Aqua-(4-nitro-phthalato-κO)bis-[2-(1H-pyrazol-3-yl-κN)pyridine-κN]-mangan-ese(II) hemihydrate.

In the title compound, [Mn(C(8)H(3)NO(6))(C(8)H(7)N(3))(2)(H(2)O)]·0.5H(2)O, the Mn(2+) ion is octa-hedrally coordinated by two 2-(1H-pyrazol-3-yl)pyridine ligands, one 4-nitro-phthalate ligand and one coordinated water mol-ecule leading to an overall MnN(4)O(2) coordination environment. The two 2-(1H-pyrazol-3-yl)pyridine ligands, which deviate from planarity by 0.0187 (2) and 0.0601 (2) Å, make a dihedral angle of 81.90 (6)°. An intra-molecular N-H⋯O hydrogen bond occurs. Inter-molecular π-π stacking inter-actions with a face-to-face separation of 3.61 (1) Å between the 2-(1H-pyrazol-3-yl)pyridine ligands is observed. Additionally, O-H⋯O hydrogen bonding involving the uncoordinated water (which is situated on an inversion center), coordinated water mol-ecules and 2-(1H-pyrazol-3-yl)pyridine ligands leads to a three-dimensional network in the crystal structure.

Related literature

For the use of 4-nitro-phthalic acid for metal-organic frameworks, see: Xu et al. (2009 ▶); Guo & Guo (2007 ▶).

Experimental

Crystal data

[Mn(C8H3NO6)(C8H7N3)2(H2O)]·0.5H2O

M = 581.41

Triclinic,

a = 10.5996 (7) Å

b = 11.2654 (7) Å

c = 11.9493 (7) Å

α = 96.275 (2)°

β = 112.485 (2)°

γ = 96.902 (2)°

V = 1289.94 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.57 mm−1

T = 294 K

0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.935, T max = 0.956

13775 measured reflections

4492 independent reflections

4112 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.107

S = 1.00

4492 reflections

364 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.67 e Å−3

Δρmin = −0.56 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810045952/im2225sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045952/im2225Isup2.hkl

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

[Mn(C8H3NO6)(C8H7N3)2(H2O)]·0.5H2O	Z = 2
Mr = 581.41	F(000) = 594
Triclinic, P1	Dx = 1.497 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5996 (7) Å	Cell parameters from 4492 reflections
b = 11.2654 (7) Å	θ = 1.9–25.0°
c = 11.9493 (7) Å	µ = 0.57 mm−1
α = 96.275 (2)°	T = 294 K
β = 112.485 (2)°	Block, pink
γ = 96.902 (2)°	0.12 × 0.10 × 0.08 mm
V = 1289.94 (14) Å3

Bruker APEXII CCD diffractometer	4492 independent reflections
Radiation source: fine-focus sealed tube	4112 reflections with I > 2σ(I)
graphite	Rint = 0.016
phi and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.935, Tmax = 0.956	k = −13→12
13775 measured reflections	l = −14→14

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) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.065P)2 + 0.6953P] where P = (Fo2 + 2Fc2)/3
4492 reflections	(Δ/σ)max = 0.001
364 parameters	Δρmax = 0.67 e Å−3
3 restraints	Δρmin = −0.56 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
C1	0.7173 (4)	0.2731 (3)	0.9226 (3)	0.0712 (8)
H1	0.6343	0.2568	0.9323	0.085*
C2	0.8448 (4)	0.3131 (3)	1.0143 (3)	0.0697 (8)
H2	0.8668	0.3294	1.0983	0.084*
C3	0.9359 (3)	0.3247 (2)	0.9554 (2)	0.0518 (6)
C4	1.0853 (3)	0.3638 (2)	1.0005 (2)	0.0537 (6)
C5	1.1703 (4)	0.4045 (3)	1.1239 (2)	0.0695 (8)
H5	1.1328	0.4073	1.1828	0.083*
C6	1.3098 (4)	0.4403 (3)	1.1578 (3)	0.0831 (10)
H6	1.3680	0.4673	1.2401	0.100*
C7	1.3632 (4)	0.4362 (3)	1.0692 (3)	0.0802 (9)
H7	1.4576	0.4607	1.0903	0.096*
C8	1.2730 (3)	0.3948 (3)	0.9483 (3)	0.0670 (7)
H8	1.3090	0.3916	0.8884	0.080*
C9	1.3004 (3)	0.2422 (3)	0.5695 (3)	0.0635 (7)
H9	1.3674	0.2662	0.5403	0.076*
C10	1.2660 (3)	0.1287 (3)	0.5905 (3)	0.0611 (7)
H10	1.3037	0.0604	0.5786	0.073*
C11	1.1618 (2)	0.13717 (19)	0.63382 (19)	0.0406 (4)
C12	1.0839 (2)	0.04615 (18)	0.67283 (18)	0.0404 (4)
C13	1.0928 (3)	−0.0766 (2)	0.6586 (2)	0.0526 (6)
H13	1.1490	−0.1049	0.6217	0.063*
C14	1.0177 (3)	−0.1549 (2)	0.6995 (3)	0.0663 (7)
H14	1.0218	−0.2372	0.6906	0.080*
C15	0.9309 (3)	0.0111 (2)	0.7633 (3)	0.0688 (8)
H15	0.8747	0.0405	0.7995	0.083*
C16	0.9367 (4)	−0.1107 (3)	0.7536 (3)	0.0761 (8)
H16	0.8861	−0.1620	0.7834	0.091*
C17	0.6605 (2)	0.2144 (2)	0.5118 (2)	0.0513 (6)
C18	0.5813 (2)	0.1929 (2)	0.3746 (2)	0.0427 (5)
C19	0.4714 (3)	0.0954 (2)	0.3232 (2)	0.0572 (6)
H19	0.4438	0.0523	0.3746	0.069*
C20	0.4030 (3)	0.0616 (2)	0.1979 (3)	0.0619 (7)
H20	0.3294	−0.0034	0.1639	0.074*
C21	0.4462 (2)	0.1264 (2)	0.1246 (2)	0.0545 (6)
C22	0.5544 (2)	0.2235 (2)	0.1721 (2)	0.0479 (5)
H22	0.5820	0.2648	0.1197	0.058*
C23	0.6216 (2)	0.25915 (18)	0.29779 (19)	0.0400 (4)
C24	0.7320 (2)	0.3719 (2)	0.3445 (2)	0.0462 (5)
Mn1	0.97367 (3)	0.28597 (3)	0.71009 (3)	0.03701 (12)
N1	0.7320 (2)	0.26121 (19)	0.8159 (2)	0.0564 (5)
H1A	0.6650	0.2366	0.7450	0.068*
N2	0.8652 (2)	0.29291 (17)	0.83442 (17)	0.0485 (4)
N3	1.1369 (2)	0.35929 (18)	0.91298 (18)	0.0528 (5)
N4	1.22077 (19)	0.31285 (17)	0.59823 (18)	0.0474 (4)
H4	1.2240	0.3884	0.5919	0.057*
N5	1.13476 (17)	0.25018 (15)	0.63847 (16)	0.0393 (4)
N6	1.0021 (2)	0.08928 (16)	0.72337 (18)	0.0467 (4)
N7	0.3749 (3)	0.0899 (3)	−0.0097 (2)	0.0805 (7)
O1	0.5935 (2)	0.2119 (4)	0.5746 (2)	0.1504 (16)
O2	0.78795 (15)	0.22449 (14)	0.54996 (14)	0.0475 (4)
O3	0.7370 (2)	0.44475 (15)	0.43391 (16)	0.0596 (4)
O4	0.8061 (2)	0.38723 (19)	0.2870 (2)	0.0791 (6)
O5	0.4122 (3)	0.1463 (3)	−0.0749 (2)	0.1086 (9)
O6	0.2814 (4)	0.0044 (3)	−0.0487 (3)	0.1654 (18)
O1W	0.96188 (16)	0.46463 (14)	0.66095 (15)	0.0479 (4)
O2W	0.5000	0.5000	0.5000	0.208 (3)
H1W	0.9011 (17)	0.454 (3)	0.5913 (10)	0.080*
H2W	1.0347 (14)	0.507 (2)	0.670 (2)	0.080*

	U11	U22	U33	U12	U13	U23
C1	0.097 (2)	0.0723 (18)	0.0770 (19)	0.0202 (16)	0.0667 (19)	0.0216 (15)
C2	0.109 (2)	0.0717 (18)	0.0557 (16)	0.0283 (17)	0.0556 (18)	0.0216 (13)
C3	0.0855 (18)	0.0398 (11)	0.0455 (12)	0.0208 (11)	0.0388 (12)	0.0118 (9)
C4	0.0838 (18)	0.0380 (12)	0.0446 (12)	0.0213 (11)	0.0277 (12)	0.0100 (9)
C5	0.106 (2)	0.0573 (16)	0.0450 (14)	0.0253 (15)	0.0264 (15)	0.0096 (12)
C6	0.104 (3)	0.0694 (19)	0.0505 (16)	0.0196 (18)	0.0035 (17)	0.0064 (14)
C7	0.073 (2)	0.076 (2)	0.0705 (19)	0.0113 (16)	0.0083 (16)	0.0066 (15)
C8	0.0655 (17)	0.0692 (17)	0.0592 (16)	0.0113 (14)	0.0192 (13)	0.0037 (13)
C9	0.0590 (15)	0.0756 (18)	0.0797 (18)	0.0222 (13)	0.0481 (14)	0.0230 (14)
C10	0.0679 (16)	0.0625 (16)	0.0775 (17)	0.0340 (13)	0.0465 (14)	0.0217 (13)
C11	0.0430 (11)	0.0413 (11)	0.0400 (11)	0.0145 (9)	0.0174 (9)	0.0070 (8)
C12	0.0442 (11)	0.0390 (11)	0.0347 (10)	0.0117 (9)	0.0112 (9)	0.0057 (8)
C13	0.0630 (14)	0.0435 (12)	0.0492 (13)	0.0197 (11)	0.0175 (11)	0.0072 (10)
C14	0.0842 (19)	0.0372 (13)	0.0728 (17)	0.0156 (12)	0.0235 (15)	0.0146 (12)
C15	0.0821 (19)	0.0506 (14)	0.101 (2)	0.0164 (13)	0.0608 (17)	0.0260 (14)
C16	0.092 (2)	0.0478 (15)	0.105 (2)	0.0101 (14)	0.0540 (19)	0.0311 (15)
C17	0.0418 (12)	0.0668 (15)	0.0513 (13)	0.0064 (10)	0.0257 (10)	0.0111 (11)
C18	0.0337 (10)	0.0464 (12)	0.0515 (12)	0.0080 (9)	0.0206 (9)	0.0084 (9)
C19	0.0470 (13)	0.0583 (14)	0.0676 (16)	−0.0026 (11)	0.0259 (12)	0.0176 (12)
C20	0.0428 (13)	0.0561 (15)	0.0722 (17)	−0.0106 (11)	0.0149 (12)	0.0028 (12)
C21	0.0420 (12)	0.0584 (14)	0.0500 (13)	0.0027 (10)	0.0089 (10)	−0.0010 (11)
C22	0.0416 (11)	0.0532 (13)	0.0472 (12)	0.0032 (10)	0.0170 (10)	0.0096 (10)
C23	0.0338 (10)	0.0382 (11)	0.0475 (11)	0.0056 (8)	0.0162 (9)	0.0067 (9)
C24	0.0433 (11)	0.0391 (11)	0.0504 (12)	0.0008 (9)	0.0143 (10)	0.0085 (10)
Mn1	0.0428 (2)	0.03495 (19)	0.03942 (19)	0.00804 (13)	0.02298 (15)	0.00565 (13)
N1	0.0672 (13)	0.0579 (12)	0.0593 (12)	0.0069 (10)	0.0432 (11)	0.0088 (9)
N2	0.0655 (12)	0.0437 (10)	0.0483 (11)	0.0105 (9)	0.0356 (10)	0.0075 (8)
N3	0.0663 (13)	0.0466 (11)	0.0465 (11)	0.0141 (9)	0.0234 (10)	0.0048 (8)
N4	0.0476 (10)	0.0460 (10)	0.0576 (11)	0.0075 (8)	0.0302 (9)	0.0124 (8)
N5	0.0414 (9)	0.0379 (9)	0.0432 (9)	0.0072 (7)	0.0221 (8)	0.0062 (7)
N6	0.0541 (11)	0.0376 (9)	0.0570 (11)	0.0102 (8)	0.0298 (9)	0.0121 (8)
N7	0.0622 (15)	0.0935 (19)	0.0578 (15)	−0.0044 (14)	0.0031 (12)	−0.0036 (14)
O1	0.0515 (13)	0.342 (5)	0.0589 (13)	0.015 (2)	0.0337 (11)	0.016 (2)
O2	0.0402 (8)	0.0541 (9)	0.0470 (8)	0.0068 (7)	0.0177 (7)	0.0041 (7)
O3	0.0743 (12)	0.0413 (9)	0.0559 (10)	−0.0013 (8)	0.0228 (9)	0.0036 (8)
O4	0.0715 (13)	0.0731 (13)	0.0920 (14)	−0.0272 (10)	0.0501 (12)	−0.0099 (11)
O5	0.0866 (17)	0.167 (3)	0.0508 (12)	−0.0142 (17)	0.0190 (12)	0.0042 (14)
O6	0.160 (3)	0.160 (3)	0.0776 (18)	−0.088 (3)	−0.0201 (19)	−0.0018 (18)
O1W	0.0464 (9)	0.0414 (8)	0.0532 (9)	0.0005 (7)	0.0182 (7)	0.0109 (7)
O2W	0.190 (6)	0.278 (8)	0.248 (8)	0.101 (6)	0.165 (6)	0.066 (6)

C1—N1	1.338 (3)	C15—H15	0.9300
C1—C2	1.357 (5)	C16—H16	0.9300
C1—H1	0.9300	C17—O1	1.216 (3)
C2—C3	1.398 (4)	C17—O2	1.235 (3)
C2—H2	0.9300	C17—C18	1.504 (3)
C3—N2	1.332 (3)	C18—C19	1.393 (3)
C3—C4	1.456 (4)	C18—C23	1.398 (3)
C4—N3	1.352 (3)	C19—C20	1.375 (4)
C4—C5	1.390 (4)	C19—H19	0.9300
C5—C6	1.370 (5)	C20—C21	1.370 (4)
C5—H5	0.9300	C20—H20	0.9300
C6—C7	1.378 (5)	C21—C22	1.378 (3)
C6—H6	0.9300	C21—N7	1.473 (3)
C7—C8	1.382 (4)	C22—C23	1.380 (3)
C7—H7	0.9300	C22—H22	0.9300
C8—N3	1.334 (4)	C23—C24	1.511 (3)
C8—H8	0.9300	C24—O4	1.235 (3)
C9—N4	1.337 (3)	C24—O3	1.253 (3)
C9—C10	1.364 (4)	Mn1—O2	2.1255 (15)
C9—H9	0.9300	Mn1—O1W	2.1619 (15)
C10—C11	1.396 (3)	Mn1—N2	2.1995 (17)
C10—H10	0.9300	Mn1—N5	2.2401 (16)
C11—N5	1.338 (3)	Mn1—N6	2.2861 (18)
C11—C12	1.465 (3)	Mn1—N3	2.359 (2)
C12—N6	1.338 (3)	N1—N2	1.339 (3)
C12—C13	1.393 (3)	N1—H1A	0.8600
C13—C14	1.370 (4)	N4—N5	1.347 (2)
C13—H13	0.9300	N4—H4	0.8600
C14—C16	1.364 (4)	N7—O6	1.203 (4)
C14—H14	0.9300	N7—O5	1.203 (4)
C15—N6	1.334 (3)	O1W—H1W	0.820 (12)
C15—C16	1.375 (4)	O1W—H2W	0.82 (2)
N1—C1—C2	108.0 (3)	C18—C19—H19	119.5
N1—C1—H1	126.0	C21—C20—C19	118.2 (2)
C2—C1—H1	126.0	C21—C20—H20	120.9
C1—C2—C3	105.2 (2)	C19—C20—H20	120.9
C1—C2—H2	127.4	C20—C21—C22	122.3 (2)
C3—C2—H2	127.4	C20—C21—N7	118.6 (2)
N2—C3—C2	109.7 (3)	C22—C21—N7	119.0 (2)
N2—C3—C4	117.4 (2)	C21—C22—C23	119.7 (2)
C2—C3—C4	132.9 (2)	C21—C22—H22	120.2
N3—C4—C5	121.6 (3)	C23—C22—H22	120.2
N3—C4—C3	115.1 (2)	C22—C23—C18	119.03 (19)
C5—C4—C3	123.3 (2)	C22—C23—C24	117.40 (19)
C6—C5—C4	119.2 (3)	C18—C23—C24	123.52 (19)
C6—C5—H5	120.4	O4—C24—O3	125.3 (2)
C4—C5—H5	120.4	O4—C24—C23	116.6 (2)
C5—C6—C7	119.5 (3)	O3—C24—C23	118.0 (2)
C5—C6—H6	120.2	O2—Mn1—O1W	86.45 (6)
C7—C6—H6	120.2	O2—Mn1—N2	93.74 (7)
C6—C7—C8	118.3 (3)	O1W—Mn1—N2	99.70 (7)
C6—C7—H7	120.9	O2—Mn1—N5	101.41 (6)
C8—C7—H7	120.9	O1W—Mn1—N5	95.17 (6)
N3—C8—C7	123.3 (3)	N2—Mn1—N5	159.38 (7)
N3—C8—H8	118.3	O2—Mn1—N6	89.68 (7)
C7—C8—H8	118.3	O1W—Mn1—N6	166.14 (7)
N4—C9—C10	108.0 (2)	N2—Mn1—N6	93.83 (7)
N4—C9—H9	126.0	N5—Mn1—N6	72.55 (6)
C10—C9—H9	126.0	O2—Mn1—N3	164.44 (7)
C9—C10—C11	105.0 (2)	O1W—Mn1—N3	94.04 (7)
C9—C10—H10	127.5	N2—Mn1—N3	70.82 (8)
C11—C10—H10	127.5	N5—Mn1—N3	94.05 (7)
N5—C11—C10	110.3 (2)	N6—Mn1—N3	93.24 (7)
N5—C11—C12	118.75 (18)	C1—N1—N2	110.7 (2)
C10—C11—C12	131.0 (2)	C1—N1—H1A	124.6
N6—C12—C13	121.9 (2)	N2—N1—H1A	124.6
N6—C12—C11	115.00 (18)	C3—N2—N1	106.40 (18)
C13—C12—C11	123.1 (2)	C3—N2—Mn1	120.74 (17)
C14—C13—C12	119.1 (2)	N1—N2—Mn1	132.63 (15)
C14—C13—H13	120.5	C8—N3—C4	118.0 (2)
C12—C13—H13	120.5	C8—N3—Mn1	126.27 (17)
C16—C14—C13	119.2 (2)	C4—N3—Mn1	115.70 (17)
C16—C14—H14	120.4	C9—N4—N5	111.07 (19)
C13—C14—H14	120.4	C9—N4—H4	124.5
N6—C15—C16	123.2 (3)	N5—N4—H4	124.5
N6—C15—H15	118.4	C11—N5—N4	105.65 (16)
C16—C15—H15	118.4	C11—N5—Mn1	116.41 (13)
C14—C16—C15	118.9 (3)	N4—N5—Mn1	137.92 (13)
C14—C16—H16	120.6	C15—N6—C12	117.8 (2)
C15—C16—H16	120.6	C15—N6—Mn1	125.06 (16)
O1—C17—O2	125.8 (2)	C12—N6—Mn1	116.60 (14)
O1—C17—C18	117.3 (2)	O6—N7—O5	123.3 (3)
O2—C17—C18	116.67 (19)	O6—N7—C21	117.6 (3)
C19—C18—C23	119.6 (2)	O5—N7—C21	119.1 (3)
C19—C18—C17	117.4 (2)	C17—O2—Mn1	142.44 (15)
C23—C18—C17	122.66 (19)	Mn1—O1W—H1W	106 (2)
C20—C19—C18	121.1 (2)	Mn1—O1W—H2W	117 (2)
C20—C19—H19	119.5	H1W—O1W—H2W	115 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O4i	0.82 (2)	1.80 (2)	2.615 (2)	171 (3)
N1—H1A···O1	0.86	1.86	2.644 (3)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O4i	0.82 (2)	1.80 (2)	2.615 (2)	171 (3)
N1—H1A⋯O1	0.86	1.86	2.644 (3)	152

Symmetry code: (i) .