	0.32484 (17)	−0.26988 (12)	0.00330 (5)	0.0168 (3)
O2	0.56738 (16)	−0.17869 (12)	0.01144 (5)	0.0184 (3)
O3	0.86399 (16)	−0.04378 (12)	0.10998 (5)	0.0162 (3)
O4	1.08825 (16)	−0.05210 (13)	0.07062 (5)	0.0167 (3)
O5	0.41531 (17)	0.00670 (13)	0.07223 (5)	0.0192 (3)
H51	0.474 (3)	−0.037 (2)	0.0985 (8)	0.045 (8)*
H52	0.308 (2)	−0.011 (2)	0.0734 (10)	0.047 (8)*
O6	0.75988 (16)	0.05770 (13)	0.02674 (5)	0.0134 (3)
H61	0.790 (3)	0.043 (2)	0.0592 (6)	0.037 (7)*
H62	0.742 (3)	0.1359 (16)	0.0247 (10)	0.057 (9)*
O7	1.11543 (18)	0.17328 (13)	0.01223 (5)	0.0188 (3)
H71	1.062 (3)	0.2483 (18)	0.0034 (9)	0.050 (8)*
H72	1.221 (2)	0.182 (3)	0.0070 (10)	0.055 (9)*
O8	0.5861 (2)	−0.10881 (17)	0.14777 (6)	0.0313 (4)
H81	0.568 (4)	−0.1863 (17)	0.1430 (13)	0.094 (14)*
H82	0.697 (3)	−0.096 (3)	0.1402 (14)	0.098 (13)*
O9	0.03985 (19)	−0.38092 (14)	0.01543 (7)	0.0276 (4)
H91	0.148 (2)	−0.360 (3)	0.0120 (11)	0.070 (10)*
H92	0.035 (6)	−0.390 (5)	0.0472 (8)	0.20 (3)*
N1	0.7834 (2)	−0.64050 (15)	0.13131 (6)	0.0173 (4)
N2	1.2766 (2)	−0.45986 (16)	0.22433 (6)	0.0190 (4)
C1	0.4744 (2)	−0.26580 (17)	0.01995 (7)	0.0147 (4)
C2	0.5485 (2)	−0.36230 (17)	0.05081 (7)	0.0134 (4)
C3	0.4689 (2)	−0.47050 (18)	0.05580 (7)	0.0150 (4)
H3	0.3633	−0.4813	0.0406	0.018*
C4	0.5434 (2)	−0.56160 (18)	0.08273 (7)	0.0151 (4)
H4	0.4869	−0.6324	0.0856	0.018*
C5	0.7046 (2)	−0.54916 (18)	0.10611 (7)	0.0148 (4)
C6	0.7801 (2)	−0.43779 (18)	0.10262 (7)	0.0181 (4)
H6	0.8834	−0.4245	0.1189	0.022*
C7	0.7036 (2)	−0.34842 (18)	0.07551 (7)	0.0161 (4)
H7	0.7574	−0.2762	0.0736	0.019*
C8	0.7200 (3)	−0.76135 (18)	0.12893 (7)	0.0187 (4)
H8A	0.8115	−0.8161	0.1285	0.022*
H8B	0.6497	−0.7715	0.0991	0.022*
C9	0.6227 (3)	−0.7917 (2)	0.17097 (8)	0.0276 (5)
H9A	0.5955	−0.8745	0.1699	0.041*
H9B	0.5234	−0.7457	0.1689	0.041*
H9C	0.6878	−0.7743	0.2007	0.041*
C10	0.9497 (3)	−0.62677 (19)	0.15495 (8)	0.0212 (5)
H10A	0.9669	−0.6842	0.1809	0.025*
H10B	0.9606	−0.5484	0.1691	0.025*
C11	1.0821 (3)	−0.6433 (2)	0.12076 (9)	0.0298 (5)
H11A	1.1888	−0.6344	0.1382	0.045*
H11B	1.0684	−0.5849	0.0957	0.045*
H11C	1.0727	−0.7210	0.1068	0.045*
C12	1.0033 (2)	−0.08717 (17)	0.10404 (7)	0.0135 (4)
C13	1.0729 (2)	−0.18313 (17)	0.13585 (6)	0.0126 (4)
C14	1.0042 (2)	−0.21580 (17)	0.17791 (6)	0.0131 (4)
H14	0.9107	−0.1766	0.1861	0.016*
C15	1.0717 (2)	−0.30486 (18)	0.20755 (7)	0.0152 (4)
H15	1.0237	−0.3236	0.2355	0.018*
C16	1.2121 (2)	−0.36804 (17)	0.19621 (7)	0.0152 (4)
C17	1.2802 (2)	−0.33497 (18)	0.15330 (7)	0.0163 (4)
H17	1.3729	−0.3743	0.1445	0.020*
C18	1.2114 (2)	−0.24579 (17)	0.12450 (7)	0.0147 (4)
H18	1.2586	−0.2265	0.0965	0.018*
C19	1.2123 (3)	−0.48833 (19)	0.27032 (7)	0.0230 (5)
H19A	1.2418	−0.5693	0.2790	0.028*
H19B	1.0931	−0.4835	0.2662	0.028*
C20	1.2764 (3)	−0.4072 (2)	0.31101 (8)	0.0293 (5)
H20A	1.2227	−0.4254	0.3393	0.044*
H20B	1.2542	−0.3264	0.3018	0.044*
H20C	1.3931	−0.4182	0.3178	0.044*
C21	1.4284 (3)	−0.51786 (19)	0.21392 (8)	0.0223 (5)
H21A	1.4247	−0.5299	0.1794	0.027*
H21B	1.4330	−0.5954	0.2290	0.027*
C22	1.5858 (3)	−0.4513 (2)	0.23068 (9)	0.0343 (6)
H22A	1.6787	−0.4933	0.2206	0.051*
H22B	1.5964	−0.4453	0.2652	0.051*
H22C	1.5815	−0.3733	0.2169	0.051*

	U11	U22	U33	U12	U13	U23
Mn1	0.0105 (2)	0.0107 (2)	0.01513 (19)	0.00024 (17)	0.00158 (15)	0.00282 (17)
Mn2	0.0106 (2)	0.0136 (2)	0.01241 (19)	0.00140 (17)	0.00160 (15)	0.00314 (17)
O1	0.0156 (7)	0.0125 (8)	0.0219 (7)	0.0011 (6)	0.0006 (6)	0.0018 (6)
O2	0.0145 (7)	0.0122 (8)	0.0294 (8)	0.0013 (6)	0.0073 (6)	0.0067 (6)
O3	0.0157 (7)	0.0159 (8)	0.0172 (7)	0.0028 (6)	0.0028 (6)	0.0034 (6)
O4	0.0148 (7)	0.0202 (8)	0.0151 (7)	−0.0004 (6)	0.0017 (5)	0.0059 (6)
O5	0.0142 (7)	0.0260 (9)	0.0175 (7)	0.0000 (7)	0.0023 (6)	0.0031 (6)
O6	0.0131 (7)	0.0132 (8)	0.0139 (7)	0.0011 (6)	0.0008 (5)	0.0016 (6)
O7	0.0146 (8)	0.0148 (8)	0.0278 (8)	0.0007 (6)	0.0053 (6)	0.0022 (6)
O8	0.0217 (9)	0.0393 (12)	0.0325 (9)	−0.0029 (8)	0.0008 (7)	0.0125 (8)
O9	0.0172 (8)	0.0201 (9)	0.0458 (10)	0.0001 (7)	0.0056 (7)	0.0033 (8)
N1	0.0199 (9)	0.0104 (9)	0.0210 (9)	0.0007 (7)	−0.0011 (7)	0.0030 (7)
N2	0.0240 (9)	0.0180 (9)	0.0155 (8)	0.0083 (8)	0.0043 (7)	0.0051 (7)
C1	0.0194 (10)	0.0109 (11)	0.0146 (9)	0.0014 (8)	0.0069 (8)	−0.0004 (8)
C2	0.0152 (10)	0.0114 (10)	0.0144 (9)	0.0035 (8)	0.0048 (8)	0.0006 (8)
C3	0.0147 (10)	0.0155 (11)	0.0152 (9)	0.0021 (8)	0.0036 (8)	0.0006 (8)
C4	0.0177 (10)	0.0118 (11)	0.0164 (9)	−0.0006 (8)	0.0044 (8)	0.0006 (8)
C5	0.0195 (10)	0.0130 (10)	0.0126 (9)	0.0026 (8)	0.0043 (8)	0.0005 (8)
C6	0.0152 (10)	0.0171 (12)	0.0212 (10)	−0.0004 (9)	−0.0016 (8)	0.0014 (8)
C7	0.0185 (10)	0.0106 (10)	0.0194 (10)	−0.0013 (8)	0.0034 (8)	0.0008 (8)
C8	0.0238 (11)	0.0104 (11)	0.0218 (10)	0.0042 (9)	0.0017 (9)	0.0014 (8)
C9	0.0349 (13)	0.0199 (13)	0.0294 (12)	−0.0011 (10)	0.0104 (10)	0.0038 (10)
C10	0.0221 (11)	0.0165 (12)	0.0234 (10)	0.0015 (9)	−0.0050 (9)	0.0044 (9)
C11	0.0230 (12)	0.0307 (14)	0.0354 (13)	0.0032 (10)	0.0021 (10)	0.0035 (11)
C12	0.0147 (10)	0.0114 (10)	0.0138 (9)	−0.0025 (8)	−0.0012 (7)	−0.0011 (7)
C13	0.0146 (10)	0.0105 (10)	0.0120 (9)	−0.0013 (8)	−0.0020 (7)	0.0001 (7)
C14	0.0147 (10)	0.0106 (10)	0.0141 (9)	−0.0005 (8)	0.0008 (7)	−0.0011 (7)
C15	0.0199 (10)	0.0152 (11)	0.0108 (9)	−0.0016 (8)	0.0028 (8)	0.0002 (8)
C16	0.0202 (11)	0.0121 (11)	0.0130 (9)	0.0021 (8)	−0.0007 (8)	0.0012 (8)
C17	0.0170 (10)	0.0172 (11)	0.0150 (9)	0.0036 (8)	0.0029 (8)	−0.0008 (8)
C18	0.0168 (10)	0.0168 (11)	0.0108 (9)	−0.0003 (8)	0.0025 (7)	0.0019 (7)
C19	0.0281 (12)	0.0221 (13)	0.0193 (10)	0.0117 (10)	0.0040 (9)	0.0082 (9)
C20	0.0313 (13)	0.0348 (15)	0.0218 (11)	0.0047 (11)	0.0018 (10)	0.0026 (10)
C21	0.0275 (12)	0.0201 (13)	0.0196 (10)	0.0105 (9)	0.0039 (9)	0.0043 (9)
C22	0.0265 (13)	0.0452 (16)	0.0318 (13)	0.0062 (12)	0.0059 (10)	0.0009 (12)

Mn1—O2	2.1071 (14)	C6—C5	1.408 (3)
Mn1—O2i	2.1071 (14)	C6—C7	1.373 (3)
Mn1—O5	2.1932 (14)	C6—H6	0.9300
Mn1—O5i	2.1932 (14)	C7—H7	0.9300
Mn1—O6	2.2725 (13)	C8—C9	1.518 (3)
Mn1—O6i	2.2725 (13)	C8—H8A	0.9700
Mn2—O4	2.1120 (13)	C8—H8B	0.9700
Mn2—O4ii	2.1120 (13)	C9—H9A	0.9600
Mn2—O6	2.2594 (13)	C9—H9B	0.9600
Mn2—O6ii	2.2594 (13)	C9—H9C	0.9600
Mn2—O7	2.1835 (14)	C10—C11	1.520 (3)
Mn2—O7ii	2.1835 (14)	C10—H10A	0.9700
O1—C1	1.263 (2)	C10—H10B	0.9700
O2—C1	1.279 (2)	C11—H11A	0.9600
O3—C12	1.263 (2)	C11—H11B	0.9600
O4—C12	1.278 (2)	C11—H11C	0.9600
O5—H51	0.970 (16)	C12—C13	1.478 (3)
O5—H52	0.903 (17)	C13—C18	1.396 (3)
O6—H61	0.931 (16)	C14—C13	1.398 (3)
O6—H62	0.896 (18)	C14—C15	1.381 (3)
O7—H71	0.973 (16)	C14—H14	0.9300
O7—H72	0.894 (17)	C15—H15	0.9300
O8—H81	0.895 (17)	C16—C15	1.412 (3)
O8—H82	0.957 (19)	C16—C17	1.417 (3)
O9—H91	0.930 (17)	C17—C18	1.373 (3)
O9—H92	0.90 (2)	C17—H17	0.9300
N1—C5	1.372 (2)	C18—H18	0.9300
N1—C8	1.458 (3)	C19—C20	1.511 (3)
N1—C10	1.457 (3)	C19—H19A	0.9700
N2—C16	1.373 (2)	C19—H19B	0.9700
N2—C19	1.468 (2)	C20—H20A	0.9600
N2—C21	1.455 (3)	C20—H20B	0.9600
C1—C2	1.480 (3)	C20—H20C	0.9600
C2—C3	1.397 (3)	C21—C22	1.521 (3)
C2—C7	1.389 (3)	C21—H21A	0.9700
C3—H3	0.9300	C21—H21B	0.9700
C4—C3	1.379 (3)	C22—H22A	0.9600
C4—C5	1.416 (3)	C22—H22B	0.9600
C4—H4	0.9300	C22—H22C	0.9600
O2i—Mn1—O2	180.00 (11)	C6—C7—C2	122.17 (19)
O2i—Mn1—O5	90.28 (5)	C6—C7—H7	118.9
O2—Mn1—O5	89.72 (5)	N1—C8—C9	112.74 (17)
O2i—Mn1—O5i	89.72 (5)	N1—C8—H8A	109.0
O2—Mn1—O5i	90.28 (5)	N1—C8—H8B	109.0
O2i—Mn1—O6	89.78 (5)	C9—C8—H8A	109.0
O2—Mn1—O6	90.22 (5)	C9—C8—H8B	109.0
O2—Mn1—O6i	89.78 (5)	H8A—C8—H8B	107.8
O2i—Mn1—O6i	90.22 (5)	C8—C9—H9A	109.5
O5—Mn1—O5i	180.00 (7)	C8—C9—H9B	109.5
O5—Mn1—O6	93.27 (5)	C8—C9—H9C	109.5
O5i—Mn1—O6	86.73 (5)	H9A—C9—H9B	109.5
O5—Mn1—O6i	86.73 (5)	H9A—C9—H9C	109.5
O5i—Mn1—O6i	93.27 (5)	H9B—C9—H9C	109.5
O6—Mn1—O6i	180.00 (10)	N1—C10—C11	113.00 (18)
O4—Mn2—O4ii	180.00 (8)	N1—C10—H10A	109.0
O4—Mn2—O6ii	90.00 (5)	N1—C10—H10B	109.0
O4ii—Mn2—O6ii	90.00 (5)	C11—C10—H10A	109.0
O4—Mn2—O6	90.00 (5)	C11—C10—H10B	109.0
O4ii—Mn2—O6	90.00 (5)	H10A—C10—H10B	107.8
O4—Mn2—O7	90.10 (5)	C10—C11—H11A	109.5
O4ii—Mn2—O7	89.90 (5)	C10—C11—H11B	109.5
O4—Mn2—O7ii	89.90 (5)	C10—C11—H11C	109.5
O4ii—Mn2—O7ii	90.10 (5)	H11A—C11—H11B	109.5
O6ii—Mn2—O6	180.00 (6)	H11A—C11—H11C	109.5
O7—Mn2—O7ii	180.00 (8)	H11B—C11—H11C	109.5
O7—Mn2—O6ii	86.29 (5)	O3—C12—O4	122.35 (18)
O7ii—Mn2—O6ii	93.71 (5)	O3—C12—C13	120.23 (17)
O7—Mn2—O6	93.71 (5)	O4—C12—C13	117.42 (17)
O7ii—Mn2—O6	86.29 (5)	C14—C13—C12	122.31 (17)
C1—O2—Mn1	127.87 (12)	C18—C13—C12	120.51 (17)
C12—O4—Mn2	127.31 (12)	C18—C13—C14	117.18 (17)
Mn1—O5—H51	120.1 (16)	C13—C14—H14	119.2
Mn1—O5—H52	114.8 (18)	C15—C14—C13	121.64 (18)
H52—O5—H51	105 (2)	C15—C14—H14	119.2
Mn1—O6—H61	114.7 (15)	C14—C15—C16	121.24 (18)
Mn1—O6—H62	97.0 (18)	C14—C15—H15	119.4
Mn2—O6—Mn1	128.35 (6)	C16—C15—H15	119.4
Mn2—O6—H61	96.4 (15)	N2—C16—C15	121.84 (17)
Mn2—O6—H62	113.8 (19)	N2—C16—C17	121.39 (18)
H61—O6—H62	106 (2)	C15—C16—C17	116.73 (18)
Mn2—O7—H71	124.4 (16)	C18—C17—C16	121.00 (18)
Mn2—O7—H72	118.9 (19)	C18—C17—H17	119.5
H72—O7—H71	106 (2)	C16—C17—H17	119.5
H81—O8—H82	105 (3)	C17—C18—C13	122.20 (18)
H91—O9—H92	105 (3)	C17—C18—H18	118.9
C5—N1—C8	122.25 (17)	C13—C18—H18	118.9
C5—N1—C10	121.36 (17)	N2—C19—C20	113.32 (18)
C10—N1—C8	115.50 (16)	N2—C19—H19A	108.9
C16—N2—C19	120.96 (16)	N2—C19—H19B	108.9
C16—N2—C21	120.77 (16)	C20—C19—H19A	108.9
C21—N2—C19	117.38 (16)	C20—C19—H19B	108.9
O1—C1—O2	121.96 (18)	H19A—C19—H19B	107.7
O1—C1—C2	120.75 (17)	C19—C20—H20A	109.5
O2—C1—C2	117.28 (17)	C19—C20—H20B	109.5
C3—C2—C1	122.32 (17)	C19—C20—H20C	109.5
C7—C2—C1	120.34 (18)	H20A—C20—H20B	109.5
C7—C2—C3	117.33 (18)	H20A—C20—H20C	109.5
C2—C3—H3	119.3	H20B—C20—H20C	109.5
C4—C3—C2	121.48 (18)	N2—C21—C22	115.19 (19)
C4—C3—H3	119.3	N2—C21—H21A	108.5
C3—C4—C5	121.09 (19)	N2—C21—H21B	108.5
C3—C4—H4	119.5	C22—C21—H21A	108.5
C5—C4—H4	119.5	C22—C21—H21B	108.5
N1—C5—C4	121.91 (18)	H21A—C21—H21B	107.5
N1—C5—C6	121.37 (18)	C21—C22—H22A	109.5
C6—C5—C4	116.72 (18)	C21—C22—H22B	109.5
C5—C6—H6	119.5	C21—C22—H22C	109.5
C7—C6—C5	121.07 (18)	H22A—C22—H22B	109.5
C7—C6—H6	119.5	H22A—C22—H22C	109.5
C2—C7—H7	118.9	H22B—C22—H22C	109.5
O5—Mn1—O2—C1	60.63 (16)	C16—N2—C19—C20	−79.2 (2)
O5i—Mn1—O2—C1	−119.37 (16)	C21—N2—C19—C20	90.1 (2)
O6—Mn1—O2—C1	153.90 (16)	C16—N2—C21—C22	78.8 (2)
O6i—Mn1—O2—C1	−26.10 (16)	C19—N2—C21—C22	−90.5 (2)
O2i—Mn1—O6—Mn2	−125.04 (8)	O1—C1—C2—C3	12.0 (3)
O2—Mn1—O6—Mn2	54.96 (8)	O1—C1—C2—C7	−169.14 (18)
O5—Mn1—O6—Mn2	144.69 (8)	O2—C1—C2—C3	−168.63 (17)
O5i—Mn1—O6—Mn2	−35.31 (8)	O2—C1—C2—C7	10.2 (3)
O6ii—Mn2—O4—C12	−151.88 (16)	C1—C2—C3—C4	176.60 (18)
O6—Mn2—O4—C12	28.12 (16)	C7—C2—C3—C4	−2.3 (3)
O7—Mn2—O4—C12	121.83 (16)	C1—C2—C7—C6	−176.75 (18)
O7ii—Mn2—O4—C12	−58.17 (16)	C3—C2—C7—C6	2.2 (3)
O4—Mn2—O6—Mn1	−124.77 (8)	C5—C4—C3—C2	−0.5 (3)
O4ii—Mn2—O6—Mn1	55.23 (8)	C3—C4—C5—N1	−177.13 (18)
O7—Mn2—O6—Mn1	145.13 (8)	C3—C4—C5—C6	3.4 (3)
O7ii—Mn2—O6—Mn1	−34.87 (8)	C7—C6—C5—N1	176.98 (18)
Mn1—O2—C1—O1	31.0 (3)	C7—C6—C5—C4	−3.5 (3)
Mn1—O2—C1—C2	−148.33 (13)	C5—C6—C7—C2	0.8 (3)
Mn2—O4—C12—O3	−36.7 (3)	O3—C12—C13—C14	−11.0 (3)
Mn2—O4—C12—C13	142.49 (14)	O3—C12—C13—C18	168.54 (18)
C8—N1—C5—C4	10.9 (3)	O4—C12—C13—C14	169.77 (17)
C8—N1—C5—C6	−169.68 (18)	O4—C12—C13—C18	−10.7 (3)
C10—N1—C5—C4	179.60 (18)	C12—C13—C18—C17	179.60 (18)
C10—N1—C5—C6	−0.9 (3)	C14—C13—C18—C17	−0.8 (3)
C5—N1—C8—C9	−97.7 (2)	C15—C14—C13—C12	−179.32 (18)
C10—N1—C8—C9	92.9 (2)	C15—C14—C13—C18	1.1 (3)
C5—N1—C10—C11	−82.3 (2)	C13—C14—C15—C16	−0.9 (3)
C8—N1—C10—C11	87.2 (2)	N2—C16—C15—C14	−177.38 (18)
C19—N2—C16—C17	175.89 (19)	C17—C16—C15—C14	0.4 (3)
C19—N2—C16—C15	−6.5 (3)	N2—C16—C17—C18	177.68 (19)
C21—N2—C16—C15	−175.42 (19)	C15—C16—C17—C18	−0.1 (3)
C21—N2—C16—C17	6.9 (3)	C16—C17—C18—C13	0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H51···O8	0.97 (2)	1.77 (2)	2.738 (2)	177 (2)
O5—H52···O4iii	0.90 (2)	1.85 (2)	2.7457 (19)	175 (3)
O6—H61···O3	0.93 (2)	1.78 (2)	2.651 (2)	156 (2)
O6—H62···O1i	0.90 (2)	1.76 (2)	2.608 (2)	156 (3)
O7—H71···O9i	0.97 (2)	1.77 (2)	2.739 (2)	177 (1)
O7—H72···O2ii	0.89 (2)	1.85 (2)	2.733 (2)	170 (3)
O8—H82···O3	0.96 (3)	1.77 (3)	2.694 (2)	160 (3)
O9—H91···O1	0.93 (2)	1.80 (2)	2.692 (2)	160 (3)
C6—H6···Cg2	0.93	2.91	3.764 (2)	154
C19—H19A···Cg2iv	0.97	2.90	3.830 (2)	162

Table 1

Selected geometric parameters (Å, °)

Mn1—O2	2.1071 (14)
Mn1—O5	2.1932 (14)
Mn1—O6	2.2725 (13)
Mn2—O4	2.1120 (13)
Mn2—O6	2.2594 (13)
Mn2—O7	2.1835 (14)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H51⋯O8	0.97 (2)	1.77 (2)	2.738 (2)	177 (2)
O5—H52⋯O4iii	0.902 (17)	1.846 (17)	2.7457 (19)	175 (3)
O6—H61⋯O3	0.929 (17)	1.778 (19)	2.651 (2)	156 (2)
O6—H62⋯O1i	0.896 (18)	1.76 (2)	2.608 (2)	156 (3)
O7—H71⋯O9i	0.97 (2)	1.77 (2)	2.739 (2)	177.0 (2)
O7—H72⋯O2ii	0.893 (18)	1.850 (18)	2.733 (2)	170 (3)
O8—H82⋯O3	0.96 (3)	1.77 (3)	2.694 (2)	160 (3)
O9—H91⋯O1	0.927 (19)	1.80 (2)	2.692 (2)	160 (3)
C6—H6⋯Cg2	0.93	2.91	3.764 (2)	154
C19—H19A⋯Cg2iv	0.97	2.90	3.830 (2)	162

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the C13–C18 ring.