Di-μ-sulfato-κ⁴O:O′-bis­[diaqua­(1H-imidazo[4,5-f][1,10]phenanthroline)manganese(II)] dihydrate

In the title centrosymmetric dinuclear compound, [Mn₂(SO₄)₂(C₁₃H₈N₄)₂(H₂O)₄]·2H₂O, the Mn^II atom is octa­hedrally coordinated by two N atoms from a 1H-imidazo[4,5-f][1,10]phenanthroline (ip) ligand, two O atoms belonging to two bridging sulfate anions and two water O atoms. In the crystal structure, the complex mol­ecules and the uncoodinated water mol­ecules are connected by O—H...O, O—H...N and N—H...O hydrogen bonds into a three-dimensional network. A π–π stacking inter­action between the pyridyl ring of the ip ligand and the benzene ring of the neighboring ligand [centroid–centroid distance = 3.579 (2) Å] is also observed.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.082
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    --  O5      ..       7.10 su
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         69
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          6
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         52

Alert level G
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C4     -C12           1.43 Ang.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       1.00 mm
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

An important aspect of crystal engineering is to understand and attempt to control the manner in which molecules are arranged in crystal lattices through the use of noncovalent interactions such as electrostatic interactions, hydrogen bonding, dispersion and induction forces, and π-π stacking interactions. These materials have attracted much interest due to their strong potential for a variety of applications including gas storage (Matsuda et al., 2005; Rowsell et al., 2004), catalytic properties (Aoyama, 1998; Bassani et al., 2000) and magnetism (Kahn, 2000; Miller, 2000). One approach to forming networks of discrete transition metal complexes is to use a chelating ligand that has additional interactional functionality attached to its backbone, such as additional coordination sites or hydrogen bonding groups, or extended π systems. 1H-Imidazo[5,f][1,10]phenanthroline (ip) has been used to form metal complexes with novel supramolecular architectures due to their excellent coordinating ability, large conjugated systems and strong hydrogen bonding donor and acceptor groups (Gong et al., 2009; Wang et al., 2008; Wu et al., 1997; Yang et al., 2010; Yu, 2009; Zeng et al., 2009). In the present paper,we hydrothermally synthesized a new coordination complex constructed from MnSO₄ and ip.

The title dimeric complex is generated by an inversion center (Fig. 1). The Mn^II atom is six-coordinated by two N atoms from one ip ligand, two O atoms from water molecules and two O atoms from two sulfate anions in a distorted octahedral geometry (Table 1). The equatorial plane is defined by N2, O6, O1 and O5 and the axial coordination sites are occupied by N1 and O3ⁱ atoms [symmetry code: (i) -x, 1-y, -z]. The sulfate anion acts as a bidentate bridging ligand connecting two Mn^II ions, thus generating a binuclear complex. The hydrogen bonds play a key role in the structural stability (Table 2). The uncoordinated water molecule is a hydrogen bond acceptor from the coordinated water, and a hydrogen bond donor to two O atoms of two sulfate anions in two neighboring complex molecules. So each free water is hydrogen bonded to three different complex molecules. The ip ligand is a hydrogen bond donor through the imidazolyl NH group to a sulfate O atom of an adjacent complex molecule and a hydrogen bond acceptor from the coordinated water molecule (O5) of another adjacent complex molecule through the other imidazolyl N atom, forming a three-dimensional network structure, as illustrated in Fig. 2. There is also a π–π stacking interaction between the pyridyl ring of the ip ligand and the benzene ring of the neighboring ip ligand, with a centroid–centroid distance of 3.579 (2) Å.

Related literature

For general background to the crystal engineering of functional materials, see: Aoyama (1998); Bassani et al. (2000); Kahn (2000); Matsuda et al. (2005); Miller (2000); Rowsell et al. (2004). For related structures, see: Gong et al. (2009); Wang et al. (2008); Wu et al. (1997); Yang et al. (2010); Yu (2009); Zeng et al. (2009).

S2. Experimental

The ip ligand was synthesized according to literature (Wu et al., 1997). A mixture of MnSO₄, ip and H₂O in a molar ratio of 1:1:556 was stirred for an hour, then sealed in an 18 ml Teflon-lined stainless steel reactor and heated for 3 d at 433 K and autogeneous pressure. After allowing the reaction mixture to cool down to room temperature, yellow crystals were collected, washed with water and dried at room temperature.

S3. Refinement

C- and N-bound H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 and N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C,N). The water H atoms were located in a difference Fourier map and refined isotropically, with restraints of O—H = 0.84 (1) and H···H = 1.44 (1) Å.

Computing details

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Molecular structure of the title compound. H atoms have been omitted for clarity. [Symmetry code: (A) -x, 1-y, -z.]
	Fig. 2. The three-dimensional hydrogen bonding network in the title compound.

Di-µ-sulfato-κ⁴O:O'- bis[diaqua(1H-imidazo-[4,5-f][1,10]phenanthroline)manganese(II)] dihydrate

Crystal data

[Mn2(SO4)2(C13H8N4)2(H2O)4]·2H2O	F(000) = 868
Mr = 850.58	Dx = 1.749 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4851 reflections
a = 10.467 (7) Å	θ = 3.3–27.4°
b = 9.171 (6) Å	µ = 1.00 mm^−1
c = 17.025 (11) Å	T = 293 K
β = 98.758 (12)°	Prism, yellow
V = 1615.2 (18) Å^3	1.00 × 0.80 × 0.60 mm
Z = 2

Data collection

Rigaku Mercury CCD diffractometer	3544 independent reflections
Radiation source: fine-focus sealed tube	3251 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 14.6306 pixels mm^-1	θmax = 27.4°, θmin = 2.5°
ω scan	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	k = −11→11
Tmin = 0.432, Tmax = 1.000	l = −21→21
11099 measured 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0437P)^2 + 0.5623P] where P = (Fo^2 + 2Fc^2)/3
3544 reflections	(Δ/σ)max = 0.001
259 parameters	Δρmax = 0.30 e Å^−3
9 restraints	Δρmin = −0.39 e Å^−3

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

	x	y	z	Uiso*/Ueq
Mn1	0.18299 (2)	0.67998 (3)	0.039544 (16)	0.02452 (10)
S1	0.03061 (4)	0.40185 (4)	0.11921 (2)	0.02399 (11)
O1	0.13383 (12)	0.47205 (14)	0.08303 (9)	0.0374 (3)
O2	−0.06301 (12)	0.51435 (14)	0.13804 (8)	0.0316 (3)
O3	−0.03679 (12)	0.29274 (14)	0.06387 (8)	0.0311 (3)
O4	0.08663 (14)	0.32790 (15)	0.19348 (9)	0.0400 (3)
O5	0.29524 (13)	0.55706 (16)	−0.04252 (8)	0.0339 (3)
H1	0.2295 (19)	0.519 (3)	−0.0712 (14)	0.074 (9)*
H2	0.329 (3)	0.626 (3)	−0.0665 (16)	0.096 (12)*
O6	0.05988 (16)	0.77338 (17)	0.11855 (10)	0.0484 (4)
H3	0.065 (2)	0.8546 (15)	0.1421 (14)	0.059 (8)*
H4	0.012 (2)	0.7107 (19)	0.1349 (14)	0.056 (8)*
O7	0.0949 (3)	0.01928 (19)	0.20000 (11)	0.0714 (6)
H5	0.090 (3)	0.008 (3)	0.2492 (7)	0.076 (10)*
H6	0.088 (3)	0.1066 (16)	0.1844 (15)	0.084 (10)*
N1	0.37913 (14)	0.68351 (15)	0.11788 (9)	0.0257 (3)
N2	0.25995 (13)	0.91094 (15)	0.03511 (9)	0.0252 (3)
N3	0.74601 (14)	1.01809 (18)	0.20156 (9)	0.0321 (3)
H3B	0.8055	0.9678	0.2297	0.039*
N4	0.64434 (15)	1.21029 (17)	0.13915 (10)	0.0338 (4)
C1	0.43732 (18)	0.56818 (19)	0.15534 (11)	0.0303 (4)
H1A	0.3930	0.4800	0.1522	0.036*
C2	0.56195 (18)	0.5734 (2)	0.19914 (12)	0.0333 (4)
H2B	0.5993	0.4901	0.2240	0.040*
C3	0.62820 (17)	0.7031 (2)	0.20480 (12)	0.0314 (4)
H3C	0.7105	0.7093	0.2343	0.038*
C4	0.56986 (15)	0.82664 (18)	0.16534 (10)	0.0239 (3)
C5	0.62700 (15)	0.96855 (19)	0.16508 (10)	0.0257 (4)
C6	0.56533 (16)	1.08776 (18)	0.12661 (10)	0.0253 (3)
C7	0.43740 (15)	1.07578 (18)	0.08161 (10)	0.0236 (3)
C8	0.36759 (18)	1.19078 (18)	0.04063 (12)	0.0302 (4)
H8A	0.4032	1.2838	0.0414	0.036*
C9	0.24595 (18)	1.1648 (2)	−0.00075 (12)	0.0337 (4)
H9A	0.1977	1.2403	−0.0269	0.040*
C10	0.19618 (16)	1.0231 (2)	−0.00289 (11)	0.0306 (4)
H10A	0.1150	1.0060	−0.0321	0.037*
C11	0.37862 (15)	0.93635 (17)	0.07832 (10)	0.0220 (3)
C12	0.44406 (15)	0.81270 (17)	0.12160 (10)	0.0222 (3)
C13	0.75016 (19)	1.1614 (2)	0.18408 (12)	0.0370 (4)
H13A	0.8209	1.2205	0.2020	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02168 (14)	0.02247 (15)	0.02823 (17)	−0.00592 (9)	−0.00001 (11)	−0.00163 (10)
S1	0.0223 (2)	0.0203 (2)	0.0272 (2)	−0.00508 (14)	−0.00289 (16)	0.00196 (15)
O1	0.0317 (7)	0.0248 (6)	0.0578 (9)	−0.0043 (5)	0.0138 (6)	0.0050 (6)
O2	0.0289 (6)	0.0270 (6)	0.0384 (7)	−0.0024 (5)	0.0037 (5)	−0.0046 (5)
O3	0.0290 (6)	0.0253 (6)	0.0354 (8)	−0.0023 (5)	−0.0067 (5)	−0.0044 (5)
O4	0.0475 (8)	0.0336 (7)	0.0330 (8)	−0.0034 (6)	−0.0129 (6)	0.0068 (6)
O5	0.0305 (7)	0.0349 (7)	0.0361 (8)	−0.0022 (5)	0.0040 (6)	−0.0011 (6)
O6	0.0599 (9)	0.0302 (8)	0.0626 (10)	−0.0153 (7)	0.0334 (8)	−0.0142 (7)
O7	0.1428 (19)	0.0306 (9)	0.0456 (11)	−0.0169 (10)	0.0295 (12)	−0.0072 (7)
N1	0.0253 (7)	0.0215 (7)	0.0292 (8)	−0.0046 (5)	0.0008 (6)	0.0003 (5)
N2	0.0209 (6)	0.0247 (7)	0.0287 (8)	−0.0030 (5)	0.0000 (6)	0.0014 (6)
N3	0.0235 (7)	0.0369 (9)	0.0323 (9)	−0.0062 (6)	−0.0073 (6)	0.0023 (7)
N4	0.0326 (8)	0.0295 (8)	0.0376 (9)	−0.0113 (6)	−0.0004 (7)	0.0004 (7)
C1	0.0348 (9)	0.0221 (8)	0.0330 (10)	−0.0035 (7)	0.0026 (8)	0.0010 (7)
C2	0.0363 (9)	0.0266 (9)	0.0352 (11)	0.0049 (7)	0.0002 (8)	0.0060 (7)
C3	0.0244 (8)	0.0342 (10)	0.0335 (10)	0.0018 (7)	−0.0023 (7)	0.0032 (8)
C4	0.0217 (7)	0.0251 (8)	0.0240 (9)	−0.0023 (6)	0.0006 (6)	−0.0010 (6)
C5	0.0200 (7)	0.0293 (9)	0.0263 (9)	−0.0046 (6)	−0.0011 (6)	−0.0012 (7)
C6	0.0253 (8)	0.0234 (8)	0.0266 (9)	−0.0068 (6)	0.0022 (7)	−0.0018 (6)
C7	0.0241 (8)	0.0224 (8)	0.0241 (8)	−0.0032 (6)	0.0032 (7)	−0.0012 (6)
C8	0.0327 (9)	0.0207 (8)	0.0364 (11)	−0.0025 (6)	0.0029 (8)	0.0005 (7)
C9	0.0319 (9)	0.0278 (9)	0.0393 (11)	0.0050 (7)	−0.0019 (8)	0.0064 (8)
C10	0.0218 (8)	0.0316 (9)	0.0362 (10)	0.0006 (7)	−0.0023 (7)	0.0042 (8)
C11	0.0196 (7)	0.0220 (8)	0.0240 (9)	−0.0025 (6)	0.0024 (6)	−0.0007 (6)
C12	0.0214 (7)	0.0216 (8)	0.0232 (9)	−0.0030 (6)	0.0019 (6)	−0.0008 (6)
C13	0.0318 (9)	0.0387 (11)	0.0380 (11)	−0.0177 (8)	−0.0029 (8)	−0.0020 (8)

Geometric parameters (Å, º)

Mn1—O1	2.1366 (17)	N3—H3B	0.8600
Mn1—O3^i	2.1641 (16)	N4—C13	1.325 (3)
Mn1—O5	2.2590 (16)	N4—C6	1.392 (2)
Mn1—O6	2.1751 (17)	C1—C2	1.401 (3)
Mn1—N1	2.2718 (19)	C1—H1A	0.9300
Mn1—N2	2.2715 (19)	C2—C3	1.373 (3)
S1—O1	1.4711 (14)	C2—H2B	0.9300
S1—O4	1.4753 (16)	C3—C4	1.408 (2)
S1—O3	1.4779 (14)	C3—H3C	0.9300
S1—O2	1.4910 (14)	C4—C12	1.416 (2)
O3—Mn1^i	2.1641 (16)	C4—C5	1.433 (2)
O5—H1	0.85 (1)	C5—C6	1.383 (2)
O5—H2	0.86 (3)	C6—C7	1.442 (2)
O6—H3	0.84 (1)	C7—C8	1.406 (2)
O6—H4	0.84 (2)	C7—C11	1.416 (2)
O7—H5	0.85 (1)	C8—C9	1.379 (3)
O7—H6	0.84 (1)	C8—H8A	0.9300
N1—C1	1.333 (2)	C9—C10	1.398 (3)
N1—C12	1.363 (2)	C9—H9A	0.9300
N2—C10	1.338 (2)	C10—H10A	0.9300
N2—C11	1.364 (2)	C11—C12	1.464 (2)
N3—C13	1.350 (3)	C13—H13A	0.9300
N3—C5	1.381 (2)
O1—Mn1—O3^i	101.97 (6)	N1—C1—C2	123.22 (16)
O1—Mn1—O6	86.60 (7)	N1—C1—H1A	118.4
O3^i—Mn1—O6	92.60 (8)	C2—C1—H1A	118.4
O1—Mn1—O5	86.81 (6)	C3—C2—C1	119.08 (17)
O3^i—Mn1—O5	85.67 (7)	C3—C2—H2B	120.5
O6—Mn1—O5	172.68 (5)	C1—C2—H2B	120.5
O1—Mn1—N2	161.64 (6)	C2—C3—C4	119.07 (17)
O3^i—Mn1—N2	94.33 (5)	C2—C3—H3C	120.5
O6—Mn1—N2	84.25 (6)	C4—C3—H3C	120.5
O5—Mn1—N2	102.96 (6)	C3—C4—C12	118.63 (15)
O1—Mn1—N1	93.04 (6)	C3—C4—C5	125.55 (16)
O3^i—Mn1—N1	160.02 (5)	C12—C4—C5	115.82 (15)
O6—Mn1—N1	101.47 (8)	N3—C5—C6	106.07 (15)
O5—Mn1—N1	82.04 (7)	N3—C5—C4	130.22 (16)
N2—Mn1—N1	73.31 (5)	C6—C5—C4	123.70 (15)
O1—S1—O4	109.79 (9)	C5—C6—N4	110.00 (16)
O1—S1—O3	109.82 (9)	C5—C6—C7	121.34 (15)
O4—S1—O3	108.90 (9)	N4—C6—C7	128.66 (16)
O1—S1—O2	109.62 (9)	C8—C7—C11	117.88 (16)
O4—S1—O2	108.80 (9)	C8—C7—C6	125.22 (15)
O3—S1—O2	109.88 (8)	C11—C7—C6	116.90 (15)
S1—O1—Mn1	140.06 (8)	C9—C8—C7	119.55 (16)
S1—O3—Mn1^i	130.55 (8)	C9—C8—H8A	120.2
Mn1—O5—H1	96 (2)	C7—C8—H8A	120.2
Mn1—O5—H2	102 (2)	C8—C9—C10	119.05 (16)
H1—O5—H2	112.2 (16)	C8—C9—H9A	120.5
Mn1—O6—H3	129.9 (16)	C10—C9—H9A	120.5
Mn1—O6—H4	112.2 (16)	N2—C10—C9	123.04 (17)
H3—O6—H4	116.3 (16)	N2—C10—H10A	118.5
H5—O7—H6	114.1 (16)	C9—C10—H10A	118.5
C1—N1—C12	118.64 (15)	N2—C11—C7	122.01 (15)
C1—N1—Mn1	125.14 (11)	N2—C11—C12	117.19 (14)
C12—N1—Mn1	116.06 (11)	C7—C11—C12	120.81 (15)
C10—N2—C11	118.41 (15)	N1—C12—C4	121.34 (15)
C10—N2—Mn1	125.42 (12)	N1—C12—C11	117.28 (15)
C11—N2—Mn1	116.10 (11)	C4—C12—C11	121.39 (14)
C13—N3—C5	106.16 (15)	N4—C13—N3	113.86 (16)
C13—N3—H3B	126.9	N4—C13—H13A	123.1
C5—N3—H3B	126.9	N3—C13—H13A	123.1
C13—N4—C6	103.91 (16)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O2^i	0.85 (1)	1.95 (1)	2.789 (2)	165 (3)
O5—H2···N4^ii	0.86 (3)	1.99 (3)	2.824 (2)	164 (3)
O6—H3···O7^iii	0.84 (1)	1.80 (1)	2.644 (3)	172 (3)
O6—H4···O2	0.84 (2)	1.97 (1)	2.745 (2)	154 (2)
O7—H5···O2^iv	0.85 (1)	1.98 (1)	2.828 (3)	171 (3)
O7—H6···O4	0.84 (1)	2.04 (2)	2.833 (3)	157 (3)
N3—H3B···O4^v	0.86	2.04	2.890 (2)	167

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