[2,6-Bis(2-pyridylamino)pyridine]dinitratocadmium monohydrate

The Cd atom in the title complex, [Cd(NO₃)₂(C₁₅H₁₃N₅)]·H₂O or [Cd(NO₃)₂(tpdaH₂)]·H₂O (tpdaH₂ is tripyridyldiamine), has a penta­gonal-bipyramidal coordination formed by the tridentate tpdaH₂ ligand and two chelate nitrate groups. The tpdaH₂ ligand is mer-coordinated, with the N atom of the central pyridine ring in the equatorial position [Cd-N = 2.3148 (17) Å] and the N atoms of the peripheral pyridine rings in the axial positions [Cd-N = 2.2345 (19) and 2.2351 (19) Å, and N-Cd-N = 169.39 (6)°]. The remaining four equatorial positions are occupied by the four O atoms of two nitrate groups, one of which has almost equal Cd-O bond lengths [2.431 (2) and 2.4644 (19) Å], whereas the other shows a significant difference between the Cd-O bond lengths [2.441 (2) and 2.603 (2) Å]. The H atoms of both NH groups of the tpdaH₂ ligand are involved in hydrogen bonds with water O atoms as acceptors, whereas both water H atoms form hydrogen bonds with the O atoms of one of the nitrate groups. The hydrogen bonds link the mol­ecules of the title complex and solvent mol­ecules into an infinite three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.026
• wR factor = 0.060
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cd1    -   O2      ..      19.88 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cd1    -   O5      ..      21.99 su
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O4
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for         O5

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.02
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cd1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N7
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C15 H13 Cd N7 O6

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

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

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL-Plus (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL-Plus.

[2,6-Bis(2-pyridylamino)pyridine]dinitratocadmium monohydrate

Crystal data

[Cd(NO3)2(C15H13N5)]·H2O	F(000) = 1032
Mr = 517.74	Dx = 1.815 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6355 reflections
a = 9.3371 (3) Å	θ = 2.1–27.5°
b = 17.5155 (5) Å	µ = 1.21 mm^−1
c = 11.6735 (3) Å	T = 295 K
β = 96.964 (1)°	Irregular, yellow
V = 1895.05 (9) Å^3	0.25 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4346 independent reflections
Radiation source: fine-focus sealed tube	3059 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (symmetry-related measurements; Blessing, 1995)	h = −12→12
Tmin = 0.687, Tmax = 0.773	k = −22→22
16790 measured reflections	l = −15→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.03P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.003
4346 reflections	Δρmax = 0.37 e Å^−3
278 parameters	Δρmin = −0.50 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00097 (18)

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cd1	−0.22093 (2)	0.580916 (9)	0.241872 (16)	0.05142 (8)
N1	−0.4436 (2)	0.56444 (9)	0.15111 (16)	0.0475 (5)
N2	−0.4763 (2)	0.44358 (10)	0.23418 (17)	0.0497 (5)
H2A	−0.5398	0.4230	0.2720	0.060*
N3	−0.21821 (19)	0.44965 (10)	0.26503 (14)	0.0407 (4)
N4	0.0387 (2)	0.44884 (10)	0.30035 (18)	0.0547 (5)
H4A	0.1069	0.4235	0.2745	0.066*
N5	−0.0055 (2)	0.57695 (10)	0.34863 (16)	0.0497 (5)
N6	−0.0945 (2)	0.64868 (13)	0.0541 (2)	0.0684 (6)
N7	−0.3571 (2)	0.67571 (13)	0.4080 (2)	0.0655 (6)
O1	−0.0964 (2)	0.57849 (10)	0.06744 (17)	0.0757 (5)
O2	−0.1512 (2)	0.68745 (10)	0.1272 (2)	0.0879 (6)
O3	−0.0410 (3)	0.67796 (14)	−0.0246 (2)	0.1250 (10)
O4	−0.3324 (2)	0.60840 (12)	0.43157 (18)	0.0895 (7)
O5	−0.3134 (3)	0.69907 (10)	0.31589 (19)	0.0903 (7)
O6	−0.4181 (2)	0.71684 (13)	0.4697 (2)	0.1067 (8)
C1	−0.5017 (3)	0.62350 (13)	0.0861 (2)	0.0568 (6)
H1A	−0.4426	0.6644	0.0726	0.068*
C2	−0.6429 (3)	0.62553 (15)	0.0395 (2)	0.0611 (7)
H2B	−0.6797	0.6675	−0.0031	0.073*
C3	−0.7301 (3)	0.56422 (15)	0.0568 (2)	0.0599 (7)
H3A	−0.8266	0.5641	0.0257	0.072*
C4	−0.6729 (3)	0.50356 (13)	0.1201 (2)	0.0532 (6)
H4B	−0.7301	0.4614	0.1316	0.064*
C5	−0.5282 (2)	0.50510 (12)	0.16760 (19)	0.0429 (5)
C6	−0.3413 (3)	0.40808 (11)	0.25235 (18)	0.0413 (5)
C7	−0.3422 (3)	0.32918 (12)	0.2591 (2)	0.0492 (5)
H7A	−0.4289	0.3024	0.2514	0.059*
C8	−0.2131 (3)	0.29129 (13)	0.2773 (2)	0.0541 (6)
H8A	−0.2114	0.2383	0.2814	0.065*
C9	−0.0865 (3)	0.33173 (12)	0.2896 (2)	0.0510 (6)
H9A	0.0020	0.3068	0.3011	0.061*
C10	−0.0936 (2)	0.41097 (11)	0.28450 (19)	0.0433 (5)
C11	0.0846 (2)	0.51810 (12)	0.34837 (19)	0.0455 (5)
C12	0.2296 (3)	0.52465 (14)	0.3938 (2)	0.0573 (6)
H12A	0.2912	0.4829	0.3934	0.069*
C13	0.2801 (3)	0.59257 (15)	0.4388 (2)	0.0644 (7)
H13A	0.3766	0.5978	0.4684	0.077*
C14	0.1867 (3)	0.65355 (15)	0.4400 (2)	0.0658 (7)
H14A	0.2189	0.7005	0.4701	0.079*
C15	0.0468 (3)	0.64329 (13)	0.3960 (2)	0.0605 (7)
H15A	−0.0165	0.6840	0.3986	0.073*
O7	0.2914 (2)	0.34309 (11)	0.29289 (18)	0.0646 (5)
H7B	0.277 (3)	0.304 (2)	0.248 (2)	0.097*
H7C	0.310 (4)	0.3213 (19)	0.351 (3)	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.05242 (12)	0.02919 (9)	0.07100 (14)	−0.00053 (7)	0.00080 (8)	0.00281 (8)
N1	0.0508 (12)	0.0375 (10)	0.0537 (12)	0.0027 (8)	0.0049 (9)	0.0049 (8)
N2	0.0423 (11)	0.0419 (10)	0.0658 (13)	−0.0018 (8)	0.0106 (9)	0.0119 (9)
N3	0.0451 (10)	0.0286 (8)	0.0489 (11)	−0.0006 (8)	0.0077 (8)	0.0007 (7)
N4	0.0424 (11)	0.0374 (10)	0.0857 (15)	0.0013 (8)	0.0139 (10)	−0.0086 (10)
N5	0.0553 (12)	0.0365 (10)	0.0567 (12)	−0.0021 (9)	0.0048 (9)	−0.0052 (9)
N6	0.0652 (15)	0.0551 (15)	0.0853 (18)	−0.0095 (11)	0.0105 (13)	0.0103 (13)
N7	0.0673 (15)	0.0573 (14)	0.0698 (17)	0.0056 (11)	−0.0002 (12)	−0.0116 (12)
O1	0.0928 (15)	0.0498 (11)	0.0878 (14)	−0.0128 (9)	0.0247 (11)	−0.0028 (10)
O2	0.0933 (16)	0.0487 (11)	0.1238 (19)	−0.0015 (10)	0.0224 (14)	−0.0022 (12)
O3	0.144 (2)	0.1027 (18)	0.139 (2)	−0.0056 (16)	0.0598 (19)	0.0548 (16)
O4	0.1170 (18)	0.0683 (13)	0.0889 (15)	0.0332 (12)	0.0355 (13)	0.0237 (11)
O5	0.143 (2)	0.0493 (11)	0.0776 (15)	−0.0070 (12)	0.0100 (14)	0.0051 (10)
O6	0.0984 (17)	0.0939 (16)	0.128 (2)	0.0228 (13)	0.0159 (14)	−0.0569 (15)
C1	0.0674 (18)	0.0404 (13)	0.0620 (16)	0.0060 (11)	0.0056 (13)	0.0110 (11)
C2	0.0729 (19)	0.0557 (16)	0.0533 (16)	0.0216 (14)	0.0016 (13)	0.0062 (12)
C3	0.0534 (15)	0.0673 (17)	0.0565 (16)	0.0121 (12)	−0.0030 (12)	−0.0032 (13)
C4	0.0501 (15)	0.0530 (14)	0.0552 (16)	−0.0028 (11)	0.0010 (12)	−0.0001 (11)
C5	0.0467 (14)	0.0396 (11)	0.0430 (13)	0.0026 (9)	0.0077 (10)	0.0000 (10)
C6	0.0482 (12)	0.0362 (11)	0.0400 (12)	−0.0023 (10)	0.0072 (10)	0.0035 (9)
C7	0.0552 (14)	0.0352 (11)	0.0579 (15)	−0.0084 (11)	0.0097 (11)	−0.0005 (10)
C8	0.0697 (17)	0.0289 (11)	0.0656 (16)	0.0005 (11)	0.0163 (13)	0.0019 (10)
C9	0.0524 (14)	0.0349 (11)	0.0676 (16)	0.0077 (10)	0.0154 (12)	0.0042 (11)
C10	0.0487 (13)	0.0353 (11)	0.0469 (13)	0.0006 (10)	0.0097 (10)	−0.0002 (10)
C11	0.0492 (15)	0.0421 (12)	0.0455 (14)	−0.0009 (10)	0.0069 (11)	0.0045 (10)
C12	0.0531 (16)	0.0584 (15)	0.0596 (16)	0.0005 (12)	0.0030 (12)	0.0033 (12)
C13	0.0612 (17)	0.0734 (19)	0.0552 (16)	−0.0152 (14)	−0.0067 (13)	0.0015 (13)
C14	0.081 (2)	0.0572 (16)	0.0557 (17)	−0.0210 (14)	−0.0042 (14)	−0.0054 (13)
C15	0.0744 (19)	0.0429 (14)	0.0625 (17)	−0.0022 (12)	0.0016 (14)	−0.0078 (12)
O7	0.0635 (12)	0.0439 (10)	0.0882 (15)	−0.0020 (8)	0.0167 (11)	−0.0007 (10)

Geometric parameters (Å, º)

Cd1—N1	2.2345 (19)	C1—C2	1.365 (3)
Cd1—N3	2.3148 (17)	C2—C3	1.377 (4)
Cd1—N5	2.2351 (19)	C3—C4	1.365 (3)
Cd1—O1	2.4644 (19)	C4—C5	1.397 (3)
Cd1—O2	2.431 (2)	C6—C7	1.384 (3)
Cd1—O4	2.603 (2)	C7—C8	1.370 (3)
Cd1—O5	2.441 (2)	C8—C9	1.371 (3)
N1—C1	1.357 (3)	C9—C10	1.391 (3)
N1—C5	1.334 (3)	C11—C12	1.398 (3)
N2—C5	1.381 (3)	C12—C13	1.361 (3)
N2—C6	1.398 (3)	C13—C14	1.380 (4)
N3—C6	1.354 (3)	C14—C15	1.356 (4)
N3—C10	1.341 (3)	N2—H2A	0.8602
N4—C10	1.395 (3)	N4—H4A	0.8603
N4—C11	1.382 (3)	C1—H1A	0.9293
N5—C11	1.331 (3)	C2—H2B	0.9297
N5—C15	1.353 (3)	C3—H3A	0.9297
N6—O1	1.240 (2)	C4—H4B	0.9306
N6—O2	1.257 (3)	C7—H7A	0.9305
N6—O3	1.211 (3)	C8—H8A	0.9294
N7—O4	1.226 (3)	C9—H9A	0.9299
N7—O5	1.263 (3)	C12—H12A	0.9307
N7—O6	1.209 (3)	C13—H13A	0.9296
O7—H7B	0.86 (3)	C14—H14A	0.9298
O7—H7C	0.78 (3)	C15—H15A	0.9290
N1—Cd1—N3	85.62 (6)	N2—C5—C4	117.7 (2)
N1—Cd1—N5	169.39 (6)	N3—C6—C7	122.8 (2)
N1—Cd1—O1	96.37 (7)	N3—C6—N2	121.02 (18)
N1—Cd1—O2	97.71 (7)	N3—C10—C9	123.2 (2)
N1—Cd1—O4	88.99 (7)	N3—C10—N4	121.22 (18)
N1—Cd1—O5	85.90 (7)	N4—C11—C12	117.6 (2)
N3—Cd1—O1	94.57 (6)	N5—C11—N4	121.1 (2)
N3—Cd1—O2	145.78 (7)	N5—C11—C12	121.3 (2)
N3—Cd1—O4	94.83 (6)	N5—C15—C14	123.5 (2)
N3—Cd1—O5	143.15 (6)	N5—C15—H15A	118.24
N5—Cd1—O1	88.70 (7)	C1—C2—C3	118.7 (2)
N5—Cd1—O2	92.73 (7)	C1—C2—H2B	120.70
N5—Cd1—O4	87.53 (7)	C2—C1—H1A	118.51
N5—Cd1—O5	99.33 (7)	C2—C3—H3A	120.44
N5—Cd1—N3	84.70 (6)	C3—C2—H2B	120.55
O1—Cd1—O4	169.50 (7)	C3—C4—C5	119.7 (2)
O1—N6—O2	115.9 (2)	C3—C4—H4B	120.12
O2—Cd1—O1	51.22 (6)	C4—C3—C2	119.2 (2)
O2—Cd1—O4	119.20 (7)	C4—C3—H3A	120.43
O2—Cd1—O5	70.97 (7)	C5—N2—H2A	113.52
O3—N6—O1	121.9 (3)	C5—C4—H4B	120.16
O3—N6—O2	122.2 (3)	C6—N2—H2A	113.61
O4—N7—O5	115.5 (2)	C6—C7—H7A	120.60
O5—Cd1—O1	121.99 (6)	C7—C6—N2	116.2 (2)
O5—Cd1—O4	49.23 (6)	C7—C8—C9	119.8 (2)
O6—N7—O4	121.9 (3)	C7—C8—H8A	120.07
O6—N7—O5	122.6 (3)	C8—C7—C6	118.8 (2)
N6—O1—Cd1	95.86 (16)	C8—C7—H7A	120.64
N6—O2—Cd1	97.01 (15)	C8—C9—C10	118.4 (2)
N7—O4—Cd1	94.06 (16)	C8—C9—H9A	120.83
N7—O5—Cd1	101.03 (15)	C9—C8—H8A	120.10
C1—N1—Cd1	116.92 (15)	C9—C10—N4	115.6 (2)
C5—N1—C1	118.1 (2)	C10—N4—H4A	112.92
C5—N1—Cd1	124.44 (15)	C10—C9—H9A	120.79
C5—N2—C6	132.87 (18)	C11—N4—H4A	112.87
C6—N3—Cd1	121.62 (14)	C11—C12—H12A	120.29
C10—N3—C6	117.02 (18)	C12—C13—C14	119.4 (3)
C10—N3—Cd1	121.23 (14)	C12—C13—H13A	120.28
C11—N4—C10	134.18 (19)	C13—C12—C11	119.5 (2)
C11—N5—C15	118.0 (2)	C13—C12—H12A	120.21
C11—N5—Cd1	123.31 (15)	C13—C14—H14A	120.84
C15—N5—Cd1	117.23 (16)	C14—C13—H13A	120.34
N1—C1—C2	123.0 (2)	C14—C15—H15A	118.24
N1—C1—H1A	118.51	C15—C14—C13	118.3 (2)
N1—C5—N2	121.0 (2)	C15—C14—H14A	120.85
N1—C5—C4	121.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O7^i	0.86	2.14	2.938 (3)	153
N4—H4A···O7	0.86	2.22	3.009 (3)	153
O7—H7B···O5^ii	0.86 (3)	2.03 (3)	2.843 (2)	158
O7—H7C···O6^iii	0.78 (3)	2.31 (3)	3.063 (2)	163

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