Tetra-kis(μ-5-bromo-nicotinato)-κO,O':O';κO:O,O';κO:O'-bis-[diaqua-(5-bromo-nicotinato-κO,O')neodymium(III)] dihydrate.

In the title compound, [Nd(2)(C(6)H(3)BrNO(2))(6)(H(2)O)(4)]·2H(2)O, the Nd(III) ion is coordinated by nine O atoms from one chelating 5-bromo-nicotinate ligand, four bridging 5-bromo-nicotinate ligands and two water mol-ecules, exhibiting a distorted three-capped triangular-prismatic geometry. Two Nd(III) ions are bridged by four carboxyl-ate groups in bi- and tridentate modes, forming a centrosymmetric dinuclear unit, with an Nd⋯Nd distance of 4.0021 (5) Å, and intra-molecular π-π inter-actions between the pyridine rings [centroid-centroid distance = 3.960 (2) Å]. Inter-molecular π-π inter-actions [centroid-centroid distances = 3.820 (2) and 3.804 (2) Å] and O-H⋯N and O-H⋯O hydrogen bonds connect the dinuclear mol-ecules into a three-dimensional supra-molecular network.

Related literature

For general background to lanthanide complexes with carboxyl­ates, see: Ragunathan & Schneider (1996 ▶); Shibasaki & Yoshikawa (2002 ▶). For dimeric lanthanide carboxyl­ates, see: Rupam et al. (2010 ▶); Song et al. (2004 ▶); Yang & Chen (2009 ▶).

Experimental

Crystal data

[Nd2(C6H3BrNO2)6(H2O)4]·2H2O

M = 1602.60

Monoclinic,

a = 11.5278 (13) Å

b = 16.6616 (18) Å

c = 12.2711 (13) Å

β = 102.478 (2)°

V = 2301.3 (4) Å3

Z = 2

Mo Kα radiation

μ = 7.52 mm−1

T = 110 K

0.42 × 0.38 × 0.36 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.059, T max = 0.067

11552 measured reflections

4999 independent reflections

4295 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.054

S = 1.07

4999 reflections

331 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.02 e Å−3

Δρmin = −1.07 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811023798/hy2440sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023798/hy2440Isup2.hkl

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

[Nd2(C6H3BrNO2)6(H2O)4]·2H2O	F(000) = 1524
Mr = 1602.60	Dx = 2.313 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4999 reflections
a = 11.5278 (13) Å	θ = 2.5–27.1°
b = 16.6616 (18) Å	µ = 7.52 mm−1
c = 12.2711 (13) Å	T = 110 K
β = 102.478 (2)°	Block, brown
V = 2301.3 (4) Å3	0.42 × 0.38 × 0.36 mm
Z = 2

Bruker APEX CCD diffractometer	4999 independent reflections
Radiation source: fine-focus sealed tube	4295 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 27.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→14
Tmin = 0.059, Tmax = 0.067	k = −21→19
11552 measured reflections	l = −15→15

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0266P)2] where P = (Fo2 + 2Fc2)/3
4999 reflections	(Δ/σ)max = 0.066
331 parameters	Δρmax = 1.02 e Å−3
6 restraints	Δρmin = −1.07 e Å−3

	x	y	z	Uiso*/Ueq
Br1	−0.09938 (3)	0.096820 (19)	1.12865 (3)	0.01690 (8)
Br2	0.24543 (3)	0.605255 (19)	0.35014 (3)	0.01538 (8)
Br3	0.08252 (3)	0.38137 (2)	1.62068 (3)	0.01714 (8)
C1	0.0190 (2)	0.35415 (17)	0.9159 (2)	0.0080 (6)
C2	−0.0119 (2)	0.26663 (17)	0.9148 (2)	0.0091 (6)
C3	−0.0484 (3)	0.23220 (18)	1.0047 (2)	0.0100 (6)
H3	−0.0621	0.2641	1.0648	0.012*
C4	−0.0640 (3)	0.15010 (18)	1.0039 (3)	0.0120 (6)
C5	−0.0505 (3)	0.10527 (18)	0.9120 (3)	0.0143 (7)
H5	−0.0654	0.0492	0.9114	0.017*
C6	0.0039 (3)	0.21785 (18)	0.8270 (3)	0.0123 (6)
H6	0.0306	0.2417	0.7665	0.015*
C7	0.2081 (3)	0.60360 (18)	0.7791 (2)	0.0108 (6)
C8	0.2037 (3)	0.64877 (18)	0.6724 (2)	0.0102 (6)
C9	0.2253 (3)	0.60917 (18)	0.5792 (2)	0.0105 (6)
H9	0.2431	0.5535	0.5814	0.013*
C10	0.2200 (3)	0.65385 (18)	0.4825 (2)	0.0103 (6)
C11	0.1923 (3)	0.73465 (18)	0.4816 (3)	0.0134 (6)
H11	0.1892	0.7644	0.4150	0.016*
C12	0.1762 (3)	0.72998 (18)	0.6646 (3)	0.0119 (6)
H12	0.1611	0.7566	0.7286	0.014*
C13	0.1084 (3)	0.42457 (17)	1.1932 (2)	0.0107 (6)
C14	0.1252 (3)	0.37044 (18)	1.2944 (2)	0.0100 (6)
C15	0.0977 (3)	0.39880 (18)	1.3926 (2)	0.0107 (6)
H15	0.0718	0.4525	1.3980	0.013*
C16	0.1090 (3)	0.34655 (19)	1.4820 (2)	0.0110 (6)
C17	0.1423 (3)	0.26774 (18)	1.4697 (2)	0.0130 (6)
H17	0.1485	0.2323	1.5313	0.016*
C18	0.1593 (3)	0.29081 (18)	1.2895 (2)	0.0106 (6)
H18	0.1789	0.2718	1.2228	0.013*
H71	0.313 (4)	0.6236 (10)	1.119 (4)	0.063 (16)*
H72	0.368 (2)	0.548 (2)	1.133 (3)	0.033 (12)*
H81	0.395 (2)	0.4366 (19)	1.0285 (15)	0.010 (9)*
H82	0.340 (4)	0.3837 (7)	0.958 (4)	0.066 (17)*
H91	−0.001 (3)	0.0648 (16)	0.704 (2)	0.026 (11)*
H92	0.0725 (15)	0.017 (3)	0.656 (4)	0.052 (15)*
N1	−0.0172 (2)	0.13855 (15)	0.8243 (2)	0.0146 (6)
N2	0.1699 (2)	0.77251 (15)	0.5710 (2)	0.0126 (5)
N3	0.1659 (2)	0.23932 (15)	1.3751 (2)	0.0142 (6)
Nd1	0.157605 (13)	0.506682 (9)	0.957077 (13)	0.00682 (5)
O1	0.10185 (18)	0.37520 (12)	0.87133 (17)	0.0113 (4)
O2	0.03578 (18)	0.59795 (12)	1.03191 (17)	0.0118 (4)
O3	0.18480 (19)	0.64042 (12)	0.86189 (17)	0.0138 (5)
O4	0.23363 (18)	0.53005 (12)	0.78226 (17)	0.0126 (4)
O5	0.17948 (19)	0.41883 (13)	1.12916 (18)	0.0150 (5)
O6	−0.02224 (19)	0.52807 (13)	0.81744 (17)	0.0144 (5)
O7	0.3080 (2)	0.57471 (14)	1.1001 (2)	0.0164 (5)
O8	0.34606 (19)	0.43444 (13)	0.96599 (18)	0.0116 (4)
O9	0.0016 (2)	0.02805 (14)	0.65696 (19)	0.0140 (5)

	U11	U22	U33	U12	U13	U23
Br1	0.02332 (18)	0.01014 (16)	0.01978 (17)	0.00051 (12)	0.01028 (14)	0.00525 (13)
Br2	0.02280 (17)	0.01451 (17)	0.01077 (15)	−0.00214 (12)	0.00791 (12)	−0.00125 (12)
Br3	0.01782 (16)	0.02518 (19)	0.00977 (15)	−0.00330 (13)	0.00597 (12)	−0.00356 (13)
C1	0.0111 (14)	0.0073 (14)	0.0042 (13)	0.0020 (11)	−0.0014 (11)	0.0000 (11)
C2	0.0093 (14)	0.0054 (14)	0.0124 (15)	0.0008 (11)	0.0015 (12)	0.0000 (12)
C3	0.0099 (14)	0.0086 (15)	0.0124 (15)	0.0018 (11)	0.0047 (12)	−0.0013 (12)
C4	0.0102 (15)	0.0105 (15)	0.0159 (16)	0.0010 (11)	0.0043 (12)	0.0040 (13)
C5	0.0166 (16)	0.0051 (15)	0.0207 (17)	−0.0013 (12)	0.0033 (13)	−0.0007 (13)
C6	0.0120 (15)	0.0119 (16)	0.0129 (15)	−0.0012 (12)	0.0023 (12)	−0.0013 (12)
C7	0.0089 (14)	0.0108 (15)	0.0129 (15)	−0.0020 (11)	0.0029 (12)	0.0026 (12)
C8	0.0113 (15)	0.0081 (15)	0.0109 (15)	−0.0023 (11)	0.0015 (12)	0.0016 (12)
C9	0.0102 (14)	0.0101 (15)	0.0116 (15)	−0.0011 (11)	0.0029 (12)	−0.0011 (12)
C10	0.0117 (15)	0.0107 (15)	0.0080 (14)	−0.0032 (11)	0.0011 (12)	−0.0016 (12)
C11	0.0171 (16)	0.0118 (16)	0.0115 (15)	−0.0028 (12)	0.0038 (12)	0.0029 (12)
C12	0.0116 (15)	0.0119 (16)	0.0123 (15)	−0.0017 (12)	0.0031 (12)	−0.0011 (12)
C13	0.0150 (15)	0.0062 (15)	0.0092 (15)	−0.0059 (12)	−0.0012 (12)	0.0008 (12)
C14	0.0089 (14)	0.0089 (15)	0.0116 (15)	−0.0013 (11)	0.0011 (12)	0.0017 (12)
C15	0.0122 (15)	0.0073 (15)	0.0125 (15)	0.0002 (11)	0.0027 (12)	−0.0008 (12)
C16	0.0109 (15)	0.0143 (16)	0.0085 (14)	−0.0028 (12)	0.0035 (12)	−0.0013 (12)
C17	0.0169 (16)	0.0126 (16)	0.0091 (15)	0.0001 (12)	0.0018 (12)	0.0060 (12)
C18	0.0137 (15)	0.0111 (16)	0.0069 (14)	−0.0003 (11)	0.0019 (12)	−0.0006 (12)
N1	0.0177 (14)	0.0087 (13)	0.0179 (14)	−0.0015 (10)	0.0051 (11)	−0.0043 (11)
N2	0.0169 (13)	0.0088 (13)	0.0122 (13)	−0.0023 (10)	0.0030 (11)	0.0025 (10)
N3	0.0193 (14)	0.0095 (13)	0.0137 (14)	0.0029 (10)	0.0034 (11)	0.0044 (11)
Nd1	0.01072 (8)	0.00413 (8)	0.00615 (8)	0.00027 (6)	0.00303 (6)	0.00031 (6)
O1	0.0151 (11)	0.0077 (11)	0.0124 (11)	−0.0005 (8)	0.0059 (9)	0.0002 (8)
O2	0.0175 (11)	0.0081 (11)	0.0105 (10)	0.0025 (9)	0.0046 (9)	0.0008 (9)
O3	0.0235 (12)	0.0086 (11)	0.0110 (11)	−0.0032 (9)	0.0074 (9)	−0.0013 (9)
O4	0.0197 (11)	0.0083 (11)	0.0113 (11)	0.0020 (9)	0.0064 (9)	0.0023 (9)
O5	0.0155 (11)	0.0180 (12)	0.0112 (11)	−0.0039 (9)	0.0020 (9)	0.0056 (9)
O6	0.0198 (12)	0.0088 (11)	0.0120 (11)	0.0027 (9)	−0.0026 (9)	−0.0002 (9)
O7	0.0201 (13)	0.0080 (12)	0.0187 (12)	0.0007 (9)	−0.0009 (10)	−0.0038 (10)
O8	0.0137 (11)	0.0078 (12)	0.0124 (11)	0.0004 (9)	0.0009 (9)	−0.0017 (9)
O9	0.0157 (12)	0.0138 (12)	0.0128 (12)	0.0015 (9)	0.0039 (10)	−0.0042 (9)

Br1—C4	1.888 (3)	C13—O5	1.255 (4)
Br2—C10	1.894 (3)	C13—C14	1.513 (4)
Br3—C16	1.884 (3)	C14—C18	1.389 (4)
C1—O1	1.249 (3)	C14—C15	1.393 (4)
C1—O2i	1.273 (3)	C15—C16	1.385 (4)
C1—C2	1.500 (4)	C15—H15	0.9500
C2—C3	1.386 (4)	C16—C17	1.385 (4)
C2—C6	1.393 (4)	C17—N3	1.335 (4)
C3—C4	1.380 (4)	C17—H17	0.9500
C3—H3	0.9500	C18—N3	1.345 (4)
C4—C5	1.389 (4)	C18—H18	0.9500
C5—N1	1.340 (4)	Nd1—O2	2.384 (2)
C5—H5	0.9500	Nd1—O6	2.414 (2)
C6—N1	1.342 (4)	Nd1—O1	2.455 (2)
C6—H6	0.9500	Nd1—O7	2.461 (2)
C7—O4	1.259 (3)	Nd1—O8	2.465 (2)
C7—O3	1.264 (4)	Nd1—O4	2.517 (2)
C7—C8	1.501 (4)	Nd1—O5	2.537 (2)
C8—C9	1.389 (4)	Nd1—O3	2.566 (2)
C8—C12	1.388 (4)	Nd1—O2i	2.856 (2)
C9—C10	1.390 (4)	Nd1—Nd1i	4.0022 (5)
C9—H9	0.9500	O7—H71	0.84 (1)
C10—C11	1.383 (4)	O7—H72	0.85 (3)
C11—N2	1.338 (4)	O8—H81	0.85 (1)
C11—H11	0.9500	O8—H82	0.85 (1)
C12—N2	1.338 (4)	O9—H91	0.85 (3)
C12—H12	0.9500	O9—H92	0.84 (1)
C13—O6i	1.253 (4)
O1—C1—O2i	123.6 (3)	O7—Nd1—O8	73.44 (7)
O1—C1—C2	118.1 (3)	O2—Nd1—O4	124.90 (7)
O2i—C1—C2	118.1 (3)	O6—Nd1—O4	77.05 (7)
O1—C1—Nd1	53.38 (14)	O1—Nd1—O4	83.10 (7)
O2i—C1—Nd1	71.76 (16)	O7—Nd1—O4	102.44 (8)
C2—C1—Nd1	161.08 (19)	O8—Nd1—O4	69.36 (7)
C3—C2—C6	119.1 (3)	O2—Nd1—O5	90.48 (7)
C3—C2—C1	120.5 (3)	O6—Nd1—O5	126.28 (7)
C6—C2—C1	120.2 (3)	O1—Nd1—O5	79.14 (7)
C4—C3—C2	117.8 (3)	O7—Nd1—O5	75.17 (7)
C4—C3—H3	121.1	O8—Nd1—O5	75.71 (7)
C2—C3—H3	121.1	O4—Nd1—O5	143.95 (7)
C3—C4—C5	120.1 (3)	O2—Nd1—O3	76.21 (7)
C3—C4—Br1	120.8 (2)	O6—Nd1—O3	73.70 (7)
C5—C4—Br1	119.1 (2)	O1—Nd1—O3	128.77 (7)
N1—C5—C4	122.2 (3)	O7—Nd1—O3	77.78 (7)
N1—C5—H5	118.9	O8—Nd1—O3	104.54 (7)
C4—C5—H5	118.9	O4—Nd1—O3	51.57 (7)
N1—C6—C2	122.7 (3)	O5—Nd1—O3	151.64 (7)
N1—C6—H6	118.7	O2—Nd1—O2i	80.82 (7)
C2—C6—H6	118.7	O6—Nd1—O2i	64.17 (7)
O4—C7—O3	122.4 (3)	O1—Nd1—O2i	48.76 (6)
O4—C7—C8	118.6 (3)	O7—Nd1—O2i	133.17 (7)
O3—C7—C8	119.0 (3)	O8—Nd1—O2i	112.90 (7)
O4—C7—Nd1	60.93 (15)	O4—Nd1—O2i	123.63 (6)
O3—C7—Nd1	63.19 (15)	O5—Nd1—O2i	63.04 (6)
C8—C7—Nd1	165.9 (2)	O3—Nd1—O2i	136.46 (6)
C9—C8—C12	119.0 (3)	O2—Nd1—C7	99.62 (8)
C9—C8—C7	120.1 (3)	O6—Nd1—C7	70.22 (8)
C12—C8—C7	120.9 (3)	O1—Nd1—C7	104.64 (8)
C8—C9—C10	117.7 (3)	O7—Nd1—C7	93.22 (8)
C8—C9—H9	121.1	O8—Nd1—C7	89.25 (8)
C10—C9—H9	121.1	O4—Nd1—C7	25.93 (7)
C11—C10—C9	119.7 (3)	O5—Nd1—C7	163.03 (8)
C11—C10—Br2	119.1 (2)	O3—Nd1—C7	26.09 (7)
C9—C10—Br2	121.1 (2)	O2i—Nd1—C7	131.83 (7)
N2—C11—C10	122.5 (3)	O2—Nd1—C1	105.66 (8)
N2—C11—H11	118.8	O6—Nd1—C1	70.10 (7)
C10—C11—H11	118.8	O1—Nd1—C1	24.09 (7)
N2—C12—C8	123.0 (3)	O7—Nd1—C1	141.37 (8)
N2—C12—H12	118.5	O8—Nd1—C1	91.49 (7)
C8—C12—H12	118.5	O4—Nd1—C1	105.05 (7)
O6i—C13—O5	126.3 (3)	O5—Nd1—C1	66.61 (7)
O6i—C13—C14	114.8 (3)	O3—Nd1—C1	140.85 (7)
O5—C13—C14	118.9 (3)	O2i—Nd1—C1	25.04 (7)
C18—C14—C15	118.7 (3)	C7—Nd1—C1	122.56 (8)
C18—C14—C13	121.4 (3)	O2—Nd1—Nd1i	44.79 (5)
C15—C14—C13	119.7 (3)	O6—Nd1—Nd1i	60.37 (5)
C16—C15—C14	118.2 (3)	O1—Nd1—Nd1i	83.95 (5)
C16—C15—H15	120.9	O7—Nd1—Nd1i	112.19 (6)
C14—C15—H15	120.9	O8—Nd1—Nd1i	143.38 (5)
C17—C16—C15	119.4 (3)	O4—Nd1—Nd1i	137.40 (5)
C17—C16—Br3	119.5 (2)	O5—Nd1—Nd1i	71.42 (5)
C15—C16—Br3	121.1 (2)	O3—Nd1—Nd1i	112.04 (5)
N3—C17—C16	123.0 (3)	O2i—Nd1—Nd1i	36.03 (4)
N3—C17—H17	118.5	C7—Nd1—Nd1i	125.13 (6)
C16—C17—H17	118.5	C1—Nd1—Nd1i	60.94 (6)
N3—C18—C14	123.0 (3)	C1—O1—Nd1	102.53 (17)
N3—C18—H18	118.5	C1i—O2—Nd1	172.35 (19)
C14—C18—H18	118.5	C1i—O2—Nd1i	83.20 (17)
C5—N1—C6	118.0 (3)	Nd1—O2—Nd1i	99.18 (7)
C12—N2—C11	118.0 (3)	C7—O3—Nd1	90.72 (17)
C17—N3—C18	117.7 (3)	C7—O4—Nd1	93.14 (17)
O2—Nd1—O6	72.07 (7)	C13—O5—Nd1	121.09 (19)
O2—Nd1—O1	127.79 (7)	C13i—O6—Nd1	135.0 (2)
O6—Nd1—O1	73.88 (7)	Nd1—O7—H71	129 (3)
O2—Nd1—O7	79.30 (8)	Nd1—O7—H72	118 (3)
O6—Nd1—O7	143.42 (7)	H71—O7—H72	113 (4)
O1—Nd1—O7	142.70 (7)	Nd1—O8—H81	115 (2)
O2—Nd1—O8	151.76 (7)	Nd1—O8—H82	115 (3)
O6—Nd1—O8	135.81 (7)	H81—O8—H82	100 (4)
O1—Nd1—O8	74.33 (7)	H91—O9—H92	110 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···N3ii	0.84 (1)	1.94 (2)	2.769 (3)	165 (5)
O7—H72···O9iii	0.85 (3)	1.97 (2)	2.780 (3)	160 (4)
O8—H81···O9iii	0.85 (1)	1.87 (1)	2.699 (3)	164 (3)
O8—H82···N2iv	0.85 (1)	1.88 (1)	2.735 (3)	175 (5)
O9—H91···N1	0.85 (3)	1.96 (3)	2.801 (3)	172 (4)
O9—H92···O4iv	0.84 (1)	2.21 (2)	2.981 (3)	153 (4)
O9—H92···O8iv	0.84 (1)	2.37 (4)	2.989 (3)	131 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H71⋯N3i	0.84 (1)	1.94 (2)	2.769 (3)	165 (5)
O7—H72⋯O9ii	0.85 (3)	1.97 (2)	2.780 (3)	160 (4)
O8—H81⋯O9ii	0.85 (1)	1.87 (1)	2.699 (3)	164 (3)
O8—H82⋯N2iii	0.85 (1)	1.88 (1)	2.735 (3)	175 (5)
O9—H91⋯N1	0.85 (3)	1.96 (3)	2.801 (3)	172 (4)
O9—H92⋯O4iii	0.84 (1)	2.21 (2)	2.981 (3)	153 (4)
O9—H92⋯O8iii	0.84 (1)	2.37 (4)	2.989 (3)	131 (4)

Symmetry codes: (i) ; (ii) ; (iii) .